{"paper_id":"2187bcbc-034b-476e-8633-c235da1cb586","body_text":"Enantioselective adsorption of limonenes and α-pinenes on germanium oxide metal-organic framework | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Enantioselective adsorption of limonenes and α-pinenes on germanium oxide metal-organic framework Yulia Sharafutdinova, Klavdia Sufiyarova, Adelina Samarina, Diana Bagdanova, and 3 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-7470067/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 20 Feb, 2026 Read the published version in Adsorption → Version 1 posted 9 You are reading this latest preprint version Abstract Chiral metal-organic frameworks (CMOFs) are promising materials for catalysis, chromatography, and sensor applications. Typically, chirality in such frameworks is achieved by using chiral ligands. However, there are rare examples of CMOFs that form without any chiral source, usually via spontaneous symmetry breaking, resulting in supramolecular chirality. Germanium oxide framework SU-MB exhibits a unique mechanism of chirality emergence: during synthesis, only micropores of one handedness are selectively filled. This paper investigates the adsorption of limonene and α-pinene enantiomers on SU-MB. The framework demonstrated consistent enantioselectivity for both pairs of enantiomers, with a higher selectivity coefficient observed for α-pinenes than for limonenes. This difference arises from distinct trends in the isosteric heats of adsorption (Q st ): for limonenes and (−)-α-pinene, Q st approaches the heat of liquefaction with increasing adsorption, whereas for (+)-α-pinene, Q st remains unchanged. These findings show that even a non-chiral crystal without chiral centers can exhibit enantioselectivity in adsorption processes, because of helical pores of one handedness. chiral metal-organic frameworks helical pores adsorption isotherms enantioselectivity Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Highlights Enantiomer adsorption on germanium oxide framework SU-MB was studied SU-MB framework lacks asymmetric carbon, but has helical micropores Only one type of chiral micropores is available for adsorption A selective adsorption of limonene and α-pinene enantiomers was revealed For α-pinenes selectivity was higher because of the difference in heats of adsorption 1. Introduction Since the beginning of the 20th century, the industrial application of adsorbents has driven the need for porous materials with tailored properties. One of the key requirements for adsorbents is uniform pore structure [ 1 ]. The first materials with homogeneous pores were zeolites [ 2 , 3 ]. However, their low pore variability and high polarity limited their widespread use. In 1992, mesostructured silicates of the MCM-41 type were introduced [ 4 , 5 ]. These adsorbents exhibited high uniformity and larger pore sizes compared to zeolites, with specific surface areas exceeding 1000 m²/g [ 6 , 7 ]. Nevertheless, their high cost, limited tunability in pore diameter and polarity, and excessive adsorption activity hindered broad adoption. The challenge of pore heterogeneity can be addressed using metal-organic frameworks (MOFs). The first MOF was reported by Yaghi in 1995 [ 8 ]. MOFs represent a promising class of porous materials that enable precise control over pore size and architecture [ 9 ]. By selecting specific metal ions and organic ligands, one can tailor pore polarity and structure [ 10 , 11 ]. The unique properties of MOFs make them suitable for gas capture and storage, chromatography, catalysis, chemical sensing, drug delivery, extraction and even hydrogen isotope separation [ 9 , 12 – 15 ]. All MOFs are crystalline, meaning they exhibit characteristic features such as space groups and crystal chirality [ 16 ]. Chirality in crystals can be considered at two hierarchical levels: molecular chirality (e.g., asymmetric carbon centers), and supramolecular chirality, arising from the asymmetric arrangement of atoms, molecules, or ions, leading to chiral crystal units [ 17 – 20 ] or nanostructures [ 21 – 23 ]. Supramolecular chirality often manifests as helical structures [ 24 , 25 ]. Chiral MOFs (CMOFs) are promising for enantioselective adsorption, chromatographic separation, and asymmetric catalysis [ 26 – 29 ]. Conventionally, a MOF is termed \"chiral\" if it contains asymmetric carbon atoms, typically resulting in both molecular and supramolecular chirality. However, some MOFs lack chiral centers yet exhibit crystal-level chirality due to supramolecular asymmetry, requiring them to belong to one of the 65 Sohncke space groups [ 30 ]. This class of CMOFs remains understudied, with only a few reported examples of CMOFs without asymmetric carbons [ 31 – 35 ]. This is due to formation of chiral racemate in crystal in most cases; lacking the external source of chirality during solvothermal reaction; unknown mechanism of spontaneous symmetry breaking [ 36 – 38 ]. Even when chiral conglomerates form, without external influence, they typically yield a 1:1 mixture of dextrorotatory and levorotatory crystals. To obtain CMOFs from achiral precursors, several strategies have been explored. For instance, Huang et al. synthesized a nontrivial porous CMOF from achiral CuCl₂·(H₂O)₂ and 3-amino-5-carboxy-1,2,4-triazole under hydrothermal conditions [ 33 ]. This CMOF forms a racemic conglomerate (space group I4₁22) with two distinct pore types: right-handed with diameter of 14 Å and left-handed of 4.9 Å. By selecting guest molecules sized between 4.9 Å and 14 Å, this MOF demonstrates enantioselectivity, as confirmed by limonene adsorption experiments [ 39 ]. Another example is a 3D chiral porous framework based on In(III) and 1,2,4,5-benzenetetracarboxylic acid [ 31 ]. While this CMOF crystallizes as a conglomerate, the enantiomeric ratio deviated from the expected 50:50 distribution. The observed Cotton effect confirmed spontaneous symmetry breaking during synthesis, though the mechanism remains unclear. Similar findings have been reported by other groups [ 34 , 37 , 38 , 40 ]. In this paper a CMOF based from achiral germanium dioxide and 2-methylpentamethylenediamine was studied. This CMOF (SU-MB) was firstly suggested by Zou [ 32 ]. SU-MB features two gyroidal micropore types with opposite chirality and pore diameter 12 Å. In the presence of hydrofluoric acid, one micropore type becomes selectively filled with additional clusters. This feature can be used to achieve selective adsorption of enantiomers. The Soai group previously demonstrated that chiral crystals can determine molecular chirality when acting as catalysts in the Soai reaction [ 41 – 44 ]. It proved the capability of surface with supramolecular chirality to recognize enantiomers. Our previous studies revealed differential adsorption of limonene and α-pinene enantiomers on some supramolecular CMOF [ 39 ], zeotype adsorbent [ 45 ], and non-porous crystals [ 46 , 47 ]. All of them hadn’t asymmetric carbon as SU-MB. But in the case of SU-MB the way of chirality emergence is unique. So, it was interesting to ascertain the chiral recognition mechanism during adsorption on this CMOF. 2. Materials and Methods 2.1. Materials GeO 2 (99,99%, Acros Organics, China, CAS 1310-53-8), MPMD (2-methylpentamethylenediamine, 98,0%, TCI, Japan, CAS 15520-10-2), hydrofluoric acid 99%, Reahim CAS 7664-39-3). Highly purified water obtained on a DV-10UV water deionizer (TsvetChrom, Dzerzhinsk, Russia) was used. In the inverse gas chromatography experiment, adsorption isotherms were measured for D-limonene (97%, Sigma-Aldrich, Milwaukee, USA, CAS 5969-27-5) and L-limonene (96%, SigmaAldrich, Milwaukee, USA, CAS 5989-54-8), as well as for α-(-)-pinene (99%, Sigma-Aldrich, Milwaukee, USA, CAS 7785-26-4) and α-(+)-pinene (99%, Sigma-Aldrich, Milwaukee, USA, CAS 7785-70-8). The enantiomers chosen have dimensions allowing to adsorb in 12 Å micropores of SU-MB. Helium (99.995%, Techgas, Orenburg, Russia, CAS 14762-55-1) was used as the carrier gas. 2.2. Methods According to [ 32 ] GeO 2 (1 g), MPMD (12,9 mL), water (6.88 mL), hydrofluoric acid (0.24 mL) were loaded in 100 mL autoclaves under autogenous pressure and heated at 165 °С during 11 days. Crystals were washed with water and dried at air. X-ray powder diffraction data for MOF studied were recorded on a Shimadzu XRD 7000 X-ray powder diffractometer for CuKα. Recording conditions: scanning angles: 5–40 deg, scanning step: 1 deg⸱min − 1 . The size and morphological features of zeotype material were detailed by field emission scanning electron microscopy (FE-SEM) with a Hitachi Regulus SU8220 scanning electron microscope (Tokyo, Japan). The images were taken in the mode of registration of secondary electrons at 2 kV accelerating voltage. Thermal stability of MOFs was evaluated by thermogravimetric analysis (TGA) with a TGA Q500 instrument (TA Instruments, US). The experiments were carried out in open platinum crucibles under argon flow in a temperature range of 25–670°C at a heating rate of 10°C⸱min − 1 . DSC experiments were conducted by DSC on a DSC Q-100 instrument (TA Instruments) at a constant heating rate 10 K⸱min − 1 in the temperature range from 10 to 300°C. The processing of the experimental data was performed using the TA Universal Analysis 2000 v.4.5A software. In order to ascertain the enantioselectivity, the adsorption isotherm analysis was used. Isotherms were obtained by inverse gas chromatography (IGC) [ 48 , 49 ]. IGC allows to obtain adsorption isotherms of vapors, much quickly than by other methods. Sample studied is packed in chromatographic column, and well-known substances are injected. The fraction of crystals powder of MOF studied was filled into a 300⸱3 mm stainless steel column. The column was conditioned at a temperature of 150 ˚С for 10 h; helium was used as a carrier gas. IGC studies were carried out on a CrystalLyuks 4000M gas chromatograph (Meta-Chrom, Yoshkor-Ola, Russia) equipped with a thermal conductivity detector. The column temperature ranged from 90 to 160 ˚С. The temperature of the injector and detector was 200 ˚С. The helium carrier gas flow rate varied from 2 to 20 mL min − 1. Enantiomers samples were injected as liquids with volume ranged from 1 to 10 µL. 2.3. Calculations The number of adsorbed enantiomers molecules and the vapors partial pressure were calculated described in [ 50 ]. The experimental adsorption isotherms were approximated by well-known Langmuir and Freundlich equations. From experimental chromatograms specific retention volumes, mL⸱g − 1 , were calculated: $$\\:{V}_{g}^{0}=\\frac{j\\left(t-{t}_{m}\\right)\\omega\\:}{{m}_{a}}$$ 1 t is the retention time, s, t m is the dead retention time, s, ω is the carrier gas flow rate, mL⸱s − 1 , m a is the mass of the adsorbent in the column, j is the James-Martin coefficient. The enantioselectivity coefficient was calculated as follows: $$\\:\\alpha\\:=\\frac{{V}_{g2}^{0}}{{V}_{g1}^{0}}$$ 2 where \\(\\:{V}_{g2}^{0}\\) > \\(\\:{V}_{g1}^{0}\\) . In order to prove the significance of enantioselectivity, t-test was used. The isosteric heats of adsorption q st , kJ⸱mol − 1 , were calculated from the slope of lnp vs. 1/T dependence[ 51 ]: $$\\:{\\left(\\frac{dlnp}{dt}\\right)}_{a}=\\frac{{q}_{st}}{R{T}^{2}}$$ 3 To determine whether a significant difference in adsorption values existed, a t-test was employed. This method was used to evaluate the null hypothesis that the adsorption values for the two enantiomers were statistically identical, by p-value calculating. The p-value was compared against a predetermined significance level (α = 0.05)[ 52 ]. When the p-value was found to be lower than α, the null hypothesis was rejected, indicating that a statistically significant difference in adsorption values between the enantiomers was present. The t-test was applied to all individual data points across the different adsorption isotherms. 3. Results and discussion In order to prove the accurate CMOF synthesis powder XRD and SEM images data were obtained. The comparison with [ 32 ] has shown the triangular form of the crystals in both cases (Figs. 1 ). Additionally, five peaks at 6.9, 8.0, 9.8, 12.2 and 14.4 deg were found (Fig. 2 ). It corresponds to XRD data from[ 32 ]. So, SEM and XRD data have supported the CMOF accurate synthesis. In order to estimate the temperature limit for measurements, TGA analysis was performed. The data on weight losses are presented in Fig. 3 (differential curve) and Fig. 1 S (integral curve). Up to 150°C, the mass loss was insignificant (less than 3%). This allows the determination of a temperature range for IGC measurements up to 150°C. Two maxima are observed on the curve (Fig. 3 ). The first one appears at 250°C, and the second one at 400°C. The first maximum may be attributed to the loss of crystal water, while the second could result from partial decomposition of MPMD. The weight loss at temperatures above 600°C is likely due to the complete destruction of the framework. A difference in the adsorption of limonene enantiomers was observed on SU-MB (Fig. 4 , Figs. 3 S– 5 S). At 130 and 150°C, the apparent difference in limonene adsorption was maximal. As with other samples exhibiting supramolecular chirality [ 47 , 53 , 54 ], enantioselectivity increased with adsorption values. To assess the reliability of the observed chiral recognition, a t-test was employed. The p-values are listed in Table 1 and Tables 1 S– 4 S. At 110°C, no chiral recognition was observed up to 400 Pa (Table 1 ). However, at higher pressures, a statistically significant difference in adsorption values was detected. At other temperatures, p < α at all pressures, indicating enantioselectivity even in cases where no visible difference was apparent in the figures. Enantioselectivity in a wide range of pressures is observed only for porous chiral crystals [ 39 , 45 ]. In pores, a smaller amount of substance is required to form an enantiomer layer, enabling chiral recognition even at low enantiomer concentrations. For limonenes, no dependence of the enantioselectivity coefficient (α) on temperature was observed. The α values ranged from 1.06 at 110°C to 1.07 at 150°C. This is unusual, as enantioselectivity generally decreases with temperature [55] . The achieved enantioselectivity was similar to that reported for the [{Cu 12 I (trz) 8 }4Cl 8H 2 O] n MOF sample [ 39 ]. Thus, for limonenes, the studied sample exhibited a typical enantioselectivity level. All isotherms in Figs. 4 and 3 S– 5 S can be classified as BET type III. Such isotherms are well approximated by the Freundlich equation. The results of the approximation are presented in Table 2 . All isotherms were fitted with high correlation coefficients (R ≥ 0.99). The Freundlich constants differed beyond the margin of error at 130, 140, and 150°C, corresponding to the isotherms with the highest enantioselectivity. Generally, adsorption isotherm constants derived from experimental data are less sensitive to enantioselectivity, and at low enantioselectivity levels, they rarely differ significantly. For α-pinene, the difference in enantiomer vapor adsorption was higher than for limonenes (Figs. 5 – 6 , Figs. 6 S–10S). At 90 and 110°C, the first adsorption isotherm measurements for α-pinenes exhibited BET type I behavior (Fig. 5 , Fig. 6 S). Differences in enantiomer adsorption were observed at both low and high pressures (Table 3 , Table 4 S). However, at certain pressures (up to 292.3 Pa, 113–226.1 Pa, and 146.1 Pa at 90°C; 153.8 and 217.5 Pa at 110°C), no significant difference was detected. Subsequent measurements at 120°C still showed BET type I isotherms (Fig. 9S). At this temperature, the adsorption of α-pinene enantiomers was statistically different at all partial pressures. However, after heating at 120°C, the isotherm shape at 90–110°C changed to BET type III (Fig. 6 , Figs. 7 S–8S). This shift from type I to type III indicates weakened adsorbate-adsorbent interactions, likely due to the collapse of the smallest pores at 120°C. Statistical analysis of enantiomer adsorption differences in subsequent measurements revealed a broader enantioselectivity range. For instance, at 110°C, adsorption values differed significantly at all pressures (Table 4 ), as was the case at other temperatures (Tables 5 S– 6 S). In all measurements at 120 and 130°C, the isotherms had a BET type I shape. The change in isotherm shape upon reaching 120°C suggests an uneven weakening of adsorbate-adsorbate and adsorbate-adsorbent interactions with increasing temperature. Since adsorbate-adsorbate interactions weaken faster than adsorbate-adsorbent interactions, the latter eventually dominate, altering the isotherm shape. Table 1 P-values for pairs of points of limonenes vapors adsorption at 110°C (α = 0.05, n = 5) Р, Pa р Р, Pa р Р, Pa р 227 0.0906 245 0.1699 263 0.2861 335 0.9337 400 0.004 417 0.0045 435 0.0049 453 0.005 471 0.005 489 0.0046 508 0.0043 526 0.0035 Table 2 Approximation parameters of limonenes adsorption isotherms by Freundlich equation S-(-)-limonene R-(+)-limonene K f · 10 4 n R K f · 10 4 n R 110 80 ± 10 1.34 ± 0.02 0.998 100 ± 10 1.28 ± 0.02 0.9993 130 43 ± 6 1.30 ± 0.02 0.9981 65 ± 7 1.23 ± 0.02 0.9982 140 51 ± 6 1.23 ± 0.02 0.9987 69 ± 6 1.18 ± 0.01 0.9993 150 59 ± 5 1.16 ± 0.01 0.9992 79 ± 4 1.11 ± 0.01 0.9998 Table 3 P-values for pairs of points of α-pinene vapors adsorption at 110°C (α = 0.05, n = 5, first measurement) Р, Pa р Р, Pa р Р, Pa Р 64 0.0451 154 0.23 218 0.057 281 0.0227 371 0.0296 435 0.0122 499 0.0058 589 0.0045 653 0.0028 This phenomenon has been previously reported by our group for both non-porous and porous chiral crystals [ 45 , 46 ]. At 120°C, the adsorption isotherms of α-pinene enantiomers differed at all partial pressures, whereas at 130°C, the adsorption values coincided. The decrease of chiral recognition at higher temperatures can be attributed to the proximity to α-pinene’s boiling point. A surface with supramolecular chirality cannot recognize enantiomers in the gaseous state Table 4 P-values for pairs of points of α-pinene vapors adsorption at 110°C (α = 0.05, n = 5, second and any further measurements) Р, Pa р Р,kPa р Р, Pa р 108 0.00001 328 0.00001 392 0.00004 431 0.0001 504 0.0001 537 0.0001 574 0.0003 593 0.0003 610 0.0005 Table 5 Approximation parameters of α-pinenes adsorption isotherms by the Freundlich equation T (-)-α-pinene (+)-α- pinene K f ·10 4 n R K f ·10 4 n R 90 272 ± 2 1.10 ± 0.01 0.9999 220 ± 10 1.15 ± 0.01 0.9996 100 243 ± 5 1.07 ± 0.01 0.9999 180 ± 8 1.14 ± 0.01 0.9997 110 189 ± 4 1.06 ± 0.01 0.9999 136 ± 6 1.13 ± 0.01 0.9998 Table 6 Approximation parameters of α-pinenes adsorption isotherms by the Langmuir equation T (-)-α-pinene (+)-α- pinene K L ·10 2 a m R K L ·10 2 a m R 90 64 ± 2 34 ± 3 0.9996 57 ± 2 39 ± 3 0.9995 110 11 ± 1 35 ± 3 0.9998 11 ± 1 38 ± 3 0.9996 120 2.3 ± 0.5 42 ± 6 0.9822 0.19 ± 0.02 49 ± 5 0.9901 130 0.17 ± 0.02 108 ± 9 0.9955 0.17 ± 0.02 112 ± 9 0.9961 because the adsorbed layer behaves as a two-dimensional van der Waals gas, lacking short- or long-range order [ 56 ].Comparison of limonene and α-pinene isotherms reveals that for limonenes, chiral recognition persisted even at 150°C (27°C below their boiling point), particularly at high partial pressures. In contrast, for α-pinenes at 130°C (25°C below boiling), no chiral recognition was observed. This suggests that the adsorption layer of the bulkier α-pinene molecule is less stable than that of limonene. Adsorption isotherms at 90–110°C from subsequent measurements were approximated using the Freundlich equation (Table 5 ). The approximation quality was high (R ≥ 0.9996), and adsorption constants differed at all temperatures, decreasing with temperature for both enantiomers. For BET type I isotherms (90–130°C), R values were also high. The monolayer capacity ( a m ) remained constant at 90 and 110°C but increased at higher temperatures (Table 6 ). At all temperatures, a m values for both enantiomers Table 7 Enantioselectivity coefficients for limonenes and α-pinenes T α limonenes α-pinenes 90 - 1.12 100 - 1.09 110 1.06 1.15 120 - 1.06 130 1.07 1.00 140 1.05 - 150 1.07 - 160 1.05 - coincided, as expected. However, Langmuir constants at 90 and 120°C were not equal, supporting the conclusion of enantioselectivity. When comparing enantioselectivity of limonenes and α-pinenes, α-pinenes exhibited a maximum α of 1.15 at 110°C, whereas limonenes reached only 1.07 (Table 7 ). Data at 130°C could not be compared due to the loss of α-pinene enantioselectivity near its boiling point. The higher enantioselectivity for α-pinenes may result from a greater difference in the isosteric heats of adsorption (Q st ) between enantiomers (Fig. 7 ). For limonenes, Q st increased with adsorption, but the difference was notable only at low coverages. In contrast, for α-pinenes, Q st exhibited a more pronounced divergence, suggesting a different adsorption mechanism. For limonene enantiomers, Q st values at high coverages approached the heat of liquefaction (L), consistent with typical adsorption behavior. At coverages > 1, the second and further adsorption layers form, for which Q st ≈L. A similar trend was observed for (−)-α-pinene, but not for (+)-α-pinene, indicating that the latter did not form a complete monolayer. This difference in monolayer formation likely contributed to the additional enantioselectivity observed for α-pinenes. 4. Conclusion On the SU-MB sample studied, differences in the adsorption of both limonene and α-pinene enantiomers were observed. The maximal enantioselectivity coefficient (α) was found to be 1.15. The reliability of enantioselectivity was confirmed by t-test results. This CMOF sample exhibited consistent enantioselectivity, which is unusual given the absence of asymmetric carbon atoms. The observed chirality was of supramolecular origin. In this sample, half of the cavities were occupied, and all of them exhibited the same handedness [ 32 ], leading to the emergence of supramolecular chirality. This CMOF is of particular interest because chirality was manifested solely through helical cavities, while the crystal as a whole remained achiral. These findings demonstrate that the presence of an asymmetric structural element, such as pore helicity, is sufficient for enantiomer recognition during adsorption. This expands the range of adsorbents that can be utilized for enantioselective adsorption processes. Declarations Funding This work was supported by the Russian Science Foundation (project No. 25-13-20076). The authors have no competing interests to declare that are relevant to the content of this article. Acknowledgements This work was performed with the aid of equipment of the Shared Facility Center CKP FMI of the Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences. References R.T. Yang (2003) Adsorbents : fundamentals and applications. John Wiley & Sons, Hoboken, New Jersey V. Van Speybroeck, K. Hemelsoet, L. Joos, M. Waroquier, R. 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Sharafutdinova, E.L. Gilfanova, I. N.Pavlova, G.Z. Garipova Phys. Chem. Chem. Phys. 23, 11968 (2021) Additional Declarations No competing interests reported. Supplementary Files SM.docx Cite Share Download PDF Status: Published Journal Publication published 20 Feb, 2026 Read the published version in Adsorption → Version 1 posted Editorial decision: Revision requested 03 Nov, 2025 Reviews received at journal 23 Sep, 2025 Reviews received at journal 18 Sep, 2025 Reviewers agreed at journal 14 Sep, 2025 Reviewers agreed at journal 14 Sep, 2025 Reviewers invited by journal 14 Sep, 2025 Editor assigned by journal 29 Aug, 2025 Submission checks completed at journal 29 Aug, 2025 First submitted to journal 27 Aug, 2025 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. 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°C\\u003c/p\\u003e\",\"description\":\"\",\"filename\":\"floatimage4.png\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-7470067/v1/f2408f934bd12ee898e26daa.png\"},{\"id\":91831727,\"identity\":\"49ce0fdd-3189-4e61-82bc-049509b99314\",\"added_by\":\"auto\",\"created_at\":\"2025-09-22 09:10:41\",\"extension\":\"png\",\"order_by\":5,\"title\":\"Figure 5\",\"display\":\"\",\"copyAsset\":false,\"role\":\"figure\",\"size\":44645,\"visible\":true,\"origin\":\"\",\"legend\":\"\\u003cp\\u003eα-pinene enantiomers vapours adsorption isotherms at 110 °C (first measurement)\\u003c/p\\u003e\",\"description\":\"\",\"filename\":\"floatimage5.png\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-7470067/v1/a1c7ecacb3ac3cce4a12102c.png\"},{\"id\":91831717,\"identity\":\"7152dc31-44ac-42e9-80d7-66c03ccf3b2e\",\"added_by\":\"auto\",\"created_at\":\"2025-09-22 09:10:41\",\"extension\":\"png\",\"order_by\":6,\"title\":\"Figure 6\",\"display\":\"\",\"copyAsset\":false,\"role\":\"figure\",\"size\":42613,\"visible\":true,\"origin\":\"\",\"legend\":\"\\u003cp\\u003eα-pinene enantiomers vapours adsorption isotherms at 110 °C (second and any further measurements)\\u003c/p\\u003e\",\"description\":\"\",\"filename\":\"floatimage6.png\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-7470067/v1/595043515a4c29c3909fdab3.png\"},{\"id\":91834620,\"identity\":\"d197b8c5-df37-4ca9-b9f0-d4be8088591f\",\"added_by\":\"auto\",\"created_at\":\"2025-09-22 09:26:41\",\"extension\":\"png\",\"order_by\":7,\"title\":\"Figure 7\",\"display\":\"\",\"copyAsset\":false,\"role\":\"figure\",\"size\":54150,\"visible\":true,\"origin\":\"\",\"legend\":\"\\u003cp\\u003eIsosteric heats of limonenes and α-pinenes adsorption.\\u003c/p\\u003e\",\"description\":\"\",\"filename\":\"floatimage7.png\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-7470067/v1/0cefc4d3fec577eb97d1c700.png\"},{\"id\":103252219,\"identity\":\"de3dad85-7cc9-4559-8d60-9a6aed935908\",\"added_by\":\"auto\",\"created_at\":\"2026-02-23 16:13:32\",\"extension\":\"pdf\",\"order_by\":0,\"title\":\"\",\"display\":\"\",\"copyAsset\":false,\"role\":\"manuscript-pdf\",\"size\":1259452,\"visible\":true,\"origin\":\"\",\"legend\":\"\",\"description\":\"\",\"filename\":\"manuscript.pdf\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-7470067/v1/b00d19ef-78fb-4b44-b29d-d172c0fe386a.pdf\"},{\"id\":91832198,\"identity\":\"b6c63034-ffda-4a8d-b567-fc6bb0a48b34\",\"added_by\":\"auto\",\"created_at\":\"2025-09-22 09:18:41\",\"extension\":\"docx\",\"order_by\":0,\"title\":\"\",\"display\":\"\",\"copyAsset\":false,\"role\":\"supplement\",\"size\":207755,\"visible\":true,\"origin\":\"\",\"legend\":\"\",\"description\":\"\",\"filename\":\"SM.docx\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-7470067/v1/d13fa1c86e05a215deddde5d.docx\"}],\"financialInterests\":\"No competing interests reported.\",\"formattedTitle\":\"Enantioselective adsorption of limonenes and α-pinenes on germanium oxide metal-organic framework\",\"fulltext\":[{\"header\":\"Highlights\",\"content\":\"\\u003cp\\u003eEnantiomer adsorption on germanium oxide framework SU-MB was studied\\u003c/p\\u003e\\u003cp\\u003eSU-MB framework lacks asymmetric carbon, but has helical micropores\\u003c/p\\u003e\\u003cp\\u003eOnly one type of chiral micropores is available for adsorption\\u003c/p\\u003e\\u003cp\\u003eA selective adsorption of limonene and α-pinene enantiomers was revealed\\u003c/p\\u003e\\u003cp\\u003eFor α-pinenes selectivity was higher because of the difference in heats of adsorption\\u003c/p\\u003e\"},{\"header\":\"1. Introduction\",\"content\":\"\\u003cp\\u003eSince the beginning of the 20th century, the industrial application of adsorbents has driven the need for porous materials with tailored properties. One of the key requirements for adsorbents is uniform pore structure [\\u003cspan citationid=\\\"CR1\\\" class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e]. The first materials with homogeneous pores were zeolites [\\u003cspan citationid=\\\"CR2\\\" class=\\\"CitationRef\\\"\\u003e2\\u003c/span\\u003e, \\u003cspan citationid=\\\"CR3\\\" class=\\\"CitationRef\\\"\\u003e3\\u003c/span\\u003e]. However, their low pore variability and high polarity limited their widespread use. In 1992, mesostructured silicates of the MCM-41 type were introduced [\\u003cspan citationid=\\\"CR4\\\" class=\\\"CitationRef\\\"\\u003e4\\u003c/span\\u003e, \\u003cspan citationid=\\\"CR5\\\" class=\\\"CitationRef\\\"\\u003e5\\u003c/span\\u003e]. These adsorbents exhibited high uniformity and larger pore sizes compared to zeolites, with specific surface areas exceeding 1000 m\\u0026sup2;/g [\\u003cspan citationid=\\\"CR6\\\" class=\\\"CitationRef\\\"\\u003e6\\u003c/span\\u003e, \\u003cspan citationid=\\\"CR7\\\" class=\\\"CitationRef\\\"\\u003e7\\u003c/span\\u003e]. Nevertheless, their high cost, limited tunability in pore diameter and polarity, and excessive adsorption activity hindered broad adoption.\\u003c/p\\u003e\\u003cp\\u003eThe challenge of pore heterogeneity can be addressed using metal-organic frameworks (MOFs). The first MOF was reported by Yaghi in 1995 [\\u003cspan citationid=\\\"CR8\\\" class=\\\"CitationRef\\\"\\u003e8\\u003c/span\\u003e]. MOFs represent a promising class of porous materials that enable precise control over pore size and architecture [\\u003cspan citationid=\\\"CR9\\\" class=\\\"CitationRef\\\"\\u003e9\\u003c/span\\u003e]. By selecting specific metal ions and organic ligands, one can tailor pore polarity and structure [\\u003cspan citationid=\\\"CR10\\\" class=\\\"CitationRef\\\"\\u003e10\\u003c/span\\u003e, \\u003cspan citationid=\\\"CR11\\\" class=\\\"CitationRef\\\"\\u003e11\\u003c/span\\u003e]. The unique properties of MOFs make them suitable for gas capture and storage, chromatography, catalysis, chemical sensing, drug delivery, extraction and even hydrogen isotope separation [\\u003cspan citationid=\\\"CR9\\\" class=\\\"CitationRef\\\"\\u003e9\\u003c/span\\u003e, \\u003cspan additionalcitationids=\\\"CR13 CR14\\\" citationid=\\\"CR12\\\" class=\\\"CitationRef\\\"\\u003e12\\u003c/span\\u003e\\u0026ndash;\\u003cspan citationid=\\\"CR15\\\" class=\\\"CitationRef\\\"\\u003e15\\u003c/span\\u003e].\\u003c/p\\u003e\\u003cp\\u003eAll MOFs are crystalline, meaning they exhibit characteristic features such as space groups and crystal chirality [\\u003cspan citationid=\\\"CR16\\\" class=\\\"CitationRef\\\"\\u003e16\\u003c/span\\u003e]. Chirality in crystals can be considered at two hierarchical levels: molecular chirality (e.g., asymmetric carbon centers), and supramolecular chirality, arising from the asymmetric arrangement of atoms, molecules, or ions, leading to chiral crystal units [\\u003cspan additionalcitationids=\\\"CR18 CR19\\\" citationid=\\\"CR17\\\" class=\\\"CitationRef\\\"\\u003e17\\u003c/span\\u003e\\u0026ndash;\\u003cspan citationid=\\\"CR20\\\" class=\\\"CitationRef\\\"\\u003e20\\u003c/span\\u003e] or nanostructures [\\u003cspan additionalcitationids=\\\"CR22\\\" citationid=\\\"CR21\\\" class=\\\"CitationRef\\\"\\u003e21\\u003c/span\\u003e\\u0026ndash;\\u003cspan citationid=\\\"CR23\\\" class=\\\"CitationRef\\\"\\u003e23\\u003c/span\\u003e]. Supramolecular chirality often manifests as helical structures [\\u003cspan citationid=\\\"CR24\\\" class=\\\"CitationRef\\\"\\u003e24\\u003c/span\\u003e, \\u003cspan citationid=\\\"CR25\\\" class=\\\"CitationRef\\\"\\u003e25\\u003c/span\\u003e]. Chiral MOFs (CMOFs) are promising for enantioselective adsorption, chromatographic separation, and asymmetric catalysis [\\u003cspan additionalcitationids=\\\"CR27 CR28\\\" citationid=\\\"CR26\\\" class=\\\"CitationRef\\\"\\u003e26\\u003c/span\\u003e\\u0026ndash;\\u003cspan citationid=\\\"CR29\\\" class=\\\"CitationRef\\\"\\u003e29\\u003c/span\\u003e]. Conventionally, a MOF is termed \\\"chiral\\\" if it contains asymmetric carbon atoms, typically resulting in both molecular and supramolecular chirality. However, some MOFs lack chiral centers yet exhibit crystal-level chirality due to supramolecular asymmetry, requiring them to belong to one of the 65 Sohncke space groups [\\u003cspan citationid=\\\"CR30\\\" class=\\\"CitationRef\\\"\\u003e30\\u003c/span\\u003e].\\u003c/p\\u003e\\u003cp\\u003eThis class of CMOFs remains understudied, with only a few reported examples of CMOFs without asymmetric carbons [\\u003cspan additionalcitationids=\\\"CR32 CR33 CR34\\\" citationid=\\\"CR31\\\" class=\\\"CitationRef\\\"\\u003e31\\u003c/span\\u003e\\u0026ndash;\\u003cspan citationid=\\\"CR35\\\" class=\\\"CitationRef\\\"\\u003e35\\u003c/span\\u003e]. This is due to formation of chiral racemate in crystal in most cases; lacking the external source of chirality during solvothermal reaction; unknown mechanism of spontaneous symmetry breaking [\\u003cspan additionalcitationids=\\\"CR37\\\" citationid=\\\"CR36\\\" class=\\\"CitationRef\\\"\\u003e36\\u003c/span\\u003e\\u0026ndash;\\u003cspan citationid=\\\"CR38\\\" class=\\\"CitationRef\\\"\\u003e38\\u003c/span\\u003e]. Even when chiral conglomerates form, without external influence, they typically yield a 1:1 mixture of dextrorotatory and levorotatory crystals. To obtain CMOFs from achiral precursors, several strategies have been explored. For instance, Huang et al. synthesized a nontrivial porous CMOF from achiral CuCl₂\\u0026middot;(H₂O)₂ and 3-amino-5-carboxy-1,2,4-triazole under hydrothermal conditions [\\u003cspan citationid=\\\"CR33\\\" class=\\\"CitationRef\\\"\\u003e33\\u003c/span\\u003e]. This CMOF forms a racemic conglomerate (space group I4₁22) with two distinct pore types: right-handed with diameter of 14 \\u0026Aring; and left-handed of 4.9 \\u0026Aring;. By selecting guest molecules sized between 4.9 \\u0026Aring; and 14 \\u0026Aring;, this MOF demonstrates enantioselectivity, as confirmed by limonene adsorption experiments [\\u003cspan citationid=\\\"CR39\\\" class=\\\"CitationRef\\\"\\u003e39\\u003c/span\\u003e]. Another example is a 3D chiral porous framework based on In(III) and 1,2,4,5-benzenetetracarboxylic acid [\\u003cspan citationid=\\\"CR31\\\" class=\\\"CitationRef\\\"\\u003e31\\u003c/span\\u003e]. While this CMOF crystallizes as a conglomerate, the enantiomeric ratio deviated from the expected 50:50 distribution. The observed Cotton effect confirmed spontaneous symmetry breaking during synthesis, though the mechanism remains unclear. Similar findings have been reported by other groups [\\u003cspan citationid=\\\"CR34\\\" class=\\\"CitationRef\\\"\\u003e34\\u003c/span\\u003e, \\u003cspan citationid=\\\"CR37\\\" class=\\\"CitationRef\\\"\\u003e37\\u003c/span\\u003e, \\u003cspan citationid=\\\"CR38\\\" class=\\\"CitationRef\\\"\\u003e38\\u003c/span\\u003e, \\u003cspan citationid=\\\"CR40\\\" class=\\\"CitationRef\\\"\\u003e40\\u003c/span\\u003e].\\u003c/p\\u003e\\u003cp\\u003eIn this paper a CMOF based from achiral germanium dioxide and 2-methylpentamethylenediamine was studied. This CMOF (SU-MB) was firstly suggested by Zou [\\u003cspan citationid=\\\"CR32\\\" class=\\\"CitationRef\\\"\\u003e32\\u003c/span\\u003e]. SU-MB features two gyroidal micropore types with opposite chirality and pore diameter 12 \\u0026Aring;. In the presence of hydrofluoric acid, one micropore type becomes selectively filled with additional clusters. This feature can be used to achieve selective adsorption of enantiomers.\\u003c/p\\u003e\\u003cp\\u003eThe Soai group previously demonstrated that chiral crystals can determine molecular chirality when acting as catalysts in the Soai reaction [\\u003cspan additionalcitationids=\\\"CR42 CR43\\\" citationid=\\\"CR41\\\" class=\\\"CitationRef\\\"\\u003e41\\u003c/span\\u003e\\u0026ndash;\\u003cspan citationid=\\\"CR44\\\" class=\\\"CitationRef\\\"\\u003e44\\u003c/span\\u003e]. It proved the capability of surface with supramolecular chirality to recognize enantiomers. Our previous studies revealed differential adsorption of limonene and α-pinene enantiomers on some supramolecular CMOF [\\u003cspan citationid=\\\"CR39\\\" class=\\\"CitationRef\\\"\\u003e39\\u003c/span\\u003e], zeotype adsorbent [\\u003cspan citationid=\\\"CR45\\\" class=\\\"CitationRef\\\"\\u003e45\\u003c/span\\u003e], and non-porous crystals [\\u003cspan citationid=\\\"CR46\\\" class=\\\"CitationRef\\\"\\u003e46\\u003c/span\\u003e, \\u003cspan citationid=\\\"CR47\\\" class=\\\"CitationRef\\\"\\u003e47\\u003c/span\\u003e]. All of them hadn\\u0026rsquo;t asymmetric carbon as SU-MB. But in the case of SU-MB the way of chirality emergence is unique. So, it was interesting to ascertain the chiral recognition mechanism during adsorption on this CMOF.\\u003c/p\\u003e\"},{\"header\":\"2. Materials and Methods\",\"content\":\"\\u003cdiv id=\\\"Sec3\\\" class=\\\"Section2\\\"\\u003e\\u003ch2\\u003e2.1. Materials\\u003c/h2\\u003e\\u003cp\\u003eGeO\\u003csub\\u003e2\\u003c/sub\\u003e (99,99%, Acros Organics, China, CAS 1310-53-8), MPMD (2-methylpentamethylenediamine, 98,0%, TCI, Japan, CAS 15520-10-2), hydrofluoric acid 99%, Reahim CAS 7664-39-3). Highly purified water obtained on a DV-10UV water deionizer (TsvetChrom, Dzerzhinsk, Russia) was used.\\u003c/p\\u003e\\u003cp\\u003eIn the inverse gas chromatography experiment, adsorption isotherms were measured for D-limonene (97%, Sigma-Aldrich, Milwaukee, USA, CAS 5969-27-5) and L-limonene (96%, SigmaAldrich, Milwaukee, USA, CAS 5989-54-8), as well as for α-(-)-pinene (99%, Sigma-Aldrich, Milwaukee, USA, CAS 7785-26-4) and α-(+)-pinene (99%, Sigma-Aldrich, Milwaukee, USA, CAS 7785-70-8). The enantiomers chosen have dimensions allowing to adsorb in 12 \\u0026Aring; micropores of SU-MB. Helium (99.995%, Techgas, Orenburg, Russia, CAS 14762-55-1) was used as the carrier gas.\\u003c/p\\u003e\\u003c/div\\u003e\\u003cdiv id=\\\"Sec4\\\" class=\\\"Section2\\\"\\u003e\\u003ch2\\u003e2.2. Methods\\u003c/h2\\u003e\\u003cp\\u003eAccording to [\\u003cspan citationid=\\\"CR32\\\" class=\\\"CitationRef\\\"\\u003e32\\u003c/span\\u003e] GeO\\u003csub\\u003e2\\u003c/sub\\u003e (1 g), MPMD (12,9 mL), water (6.88 mL), hydrofluoric acid (0.24 mL) were loaded in 100 mL autoclaves under autogenous pressure and heated at 165 \\u0026deg;С during 11 days. Crystals were washed with water and dried at air.\\u003c/p\\u003e\\u003cp\\u003eX-ray powder diffraction data for MOF studied were recorded on a Shimadzu XRD 7000 X-ray powder diffractometer for CuKα. Recording conditions: scanning angles: 5\\u0026ndash;40 deg, scanning step: 1 deg⸱min\\u003csup\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/sup\\u003e.\\u003c/p\\u003e\\u003cp\\u003eThe size and morphological features of zeotype material were detailed by field emission scanning electron microscopy (FE-SEM) with a Hitachi Regulus SU8220 scanning electron microscope (Tokyo, Japan). The images were taken in the mode of registration of secondary electrons at 2 kV accelerating voltage.\\u003c/p\\u003e\\u003cp\\u003eThermal stability of MOFs was evaluated by thermogravimetric analysis (TGA) with a TGA Q500 instrument (TA Instruments, US). The experiments were carried out in open platinum crucibles under argon flow in a temperature range of 25\\u0026ndash;670\\u0026deg;C at a heating rate of 10\\u0026deg;C⸱min\\u003csup\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/sup\\u003e.\\u003c/p\\u003e\\u003cp\\u003eDSC experiments were conducted by DSC on a DSC Q-100 instrument (TA Instruments) at a constant heating rate 10 K⸱min\\u003csup\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/sup\\u003e in the temperature range from 10 to 300\\u0026deg;C. The processing of the experimental data was performed using the TA Universal Analysis 2000 v.4.5A software.\\u003c/p\\u003e\\u003cp\\u003eIn order to ascertain the enantioselectivity, the adsorption isotherm analysis was used. Isotherms were obtained by inverse gas chromatography (IGC) [\\u003cspan citationid=\\\"CR48\\\" class=\\\"CitationRef\\\"\\u003e48\\u003c/span\\u003e, \\u003cspan citationid=\\\"CR49\\\" class=\\\"CitationRef\\\"\\u003e49\\u003c/span\\u003e]. IGC allows to obtain adsorption isotherms of vapors, much quickly than by other methods. Sample studied is packed in chromatographic column, and well-known substances are injected.\\u003c/p\\u003e\\u003cp\\u003eThe fraction of crystals powder of MOF studied was filled into a 300⸱3 mm stainless steel column. The column was conditioned at a temperature of 150 ˚С for 10 h; helium was used as a carrier gas. IGC studies were carried out on a CrystalLyuks 4000M gas chromatograph (Meta-Chrom, Yoshkor-Ola, Russia) equipped with a thermal conductivity detector. The column temperature ranged from 90 to 160 ˚С. The temperature of the injector and detector was 200 ˚С. The helium carrier gas flow rate varied from 2 to 20 mL min\\u003csup\\u003e\\u0026minus;\\u003c/sup\\u003e1. Enantiomers samples were injected as liquids with volume ranged from 1 to 10 \\u0026micro;L.\\u003c/p\\u003e\\u003c/div\\u003e\\u003cdiv id=\\\"Sec5\\\" class=\\\"Section2\\\"\\u003e\\u003ch2\\u003e2.3. Calculations\\u003c/h2\\u003e\\u003cp\\u003eThe number of adsorbed enantiomers molecules and the vapors partial pressure were calculated described in [\\u003cspan citationid=\\\"CR50\\\" class=\\\"CitationRef\\\"\\u003e50\\u003c/span\\u003e]. The experimental adsorption isotherms were approximated by well-known Langmuir and Freundlich equations.\\u003c/p\\u003e\\u003cp\\u003eFrom experimental chromatograms specific retention volumes, mL⸱g\\u003csup\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/sup\\u003e, were calculated:\\u003cdiv id=\\\"Equ1\\\" class=\\\"Equation\\\"\\u003e\\u003cdiv format=\\\"TEX\\\" class=\\\"mathdisplay\\\" id=\\\"FileID_Equ1\\\" name=\\\"EquationSource\\\"\\u003e\\n$$\\\\:{V}_{g}^{0}=\\\\frac{j\\\\left(t-{t}_{m}\\\\right)\\\\omega\\\\:}{{m}_{a}}$$\\u003c/div\\u003e\\u003cdiv class=\\\"EquationNumber\\\"\\u003e1\\u003c/div\\u003e\\u003c/div\\u003e\\u003c/p\\u003e\\u003cp\\u003e\\u003cem\\u003et\\u003c/em\\u003e is the retention time, s, \\u003cem\\u003et\\u003c/em\\u003e\\u003csub\\u003e\\u003cem\\u003em\\u003c/em\\u003e\\u003c/sub\\u003e is the dead retention time, s, ω is the carrier gas flow rate, mL⸱s\\u003csup\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/sup\\u003e, \\u003cem\\u003em\\u003c/em\\u003e\\u003csub\\u003e\\u003cem\\u003ea\\u003c/em\\u003e\\u003c/sub\\u003e is the mass of the adsorbent in the column, j is the James-Martin coefficient.\\u003c/p\\u003e\\u003cp\\u003eThe enantioselectivity coefficient was calculated as follows:\\u003cdiv id=\\\"Equ2\\\" class=\\\"Equation\\\"\\u003e\\u003cdiv format=\\\"TEX\\\" class=\\\"mathdisplay\\\" id=\\\"FileID_Equ2\\\" name=\\\"EquationSource\\\"\\u003e\\n$$\\\\:\\\\alpha\\\\:=\\\\frac{{V}_{g2}^{0}}{{V}_{g1}^{0}}$$\\u003c/div\\u003e\\u003cdiv class=\\\"EquationNumber\\\"\\u003e2\\u003c/div\\u003e\\u003c/div\\u003e\\u003c/p\\u003e\\u003cp\\u003ewhere \\u003cspan class=\\\"InlineEquation\\\"\\u003e\\u003cspan class=\\\"mathinline\\\"\\u003e\\\\(\\\\:{V}_{g2}^{0}\\\\)\\u003c/span\\u003e\\u003c/span\\u003e \\u0026gt;\\u003cspan class=\\\"InlineEquation\\\"\\u003e\\u003cspan class=\\\"mathinline\\\"\\u003e\\\\(\\\\:{V}_{g1}^{0}\\\\)\\u003c/span\\u003e\\u003c/span\\u003e. In order to prove the significance of enantioselectivity, t-test was used.\\u003c/p\\u003e\\u003cp\\u003eThe isosteric heats of adsorption \\u003cem\\u003eq\\u003c/em\\u003e\\u003csub\\u003e\\u003cem\\u003est\\u003c/em\\u003e\\u003c/sub\\u003e, kJ⸱mol\\u003csup\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/sup\\u003e, were calculated from the slope of \\u003cem\\u003elnp\\u003c/em\\u003e vs. \\u003cem\\u003e1/T\\u003c/em\\u003e dependence[\\u003cspan citationid=\\\"CR51\\\" class=\\\"CitationRef\\\"\\u003e51\\u003c/span\\u003e]:\\u003cdiv id=\\\"Equ3\\\" class=\\\"Equation\\\"\\u003e\\u003cdiv format=\\\"TEX\\\" class=\\\"mathdisplay\\\" id=\\\"FileID_Equ3\\\" name=\\\"EquationSource\\\"\\u003e\\n$$\\\\:{\\\\left(\\\\frac{dlnp}{dt}\\\\right)}_{a}=\\\\frac{{q}_{st}}{R{T}^{2}}$$\\u003c/div\\u003e\\u003cdiv class=\\\"EquationNumber\\\"\\u003e3\\u003c/div\\u003e\\u003c/div\\u003e\\u003c/p\\u003e\\u003cp\\u003eTo determine whether a significant difference in adsorption values existed, a t-test was employed. This method was used to evaluate the null hypothesis that the adsorption values for the two enantiomers were statistically identical, by p-value calculating. The p-value was compared against a predetermined significance level (α\\u0026thinsp;=\\u0026thinsp;0.05)[\\u003cspan citationid=\\\"CR52\\\" class=\\\"CitationRef\\\"\\u003e52\\u003c/span\\u003e]. When the p-value was found to be lower than α, the null hypothesis was rejected, indicating that a statistically significant difference in adsorption values between the enantiomers was present. The t-test was applied to all individual data points across the different adsorption isotherms.\\u003c/p\\u003e\\u003c/div\\u003e\"},{\"header\":\"3. Results and discussion\",\"content\":\"\\u003cp\\u003eIn order to prove the accurate CMOF synthesis powder XRD and SEM images data were obtained. The comparison with [\\u003cspan citationid=\\\"CR32\\\" class=\\\"CitationRef\\\"\\u003e32\\u003c/span\\u003e] has shown the triangular form of the crystals in both cases (Figs.\\u0026nbsp;\\u003cspan refid=\\\"Fig1\\\" class=\\\"InternalRef\\\"\\u003e1\\u003c/span\\u003e). Additionally, five peaks at 6.9, 8.0, 9.8, 12.2 and 14.4 deg were found (Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig2\\\" class=\\\"InternalRef\\\"\\u003e2\\u003c/span\\u003e). It corresponds to XRD data from[\\u003cspan citationid=\\\"CR32\\\" class=\\\"CitationRef\\\"\\u003e32\\u003c/span\\u003e]. So, SEM and XRD data have supported the CMOF accurate synthesis.\\u003c/p\\u003e\\u003cp\\u003eIn order to estimate the temperature limit for measurements, TGA analysis was performed. The data on weight losses are presented in Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig3\\\" class=\\\"InternalRef\\\"\\u003e3\\u003c/span\\u003e (differential curve) and Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig1\\\" class=\\\"InternalRef\\\"\\u003e1\\u003c/span\\u003eS (integral curve). Up to 150\\u0026deg;C, the mass loss was insignificant (less than 3%). This allows the determination of a temperature range for IGC measurements up to 150\\u0026deg;C. Two maxima are observed on the curve (Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig3\\\" class=\\\"InternalRef\\\"\\u003e3\\u003c/span\\u003e). The first one appears at 250\\u0026deg;C, and the second one at 400\\u0026deg;C. The first maximum may be attributed to the loss of crystal water, while the second could result from partial decomposition of MPMD. The weight loss at temperatures above 600\\u0026deg;C is likely due to the complete destruction of the framework.\\u003c/p\\u003e\\u003cp\\u003eA difference in the adsorption of limonene enantiomers was observed on SU-MB (Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig4\\\" class=\\\"InternalRef\\\"\\u003e4\\u003c/span\\u003e, Figs.\\u0026nbsp;\\u003cspan refid=\\\"Fig3\\\" class=\\\"InternalRef\\\"\\u003e3\\u003c/span\\u003eS\\u0026ndash;\\u003cspan refid=\\\"Fig5\\\" class=\\\"InternalRef\\\"\\u003e5\\u003c/span\\u003eS). At 130 and 150\\u0026deg;C, the apparent difference in limonene adsorption was maximal. As with other samples exhibiting supramolecular chirality [\\u003cspan citationid=\\\"CR47\\\" class=\\\"CitationRef\\\"\\u003e47\\u003c/span\\u003e, \\u003cspan citationid=\\\"CR53\\\" class=\\\"CitationRef\\\"\\u003e53\\u003c/span\\u003e, \\u003cspan citationid=\\\"CR54\\\" class=\\\"CitationRef\\\"\\u003e54\\u003c/span\\u003e], enantioselectivity increased with adsorption values. To assess the reliability of the observed chiral recognition, a t-test was employed. The p-values are listed in Table\\u0026nbsp;\\u003cspan refid=\\\"Tab1\\\" class=\\\"InternalRef\\\"\\u003e1\\u003c/span\\u003e and Tables\\u0026nbsp;\\u003cspan refid=\\\"Tab1\\\" class=\\\"InternalRef\\\"\\u003e1\\u003c/span\\u003eS\\u0026ndash;\\u003cspan refid=\\\"Tab4\\\" class=\\\"InternalRef\\\"\\u003e4\\u003c/span\\u003eS. At 110\\u0026deg;C, no chiral recognition was observed up to 400 Pa (Table\\u0026nbsp;\\u003cspan refid=\\\"Tab1\\\" class=\\\"InternalRef\\\"\\u003e1\\u003c/span\\u003e). However, at higher pressures, a statistically significant difference in adsorption values was detected. At other temperatures, p\\u0026thinsp;\\u0026lt;\\u0026thinsp;α at all pressures, indicating enantioselectivity even in cases where no visible difference was apparent in the figures. Enantioselectivity in a wide range of pressures is observed only for porous chiral crystals [\\u003cspan citationid=\\\"CR39\\\" class=\\\"CitationRef\\\"\\u003e39\\u003c/span\\u003e, \\u003cspan citationid=\\\"CR45\\\" class=\\\"CitationRef\\\"\\u003e45\\u003c/span\\u003e]. In pores, a smaller amount of substance is required to form an enantiomer layer, enabling chiral recognition even at low enantiomer concentrations.\\u003c/p\\u003e\\u003cp\\u003eFor limonenes, no dependence of the enantioselectivity coefficient (α) on temperature was observed. The α values ranged from 1.06 at 110\\u0026deg;C to 1.07 at 150\\u0026deg;C. This is unusual, as enantioselectivity generally decreases with temperature\\u003csup\\u003e[55]\\u003c/sup\\u003e. The achieved enantioselectivity was similar to that reported for the [{Cu\\u003csub\\u003e12\\u003c/sub\\u003e\\u003csup\\u003eI\\u003c/sup\\u003e(trz)\\u003csub\\u003e8\\u003c/sub\\u003e}4Cl 8H\\u003csub\\u003e2\\u003c/sub\\u003eO]\\u003csub\\u003en\\u003c/sub\\u003e MOF sample [\\u003cspan citationid=\\\"CR39\\\" class=\\\"CitationRef\\\"\\u003e39\\u003c/span\\u003e]. Thus, for limonenes, the studied sample exhibited a typical enantioselectivity level.\\u003c/p\\u003e\\u003cp\\u003eAll isotherms in Figs.\\u0026nbsp;\\u003cspan refid=\\\"Fig4\\\" class=\\\"InternalRef\\\"\\u003e4\\u003c/span\\u003e and \\u003cspan refid=\\\"Fig3\\\" class=\\\"InternalRef\\\"\\u003e3\\u003c/span\\u003eS\\u0026ndash;\\u003cspan refid=\\\"Fig5\\\" class=\\\"InternalRef\\\"\\u003e5\\u003c/span\\u003eS can be classified as BET type III. Such isotherms are well approximated by the Freundlich equation. The results of the approximation are presented in Table\\u0026nbsp;\\u003cspan refid=\\\"Tab2\\\" class=\\\"InternalRef\\\"\\u003e2\\u003c/span\\u003e. All isotherms were fitted with high correlation coefficients (R\\u0026thinsp;\\u0026ge;\\u0026thinsp;0.99). The Freundlich constants differed beyond the margin of error at 130, 140, and 150\\u0026deg;C, corresponding to the isotherms with the highest enantioselectivity. Generally, adsorption isotherm constants derived from experimental data are less sensitive to enantioselectivity, and at low enantioselectivity levels, they rarely differ significantly.\\u003c/p\\u003e\\u003cp\\u003eFor α-pinene, the difference in enantiomer vapor adsorption was higher than for limonenes (Figs.\\u0026nbsp;\\u003cspan refid=\\\"Fig5\\\" class=\\\"InternalRef\\\"\\u003e5\\u003c/span\\u003e\\u0026ndash;\\u003cspan refid=\\\"Fig6\\\" class=\\\"InternalRef\\\"\\u003e6\\u003c/span\\u003e, Figs.\\u0026nbsp;\\u003cspan refid=\\\"Fig6\\\" class=\\\"InternalRef\\\"\\u003e6\\u003c/span\\u003eS\\u0026ndash;10S). At 90 and 110\\u0026deg;C, the first adsorption isotherm measurements for α-pinenes exhibited BET type I behavior (Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig5\\\" class=\\\"InternalRef\\\"\\u003e5\\u003c/span\\u003e, Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig6\\\" class=\\\"InternalRef\\\"\\u003e6\\u003c/span\\u003eS). Differences in enantiomer adsorption were observed at both low and high pressures (Table\\u0026nbsp;\\u003cspan refid=\\\"Tab3\\\" class=\\\"InternalRef\\\"\\u003e3\\u003c/span\\u003e, Table\\u0026nbsp;\\u003cspan refid=\\\"Tab4\\\" class=\\\"InternalRef\\\"\\u003e4\\u003c/span\\u003eS). However, at certain pressures (up to 292.3 Pa, 113\\u0026ndash;226.1 Pa, and 146.1 Pa at 90\\u0026deg;C; 153.8 and 217.5 Pa at 110\\u0026deg;C), no significant difference was detected.\\u003c/p\\u003e\\u003cp\\u003eSubsequent measurements at 120\\u0026deg;C still showed BET type I isotherms (Fig.\\u0026nbsp;9S). At this temperature, the adsorption of α-pinene enantiomers was statistically different at all partial pressures. However, after heating at 120\\u0026deg;C, the isotherm shape at 90\\u0026ndash;110\\u0026deg;C changed to BET type III (Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig6\\\" class=\\\"InternalRef\\\"\\u003e6\\u003c/span\\u003e, Figs.\\u0026nbsp;\\u003cspan refid=\\\"Fig7\\\" class=\\\"InternalRef\\\"\\u003e7\\u003c/span\\u003eS\\u0026ndash;8S). This shift from type I to type III indicates weakened adsorbate-adsorbent interactions, likely due to the collapse of the smallest pores at 120\\u0026deg;C. Statistical analysis of enantiomer adsorption differences in subsequent measurements revealed a broader enantioselectivity range. For instance, at 110\\u0026deg;C, adsorption values differed significantly at all pressures (Table\\u0026nbsp;\\u003cspan refid=\\\"Tab4\\\" class=\\\"InternalRef\\\"\\u003e4\\u003c/span\\u003e), as was the case at other temperatures (Tables\\u0026nbsp;\\u003cspan refid=\\\"Tab5\\\" class=\\\"InternalRef\\\"\\u003e5\\u003c/span\\u003eS\\u0026ndash;\\u003cspan refid=\\\"Tab6\\\" class=\\\"InternalRef\\\"\\u003e6\\u003c/span\\u003eS).\\u003c/p\\u003e\\u003cp\\u003eIn all measurements at 120 and 130\\u0026deg;C, the isotherms had a BET type I shape. The change in isotherm shape upon reaching 120\\u0026deg;C suggests an uneven weakening of adsorbate-adsorbate and adsorbate-adsorbent interactions with increasing temperature. Since adsorbate-adsorbate interactions weaken faster than adsorbate-adsorbent interactions, the latter eventually dominate, altering the isotherm shape.\\u003c/p\\u003e\\u003cp\\u003e\\u003c/p\\u003e\\u003cp\\u003e\\u003c/p\\u003e\\u003cp\\u003e\\u003cdiv class=\\\"gridtable\\\"\\u003e\\u003ctable float=\\\"Yes\\\" id=\\\"Tab1\\\" border=\\\"1\\\"\\u003e\\u003ccaption language=\\\"En\\\"\\u003e\\u003cdiv class=\\\"CaptionNumber\\\"\\u003eTable 1\\u003c/div\\u003e\\u003cdiv class=\\\"CaptionContent\\\"\\u003e\\u003cp\\u003eP-values for pairs of points of limonenes vapors adsorption at 110\\u0026deg;C (α\\u0026thinsp;=\\u0026thinsp;0.05, n\\u0026thinsp;=\\u0026thinsp;5)\\u003c/p\\u003e\\u003c/div\\u003e\\u003c/caption\\u003e\\u003ccolgroup cols=\\\"6\\\"\\u003e\\u003cdiv align=\\\"left\\\" class=\\\"colspec\\\" colname=\\\"c1\\\" colnum=\\\"1\\\"\\u003e\\u003c/div\\u003e\\u003cdiv align=\\\"char\\\" char=\\\".\\\" class=\\\"colspec\\\" colname=\\\"c2\\\" colnum=\\\"2\\\"\\u003e\\u003c/div\\u003e\\u003cdiv align=\\\"char\\\" char=\\\".\\\" class=\\\"colspec\\\" colname=\\\"c3\\\" colnum=\\\"3\\\"\\u003e\\u003c/div\\u003e\\u003cdiv align=\\\"char\\\" char=\\\".\\\" class=\\\"colspec\\\" colname=\\\"c4\\\" colnum=\\\"4\\\"\\u003e\\u003c/div\\u003e\\u003cdiv align=\\\"char\\\" char=\\\".\\\" class=\\\"colspec\\\" colname=\\\"c5\\\" colnum=\\\"5\\\"\\u003e\\u003c/div\\u003e\\u003cdiv align=\\\"char\\\" char=\\\".\\\" class=\\\"colspec\\\" colname=\\\"c6\\\" colnum=\\\"6\\\"\\u003e\\u003c/div\\u003e\\u003cthead\\u003e\\u003ctr\\u003e\\u003cth align=\\\"left\\\" colname=\\\"c1\\\"\\u003e\\u003cp\\u003eР, Pa\\u003c/p\\u003e\\u003c/th\\u003e\\u003cth align=\\\"left\\\" colname=\\\"c2\\\"\\u003e\\u003cp\\u003eр\\u003c/p\\u003e\\u003c/th\\u003e\\u003cth align=\\\"left\\\" colname=\\\"c3\\\"\\u003e\\u003cp\\u003eР, Pa\\u003c/p\\u003e\\u003c/th\\u003e\\u003cth align=\\\"left\\\" 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char=\\\".\\\" colname=\\\"c2\\\"\\u003e\\u003cp\\u003e0.0049\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c3\\\"\\u003e\\u003cp\\u003e453\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c4\\\"\\u003e\\u003cp\\u003e0.005\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c5\\\"\\u003e\\u003cp\\u003e471\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c6\\\"\\u003e\\u003cp\\u003e0.005\\u003c/p\\u003e\\u003c/td\\u003e\\u003c/tr\\u003e\\u003ctr\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e\\u003cp\\u003e489\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c2\\\"\\u003e\\u003cp\\u003e0.0046\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c3\\\"\\u003e\\u003cp\\u003e508\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c4\\\"\\u003e\\u003cp\\u003e0.0043\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c5\\\"\\u003e\\u003cp\\u003e526\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c6\\\"\\u003e\\u003cp\\u003e0.0035\\u003c/p\\u003e\\u003c/td\\u003e\\u003c/tr\\u003e\\u003c/tbody\\u003e\\u003c/colgroup\\u003e\\u003c/table\\u003e\\u003c/div\\u003e\\u003c/p\\u003e\\u003cp\\u003e\\u003c/p\\u003e\\u003cp\\u003e\\u003cdiv class=\\\"gridtable\\\"\\u003e\\u003ctable float=\\\"Yes\\\" id=\\\"Tab2\\\" border=\\\"1\\\"\\u003e\\u003ccaption language=\\\"En\\\"\\u003e\\u003cdiv class=\\\"CaptionNumber\\\"\\u003eTable 2\\u003c/div\\u003e\\u003cdiv class=\\\"CaptionContent\\\"\\u003e\\u003cp\\u003eApproximation parameters of limonenes adsorption isotherms by Freundlich equation\\u003c/p\\u003e\\u003c/div\\u003e\\u003c/caption\\u003e\\u003ccolgroup cols=\\\"7\\\"\\u003e\\u003cdiv align=\\\"left\\\" class=\\\"colspec\\\" colname=\\\"c1\\\" colnum=\\\"1\\\"\\u003e\\u003c/div\\u003e\\u003cdiv align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" class=\\\"colspec\\\" colname=\\\"c2\\\" colnum=\\\"2\\\"\\u003e\\u003c/div\\u003e\\u003cdiv align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" class=\\\"colspec\\\" colname=\\\"c3\\\" colnum=\\\"3\\\"\\u003e\\u003c/div\\u003e\\u003cdiv align=\\\"char\\\" char=\\\".\\\" class=\\\"colspec\\\" colname=\\\"c4\\\" colnum=\\\"4\\\"\\u003e\\u003c/div\\u003e\\u003cdiv align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" class=\\\"colspec\\\" colname=\\\"c5\\\" colnum=\\\"5\\\"\\u003e\\u003c/div\\u003e\\u003cdiv align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" class=\\\"colspec\\\" colname=\\\"c6\\\" colnum=\\\"6\\\"\\u003e\\u003c/div\\u003e\\u003cdiv align=\\\"char\\\" char=\\\".\\\" class=\\\"colspec\\\" colname=\\\"c7\\\" colnum=\\\"7\\\"\\u003e\\u003c/div\\u003e\\u003cthead\\u003e\\u003ctr\\u003e\\u003cth align=\\\"left\\\" colname=\\\"c1\\\" morerows=\\\"1\\\" 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colname=\\\"c5\\\"\\u003e\\u003cp\\u003e100\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;10\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c6\\\"\\u003e\\u003cp\\u003e1.28\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;0.02\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c7\\\"\\u003e\\u003cp\\u003e0.9993\\u003c/p\\u003e\\u003c/td\\u003e\\u003c/tr\\u003e\\u003ctr\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e\\u003cp\\u003e130\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c2\\\"\\u003e\\u003cp\\u003e43\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;6\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c3\\\"\\u003e\\u003cp\\u003e1.30\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;0.02\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c4\\\"\\u003e\\u003cp\\u003e0.9981\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c5\\\"\\u003e\\u003cp\\u003e65\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;7\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c6\\\"\\u003e\\u003cp\\u003e1.23\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;0.02\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c7\\\"\\u003e\\u003cp\\u003e0.9982\\u003c/p\\u003e\\u003c/td\\u003e\\u003c/tr\\u003e\\u003ctr\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e\\u003cp\\u003e140\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c2\\\"\\u003e\\u003cp\\u003e51\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;6\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c3\\\"\\u003e\\u003cp\\u003e1.23\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;0.02\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c4\\\"\\u003e\\u003cp\\u003e0.9987\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c5\\\"\\u003e\\u003cp\\u003e69\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;6\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c6\\\"\\u003e\\u003cp\\u003e1.18\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;0.01\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c7\\\"\\u003e\\u003cp\\u003e0.9993\\u003c/p\\u003e\\u003c/td\\u003e\\u003c/tr\\u003e\\u003ctr\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e\\u003cp\\u003e150\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c2\\\"\\u003e\\u003cp\\u003e59\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;5\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c3\\\"\\u003e\\u003cp\\u003e1.16\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;0.01\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c4\\\"\\u003e\\u003cp\\u003e0.9992\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c5\\\"\\u003e\\u003cp\\u003e79\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;4\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c6\\\"\\u003e\\u003cp\\u003e1.11\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;0.01\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c7\\\"\\u003e\\u003cp\\u003e0.9998\\u003c/p\\u003e\\u003c/td\\u003e\\u003c/tr\\u003e\\u003c/tbody\\u003e\\u003c/colgroup\\u003e\\u003c/table\\u003e\\u003c/div\\u003e\\u003c/p\\u003e\\u003cp\\u003e\\u003cdiv class=\\\"gridtable\\\"\\u003e\\u003ctable float=\\\"Yes\\\" id=\\\"Tab3\\\" border=\\\"1\\\"\\u003e\\u003ccaption language=\\\"En\\\"\\u003e\\u003cdiv class=\\\"CaptionNumber\\\"\\u003eTable 3\\u003c/div\\u003e\\u003cdiv class=\\\"CaptionContent\\\"\\u003e\\u003cp\\u003eP-values for pairs of points of α-pinene vapors adsorption at 110\\u0026deg;C (α\\u0026thinsp;=\\u0026thinsp;0.05, n\\u0026thinsp;=\\u0026thinsp;5, first measurement)\\u003c/p\\u003e\\u003c/div\\u003e\\u003c/caption\\u003e\\u003ccolgroup cols=\\\"6\\\"\\u003e\\u003cdiv align=\\\"left\\\" class=\\\"colspec\\\" colname=\\\"c1\\\" colnum=\\\"1\\\"\\u003e\\u003c/div\\u003e\\u003cdiv align=\\\"char\\\" char=\\\".\\\" class=\\\"colspec\\\" colname=\\\"c2\\\" colnum=\\\"2\\\"\\u003e\\u003c/div\\u003e\\u003cdiv align=\\\"char\\\" char=\\\".\\\" class=\\\"colspec\\\" colname=\\\"c3\\\" colnum=\\\"3\\\"\\u003e\\u003c/div\\u003e\\u003cdiv align=\\\"char\\\" char=\\\".\\\" class=\\\"colspec\\\" colname=\\\"c4\\\" colnum=\\\"4\\\"\\u003e\\u003c/div\\u003e\\u003cdiv align=\\\"char\\\" char=\\\".\\\" class=\\\"colspec\\\" colname=\\\"c5\\\" colnum=\\\"5\\\"\\u003e\\u003c/div\\u003e\\u003cdiv align=\\\"char\\\" char=\\\".\\\" class=\\\"colspec\\\" colname=\\\"c6\\\" colnum=\\\"6\\\"\\u003e\\u003c/div\\u003e\\u003cthead\\u003e\\u003ctr\\u003e\\u003cth align=\\\"left\\\" colname=\\\"c1\\\"\\u003e\\u003cp\\u003eР, Pa\\u003c/p\\u003e\\u003c/th\\u003e\\u003cth align=\\\"left\\\" colname=\\\"c2\\\"\\u003e\\u003cp\\u003eр\\u003c/p\\u003e\\u003c/th\\u003e\\u003cth align=\\\"left\\\" colname=\\\"c3\\\"\\u003e\\u003cp\\u003eР, Pa\\u003c/p\\u003e\\u003c/th\\u003e\\u003cth align=\\\"left\\\" colname=\\\"c4\\\"\\u003e\\u003cp\\u003eр\\u003c/p\\u003e\\u003c/th\\u003e\\u003cth align=\\\"left\\\" colname=\\\"c5\\\"\\u003e\\u003cp\\u003eР, Pa\\u003c/p\\u003e\\u003c/th\\u003e\\u003cth align=\\\"left\\\" colname=\\\"c6\\\"\\u003e\\u003cp\\u003eР\\u003c/p\\u003e\\u003c/th\\u003e\\u003c/tr\\u003e\\u003c/thead\\u003e\\u003ctbody\\u003e\\u003ctr\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e\\u003cp\\u003e64\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c2\\\"\\u003e\\u003cp\\u003e0.0451\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c3\\\"\\u003e\\u003cp\\u003e154\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c4\\\"\\u003e\\u003cp\\u003e0.23\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c5\\\"\\u003e\\u003cp\\u003e218\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c6\\\"\\u003e\\u003cp\\u003e0.057\\u003c/p\\u003e\\u003c/td\\u003e\\u003c/tr\\u003e\\u003ctr\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e\\u003cp\\u003e281\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c2\\\"\\u003e\\u003cp\\u003e0.0227\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c3\\\"\\u003e\\u003cp\\u003e371\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c4\\\"\\u003e\\u003cp\\u003e0.0296\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c5\\\"\\u003e\\u003cp\\u003e435\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c6\\\"\\u003e\\u003cp\\u003e0.0122\\u003c/p\\u003e\\u003c/td\\u003e\\u003c/tr\\u003e\\u003ctr\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e\\u003cp\\u003e499\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c2\\\"\\u003e\\u003cp\\u003e0.0058\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c3\\\"\\u003e\\u003cp\\u003e589\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c4\\\"\\u003e\\u003cp\\u003e0.0045\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c5\\\"\\u003e\\u003cp\\u003e653\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c6\\\"\\u003e\\u003cp\\u003e0.0028\\u003c/p\\u003e\\u003c/td\\u003e\\u003c/tr\\u003e\\u003c/tbody\\u003e\\u003c/colgroup\\u003e\\u003c/table\\u003e\\u003c/div\\u003e\\u003c/p\\u003e\\u003cp\\u003eThis phenomenon has been previously reported by our group for both non-porous and porous chiral crystals [\\u003cspan citationid=\\\"CR45\\\" class=\\\"CitationRef\\\"\\u003e45\\u003c/span\\u003e, \\u003cspan citationid=\\\"CR46\\\" class=\\\"CitationRef\\\"\\u003e46\\u003c/span\\u003e]. At 120\\u0026deg;C, the adsorption isotherms of α-pinene enantiomers differed at all partial pressures, whereas at 130\\u0026deg;C, the adsorption values coincided. The decrease of chiral recognition at higher temperatures can be attributed to the proximity to α-pinene\\u0026rsquo;s boiling point. A surface with supramolecular chirality cannot recognize enantiomers in the gaseous state\\u003c/p\\u003e\\u003cp\\u003e\\u003cdiv class=\\\"gridtable\\\"\\u003e\\u003ctable float=\\\"Yes\\\" id=\\\"Tab4\\\" border=\\\"1\\\"\\u003e\\u003ccaption language=\\\"En\\\"\\u003e\\u003cdiv class=\\\"CaptionNumber\\\"\\u003eTable 4\\u003c/div\\u003e\\u003cdiv class=\\\"CaptionContent\\\"\\u003e\\u003cp\\u003eP-values for pairs of points of α-pinene vapors adsorption at 110\\u0026deg;C (α\\u0026thinsp;=\\u0026thinsp;0.05, n\\u0026thinsp;=\\u0026thinsp;5, second and any further measurements)\\u003c/p\\u003e\\u003c/div\\u003e\\u003c/caption\\u003e\\u003ccolgroup cols=\\\"6\\\"\\u003e\\u003cdiv align=\\\"left\\\" class=\\\"colspec\\\" colname=\\\"c1\\\" colnum=\\\"1\\\"\\u003e\\u003c/div\\u003e\\u003cdiv align=\\\"char\\\" char=\\\".\\\" class=\\\"colspec\\\" colname=\\\"c2\\\" colnum=\\\"2\\\"\\u003e\\u003c/div\\u003e\\u003cdiv align=\\\"char\\\" char=\\\".\\\" class=\\\"colspec\\\" colname=\\\"c3\\\" colnum=\\\"3\\\"\\u003e\\u003c/div\\u003e\\u003cdiv align=\\\"char\\\" char=\\\".\\\" class=\\\"colspec\\\" colname=\\\"c4\\\" colnum=\\\"4\\\"\\u003e\\u003c/div\\u003e\\u003cdiv align=\\\"char\\\" char=\\\".\\\" class=\\\"colspec\\\" colname=\\\"c5\\\" colnum=\\\"5\\\"\\u003e\\u003c/div\\u003e\\u003cdiv align=\\\"char\\\" char=\\\".\\\" class=\\\"colspec\\\" colname=\\\"c6\\\" colnum=\\\"6\\\"\\u003e\\u003c/div\\u003e\\u003cthead\\u003e\\u003ctr\\u003e\\u003cth align=\\\"left\\\" colname=\\\"c1\\\"\\u003e\\u003cp\\u003eР, Pa\\u003c/p\\u003e\\u003c/th\\u003e\\u003cth align=\\\"left\\\" colname=\\\"c2\\\"\\u003e\\u003cp\\u003eр\\u003c/p\\u003e\\u003c/th\\u003e\\u003cth align=\\\"left\\\" colname=\\\"c3\\\"\\u003e\\u003cp\\u003eР,kPa\\u003c/p\\u003e\\u003c/th\\u003e\\u003cth align=\\\"left\\\" colname=\\\"c4\\\"\\u003e\\u003cp\\u003eр\\u003c/p\\u003e\\u003c/th\\u003e\\u003cth align=\\\"left\\\" colname=\\\"c5\\\"\\u003e\\u003cp\\u003eР, Pa\\u003c/p\\u003e\\u003c/th\\u003e\\u003cth align=\\\"left\\\" colname=\\\"c6\\\"\\u003e\\u003cp\\u003eр\\u003c/p\\u003e\\u003c/th\\u003e\\u003c/tr\\u003e\\u003c/thead\\u003e\\u003ctbody\\u003e\\u003ctr\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e\\u003cp\\u003e108\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c2\\\"\\u003e\\u003cp\\u003e0.00001\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c3\\\"\\u003e\\u003cp\\u003e328\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c4\\\"\\u003e\\u003cp\\u003e0.00001\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c5\\\"\\u003e\\u003cp\\u003e392\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c6\\\"\\u003e\\u003cp\\u003e0.00004\\u003c/p\\u003e\\u003c/td\\u003e\\u003c/tr\\u003e\\u003ctr\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e\\u003cp\\u003e431\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c2\\\"\\u003e\\u003cp\\u003e0.0001\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c3\\\"\\u003e\\u003cp\\u003e504\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c4\\\"\\u003e\\u003cp\\u003e0.0001\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c5\\\"\\u003e\\u003cp\\u003e537\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c6\\\"\\u003e\\u003cp\\u003e0.0001\\u003c/p\\u003e\\u003c/td\\u003e\\u003c/tr\\u003e\\u003ctr\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e\\u003cp\\u003e574\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c2\\\"\\u003e\\u003cp\\u003e0.0003\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c3\\\"\\u003e\\u003cp\\u003e593\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c4\\\"\\u003e\\u003cp\\u003e0.0003\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c5\\\"\\u003e\\u003cp\\u003e610\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c6\\\"\\u003e\\u003cp\\u003e0.0005\\u003c/p\\u003e\\u003c/td\\u003e\\u003c/tr\\u003e\\u003c/tbody\\u003e\\u003c/colgroup\\u003e\\u003c/table\\u003e\\u003c/div\\u003e\\u003c/p\\u003e\\u003cp\\u003e\\u003cdiv class=\\\"gridtable\\\"\\u003e\\u003ctable float=\\\"Yes\\\" id=\\\"Tab5\\\" border=\\\"1\\\"\\u003e\\u003ccaption language=\\\"En\\\"\\u003e\\u003cdiv class=\\\"CaptionNumber\\\"\\u003eTable 5\\u003c/div\\u003e\\u003cdiv class=\\\"CaptionContent\\\"\\u003e\\u003cp\\u003eApproximation parameters of α-pinenes adsorption isotherms by the Freundlich equation\\u003c/p\\u003e\\u003c/div\\u003e\\u003c/caption\\u003e\\u003ccolgroup cols=\\\"7\\\"\\u003e\\u003cdiv align=\\\"left\\\" class=\\\"colspec\\\" colname=\\\"c1\\\" colnum=\\\"1\\\"\\u003e\\u003c/div\\u003e\\u003cdiv align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" class=\\\"colspec\\\" colname=\\\"c2\\\" colnum=\\\"2\\\"\\u003e\\u003c/div\\u003e\\u003cdiv align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" class=\\\"colspec\\\" colname=\\\"c3\\\" colnum=\\\"3\\\"\\u003e\\u003c/div\\u003e\\u003cdiv align=\\\"char\\\" char=\\\".\\\" class=\\\"colspec\\\" colname=\\\"c4\\\" colnum=\\\"4\\\"\\u003e\\u003c/div\\u003e\\u003cdiv align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" class=\\\"colspec\\\" colname=\\\"c5\\\" colnum=\\\"5\\\"\\u003e\\u003c/div\\u003e\\u003cdiv align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" class=\\\"colspec\\\" colname=\\\"c6\\\" colnum=\\\"6\\\"\\u003e\\u003c/div\\u003e\\u003cdiv align=\\\"char\\\" char=\\\".\\\" class=\\\"colspec\\\" colname=\\\"c7\\\" colnum=\\\"7\\\"\\u003e\\u003c/div\\u003e\\u003cthead\\u003e\\u003ctr\\u003e\\u003cth align=\\\"left\\\" colname=\\\"c1\\\" morerows=\\\"1\\\" rowspan=\\\"2\\\"\\u003e\\u003cp\\u003eT\\u003c/p\\u003e\\u003c/th\\u003e\\u003cth align=\\\"left\\\" colspan=\\\"3\\\" nameend=\\\"c4\\\" namest=\\\"c2\\\"\\u003e\\u003cp\\u003e(-)-α-pinene\\u003c/p\\u003e\\u003c/th\\u003e\\u003cth align=\\\"left\\\" colspan=\\\"3\\\" nameend=\\\"c7\\\" namest=\\\"c5\\\"\\u003e\\u003cp\\u003e(+)-α- pinene\\u003c/p\\u003e\\u003c/th\\u003e\\u003c/tr\\u003e\\u003ctr\\u003e\\u003cth align=\\\"left\\\" colname=\\\"c2\\\"\\u003e\\u003cp\\u003eK\\u003csub\\u003ef\\u003c/sub\\u003e\\u0026middot;10\\u003csup\\u003e4\\u003c/sup\\u003e\\u003c/p\\u003e\\u003c/th\\u003e\\u003cth align=\\\"left\\\" colname=\\\"c3\\\"\\u003e\\u003cp\\u003en\\u003c/p\\u003e\\u003c/th\\u003e\\u003cth align=\\\"left\\\" colname=\\\"c4\\\"\\u003e\\u003cp\\u003eR\\u003c/p\\u003e\\u003c/th\\u003e\\u003cth align=\\\"left\\\" colname=\\\"c5\\\"\\u003e\\u003cp\\u003eK\\u003csub\\u003ef\\u003c/sub\\u003e\\u0026middot;10\\u003csup\\u003e4\\u003c/sup\\u003e\\u003c/p\\u003e\\u003c/th\\u003e\\u003cth align=\\\"left\\\" colname=\\\"c6\\\"\\u003e\\u003cp\\u003en\\u003c/p\\u003e\\u003c/th\\u003e\\u003cth align=\\\"left\\\" colname=\\\"c7\\\"\\u003e\\u003cp\\u003eR\\u003c/p\\u003e\\u003c/th\\u003e\\u003c/tr\\u003e\\u003c/thead\\u003e\\u003ctbody\\u003e\\u003ctr\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e\\u003cp\\u003e90\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c2\\\"\\u003e\\u003cp\\u003e272\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;2\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c3\\\"\\u003e\\u003cp\\u003e1.10\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;0.01\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c4\\\"\\u003e\\u003cp\\u003e0.9999\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c5\\\"\\u003e\\u003cp\\u003e220\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;10\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c6\\\"\\u003e\\u003cp\\u003e1.15\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;0.01\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c7\\\"\\u003e\\u003cp\\u003e0.9996\\u003c/p\\u003e\\u003c/td\\u003e\\u003c/tr\\u003e\\u003ctr\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e\\u003cp\\u003e100\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c2\\\"\\u003e\\u003cp\\u003e243\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;5\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c3\\\"\\u003e\\u003cp\\u003e1.07\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;0.01\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c4\\\"\\u003e\\u003cp\\u003e0.9999\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c5\\\"\\u003e\\u003cp\\u003e180\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;8\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c6\\\"\\u003e\\u003cp\\u003e1.14\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;0.01\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c7\\\"\\u003e\\u003cp\\u003e0.9997\\u003c/p\\u003e\\u003c/td\\u003e\\u003c/tr\\u003e\\u003ctr\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e\\u003cp\\u003e110\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c2\\\"\\u003e\\u003cp\\u003e189\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;4\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c3\\\"\\u003e\\u003cp\\u003e1.06\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;0.01\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c4\\\"\\u003e\\u003cp\\u003e0.9999\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c5\\\"\\u003e\\u003cp\\u003e136\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;6\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c6\\\"\\u003e\\u003cp\\u003e1.13\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;0.01\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c7\\\"\\u003e\\u003cp\\u003e0.9998\\u003c/p\\u003e\\u003c/td\\u003e\\u003c/tr\\u003e\\u003c/tbody\\u003e\\u003c/colgroup\\u003e\\u003c/table\\u003e\\u003c/div\\u003e\\u003c/p\\u003e\\u003cp\\u003e\\u003cdiv class=\\\"gridtable\\\"\\u003e\\u003ctable float=\\\"Yes\\\" id=\\\"Tab6\\\" border=\\\"1\\\"\\u003e\\u003ccaption language=\\\"En\\\"\\u003e\\u003cdiv class=\\\"CaptionNumber\\\"\\u003eTable 6\\u003c/div\\u003e\\u003cdiv class=\\\"CaptionContent\\\"\\u003e\\u003cp\\u003eApproximation parameters of α-pinenes adsorption isotherms by the Langmuir equation\\u003c/p\\u003e\\u003c/div\\u003e\\u003c/caption\\u003e\\u003ccolgroup cols=\\\"7\\\"\\u003e\\u003cdiv align=\\\"left\\\" class=\\\"colspec\\\" colname=\\\"c1\\\" colnum=\\\"1\\\"\\u003e\\u003c/div\\u003e\\u003cdiv align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" class=\\\"colspec\\\" colname=\\\"c2\\\" colnum=\\\"2\\\"\\u003e\\u003c/div\\u003e\\u003cdiv align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" class=\\\"colspec\\\" colname=\\\"c3\\\" colnum=\\\"3\\\"\\u003e\\u003c/div\\u003e\\u003cdiv align=\\\"char\\\" char=\\\".\\\" class=\\\"colspec\\\" colname=\\\"c4\\\" colnum=\\\"4\\\"\\u003e\\u003c/div\\u003e\\u003cdiv align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" class=\\\"colspec\\\" colname=\\\"c5\\\" colnum=\\\"5\\\"\\u003e\\u003c/div\\u003e\\u003cdiv align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" class=\\\"colspec\\\" colname=\\\"c6\\\" colnum=\\\"6\\\"\\u003e\\u003c/div\\u003e\\u003cdiv align=\\\"char\\\" char=\\\".\\\" class=\\\"colspec\\\" colname=\\\"c7\\\" colnum=\\\"7\\\"\\u003e\\u003c/div\\u003e\\u003cthead\\u003e\\u003ctr\\u003e\\u003cth align=\\\"left\\\" colname=\\\"c1\\\" morerows=\\\"1\\\" rowspan=\\\"2\\\"\\u003e\\u003cp\\u003eT\\u003c/p\\u003e\\u003c/th\\u003e\\u003cth align=\\\"left\\\" colspan=\\\"3\\\" nameend=\\\"c4\\\" namest=\\\"c2\\\"\\u003e\\u003cp\\u003e(-)-α-pinene\\u003c/p\\u003e\\u003c/th\\u003e\\u003cth align=\\\"left\\\" colspan=\\\"3\\\" nameend=\\\"c7\\\" namest=\\\"c5\\\"\\u003e\\u003cp\\u003e(+)-α- pinene\\u003c/p\\u003e\\u003c/th\\u003e\\u003c/tr\\u003e\\u003ctr\\u003e\\u003cth align=\\\"left\\\" colname=\\\"c2\\\"\\u003e\\u003cp\\u003eK\\u003csub\\u003eL\\u003c/sub\\u003e\\u0026middot;10\\u003csup\\u003e2\\u003c/sup\\u003e\\u003c/p\\u003e\\u003c/th\\u003e\\u003cth align=\\\"left\\\" colname=\\\"c3\\\"\\u003e\\u003cp\\u003ea\\u003csub\\u003em\\u003c/sub\\u003e\\u003c/p\\u003e\\u003c/th\\u003e\\u003cth align=\\\"left\\\" colname=\\\"c4\\\"\\u003e\\u003cp\\u003eR\\u003c/p\\u003e\\u003c/th\\u003e\\u003cth align=\\\"left\\\" colname=\\\"c5\\\"\\u003e\\u003cp\\u003eK\\u003csub\\u003eL\\u003c/sub\\u003e\\u0026middot;10\\u003csup\\u003e2\\u003c/sup\\u003e\\u003c/p\\u003e\\u003c/th\\u003e\\u003cth align=\\\"left\\\" colname=\\\"c6\\\"\\u003e\\u003cp\\u003ea\\u003csub\\u003em\\u003c/sub\\u003e\\u003c/p\\u003e\\u003c/th\\u003e\\u003cth align=\\\"left\\\" colname=\\\"c7\\\"\\u003e\\u003cp\\u003eR\\u003c/p\\u003e\\u003c/th\\u003e\\u003c/tr\\u003e\\u003c/thead\\u003e\\u003ctbody\\u003e\\u003ctr\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e\\u003cp\\u003e90\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c2\\\"\\u003e\\u003cp\\u003e64\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;2\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c3\\\"\\u003e\\u003cp\\u003e34\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;3\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c4\\\"\\u003e\\u003cp\\u003e0.9996\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c5\\\"\\u003e\\u003cp\\u003e57\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;2\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c6\\\"\\u003e\\u003cp\\u003e39\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;3\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c7\\\"\\u003e\\u003cp\\u003e0.9995\\u003c/p\\u003e\\u003c/td\\u003e\\u003c/tr\\u003e\\u003ctr\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e\\u003cp\\u003e110\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c2\\\"\\u003e\\u003cp\\u003e11\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;1\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c3\\\"\\u003e\\u003cp\\u003e35\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;3\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c4\\\"\\u003e\\u003cp\\u003e0.9998\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c5\\\"\\u003e\\u003cp\\u003e11\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;1\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c6\\\"\\u003e\\u003cp\\u003e38\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;3\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c7\\\"\\u003e\\u003cp\\u003e0.9996\\u003c/p\\u003e\\u003c/td\\u003e\\u003c/tr\\u003e\\u003ctr\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e\\u003cp\\u003e120\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c2\\\"\\u003e\\u003cp\\u003e2.3\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;0.5\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c3\\\"\\u003e\\u003cp\\u003e42\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;6\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c4\\\"\\u003e\\u003cp\\u003e0.9822\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c5\\\"\\u003e\\u003cp\\u003e0.19\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;0.02\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c6\\\"\\u003e\\u003cp\\u003e49\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;5\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c7\\\"\\u003e\\u003cp\\u003e0.9901\\u003c/p\\u003e\\u003c/td\\u003e\\u003c/tr\\u003e\\u003ctr\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e\\u003cp\\u003e130\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c2\\\"\\u003e\\u003cp\\u003e0.17\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;0.02\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c3\\\"\\u003e\\u003cp\\u003e108\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;9\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c4\\\"\\u003e\\u003cp\\u003e0.9955\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c5\\\"\\u003e\\u003cp\\u003e0.17\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;0.02\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\"\\u0026plusmn;\\\" colname=\\\"c6\\\"\\u003e\\u003cp\\u003e112\\u0026thinsp;\\u0026plusmn;\\u0026thinsp;9\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"char\\\" char=\\\".\\\" colname=\\\"c7\\\"\\u003e\\u003cp\\u003e0.9961\\u003c/p\\u003e\\u003c/td\\u003e\\u003c/tr\\u003e\\u003c/tbody\\u003e\\u003c/colgroup\\u003e\\u003c/table\\u003e\\u003c/div\\u003e\\u003c/p\\u003e\\u003cp\\u003ebecause the adsorbed layer behaves as a two-dimensional van der Waals gas, lacking short- or long-range order [\\u003cspan citationid=\\\"CR56\\\" class=\\\"CitationRef\\\"\\u003e56\\u003c/span\\u003e].Comparison of limonene and α-pinene isotherms reveals that for limonenes, chiral recognition persisted even at 150\\u0026deg;C (27\\u0026deg;C below their boiling point), particularly at high partial pressures. In contrast, for α-pinenes at 130\\u0026deg;C (25\\u0026deg;C below boiling), no chiral recognition was observed. This suggests that the adsorption layer of the bulkier α-pinene molecule is less stable than that of limonene.\\u003c/p\\u003e\\u003cp\\u003eAdsorption isotherms at 90\\u0026ndash;110\\u0026deg;C from subsequent measurements were approximated using the Freundlich equation (Table\\u0026nbsp;\\u003cspan refid=\\\"Tab5\\\" class=\\\"InternalRef\\\"\\u003e5\\u003c/span\\u003e). The approximation quality was high (R\\u0026thinsp;\\u0026ge;\\u0026thinsp;0.9996), and adsorption constants differed at all temperatures, decreasing with temperature for both enantiomers. For BET type I isotherms (90\\u0026ndash;130\\u0026deg;C), R values were also high. The monolayer capacity (\\u003cem\\u003ea\\u003c/em\\u003e\\u003csub\\u003e\\u003cem\\u003em\\u003c/em\\u003e\\u003c/sub\\u003e) remained constant at 90 and 110\\u0026deg;C but increased at higher temperatures (Table\\u0026nbsp;\\u003cspan refid=\\\"Tab6\\\" class=\\\"InternalRef\\\"\\u003e6\\u003c/span\\u003e). At all temperatures, \\u003cem\\u003ea\\u003c/em\\u003e\\u003csub\\u003e\\u003cem\\u003em\\u003c/em\\u003e\\u003c/sub\\u003e values for both enantiomers\\u003c/p\\u003e\\u003cp\\u003e\\u003cdiv class=\\\"gridtable\\\"\\u003e\\u003ctable float=\\\"Yes\\\" id=\\\"Tab7\\\" border=\\\"1\\\"\\u003e\\u003ccaption language=\\\"En\\\"\\u003e\\u003cdiv class=\\\"CaptionNumber\\\"\\u003eTable 7\\u003c/div\\u003e\\u003cdiv class=\\\"CaptionContent\\\"\\u003e\\u003cp\\u003eEnantioselectivity coefficients for limonenes and α-pinenes\\u003c/p\\u003e\\u003c/div\\u003e\\u003c/caption\\u003e\\u003ccolgroup cols=\\\"3\\\"\\u003e\\u003cdiv align=\\\"left\\\" class=\\\"colspec\\\" colname=\\\"c1\\\" colnum=\\\"1\\\"\\u003e\\u003c/div\\u003e\\u003cdiv align=\\\"left\\\" class=\\\"colspec\\\" colname=\\\"c2\\\" colnum=\\\"2\\\"\\u003e\\u003c/div\\u003e\\u003cdiv align=\\\"left\\\" class=\\\"colspec\\\" colname=\\\"c3\\\" colnum=\\\"3\\\"\\u003e\\u003c/div\\u003e\\u003cthead\\u003e\\u003ctr\\u003e\\u003cth align=\\\"left\\\" colname=\\\"c1\\\" morerows=\\\"1\\\" rowspan=\\\"2\\\"\\u003e\\u003cp\\u003eT\\u003c/p\\u003e\\u003c/th\\u003e\\u003cth align=\\\"left\\\" colspan=\\\"2\\\" nameend=\\\"c3\\\" namest=\\\"c2\\\"\\u003e\\u003cp\\u003eα\\u003c/p\\u003e\\u003c/th\\u003e\\u003c/tr\\u003e\\u003ctr\\u003e\\u003cth align=\\\"left\\\" colname=\\\"c2\\\"\\u003e\\u003cp\\u003elimonenes\\u003c/p\\u003e\\u003c/th\\u003e\\u003cth align=\\\"left\\\" colname=\\\"c3\\\"\\u003e\\u003cp\\u003eα-pinenes\\u003c/p\\u003e\\u003c/th\\u003e\\u003c/tr\\u003e\\u003c/thead\\u003e\\u003ctbody\\u003e\\u003ctr\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e\\u003cp\\u003e90\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e\\u003cp\\u003e-\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e\\u003cp\\u003e1.12\\u003c/p\\u003e\\u003c/td\\u003e\\u003c/tr\\u003e\\u003ctr\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e\\u003cp\\u003e100\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e\\u003cp\\u003e-\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e\\u003cp\\u003e1.09\\u003c/p\\u003e\\u003c/td\\u003e\\u003c/tr\\u003e\\u003ctr\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e\\u003cp\\u003e110\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e\\u003cp\\u003e1.06\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e\\u003cp\\u003e1.15\\u003c/p\\u003e\\u003c/td\\u003e\\u003c/tr\\u003e\\u003ctr\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e\\u003cp\\u003e120\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e\\u003cp\\u003e-\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e\\u003cp\\u003e1.06\\u003c/p\\u003e\\u003c/td\\u003e\\u003c/tr\\u003e\\u003ctr\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e\\u003cp\\u003e130\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e\\u003cp\\u003e1.07\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e\\u003cp\\u003e1.00\\u003c/p\\u003e\\u003c/td\\u003e\\u003c/tr\\u003e\\u003ctr\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e\\u003cp\\u003e140\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e\\u003cp\\u003e1.05\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e\\u003cp\\u003e-\\u003c/p\\u003e\\u003c/td\\u003e\\u003c/tr\\u003e\\u003ctr\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e\\u003cp\\u003e150\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e\\u003cp\\u003e1.07\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e\\u003cp\\u003e-\\u003c/p\\u003e\\u003c/td\\u003e\\u003c/tr\\u003e\\u003ctr\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c1\\\"\\u003e\\u003cp\\u003e160\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c2\\\"\\u003e\\u003cp\\u003e1.05\\u003c/p\\u003e\\u003c/td\\u003e\\u003ctd align=\\\"left\\\" colname=\\\"c3\\\"\\u003e\\u003cp\\u003e-\\u003c/p\\u003e\\u003c/td\\u003e\\u003c/tr\\u003e\\u003c/tbody\\u003e\\u003c/colgroup\\u003e\\u003c/table\\u003e\\u003c/div\\u003e\\u003c/p\\u003e\\u003cp\\u003ecoincided, as expected. However, Langmuir constants at 90 and 120\\u0026deg;C were not equal, supporting the conclusion of enantioselectivity.\\u003c/p\\u003e\\u003c/p\\u003e\\u003cp\\u003eWhen comparing enantioselectivity of limonenes and α-pinenes, α-pinenes exhibited a maximum α of 1.15 at 110\\u0026deg;C, whereas limonenes reached only 1.07 (Table\\u0026nbsp;\\u003cspan refid=\\\"Tab7\\\" class=\\\"InternalRef\\\"\\u003e7\\u003c/span\\u003e). Data at 130\\u0026deg;C could not be compared due to the loss of α-pinene enantioselectivity near its boiling point. The higher enantioselectivity for α-pinenes may result from a greater difference in the isosteric heats of adsorption (Q\\u003csub\\u003est\\u003c/sub\\u003e) between enantiomers (Fig.\\u0026nbsp;\\u003cspan refid=\\\"Fig7\\\" class=\\\"InternalRef\\\"\\u003e7\\u003c/span\\u003e). For limonenes, Q\\u003csub\\u003est\\u003c/sub\\u003e increased with adsorption, but the difference was notable only at low coverages. In contrast, for α-pinenes, Q\\u003csub\\u003est\\u003c/sub\\u003e exhibited a more pronounced divergence, suggesting a different adsorption mechanism.\\u003c/p\\u003e\\u003cp\\u003eFor limonene enantiomers, Q\\u003csub\\u003est\\u003c/sub\\u003e values at high coverages approached the heat of liquefaction (L), consistent with typical adsorption behavior. At coverages\\u0026thinsp;\\u0026gt;\\u0026thinsp;1, the second and further adsorption layers form, for which Q\\u003csub\\u003est\\u003c/sub\\u003e\\u0026asymp;L. A similar trend was observed for (\\u0026minus;)-α-pinene, but not for (+)-α-pinene, indicating that the latter did not form a complete monolayer. This difference in monolayer formation likely contributed to the additional enantioselectivity observed for α-pinenes.\\u003c/p\\u003e\"},{\"header\":\"4. Conclusion\",\"content\":\"\\u003cp\\u003eOn the SU-MB sample studied, differences in the adsorption of both limonene and α-pinene enantiomers were observed. The maximal enantioselectivity coefficient (α) was found to be 1.15. The reliability of enantioselectivity was confirmed by t-test results. This CMOF sample exhibited consistent enantioselectivity, which is unusual given the absence of asymmetric carbon atoms. The observed chirality was of supramolecular origin. In this sample, half of the cavities were occupied, and all of them exhibited the same handedness [\\u003cspan citationid=\\\"CR32\\\" class=\\\"CitationRef\\\"\\u003e32\\u003c/span\\u003e], leading to the emergence of supramolecular chirality. This CMOF is of particular interest because chirality was manifested solely through helical cavities, while the crystal as a whole remained achiral.\\u003c/p\\u003e\\u003cp\\u003eThese findings demonstrate that the presence of an asymmetric structural element, such as pore helicity, is sufficient for enantiomer recognition during adsorption. This expands the range of adsorbents that can be utilized for enantioselective adsorption processes.\\u003c/p\\u003e\"},{\"header\":\"Declarations\",\"content\":\"\\u003cp\\u003e\\u003cstrong\\u003eFunding\\u003c/strong\\u003e\\u003c/p\\u003e\\n\\u003cp\\u003eThis work was supported by the Russian Science Foundation (project No. 25-13-20076).\\u003c/p\\u003e\\n\\u003cp\\u003eThe authors have no competing interests to declare that are relevant to the content of this article.\\u003c/p\\u003e\\u003cp\\u003e\\u003cstrong\\u003eAcknowledgements\\u0026nbsp;\\u003c/strong\\u003e\\u003c/p\\u003e\\n\\u003cp\\u003eThis work was performed with the aid of equipment of the Shared Facility Center CKP FMI of the Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences.\\u003c/p\\u003e\"},{\"header\":\"References\",\"content\":\"\\u003col\\u003e\\n\\u003cli\\u003eR.T. Yang (2003) Adsorbents : fundamentals and applications. 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Schurig Journal of Chromatography A 906, 275 (2001)\\u003c/li\\u003e\\n\\u003cli\\u003eV. Yu.Gus\\u0026rsquo;kov, R.K. Shayakhmetova, D.A. Allayarova, Y.F. Sharafutdinova, E.L. Gilfanova, I. N.Pavlova, G.Z. Garipova Phys. Chem. Chem. Phys. 23, 11968 (2021)\\u003c/li\\u003e\\n\\u003c/ol\\u003e\"}],\"fulltextSource\":\"\",\"fullText\":\"\",\"funders\":[],\"hasAdminPriorityOnWorkflow\":false,\"hasManuscriptDocX\":true,\"hasOptedInToPreprint\":true,\"hasPassedJournalQc\":\"\",\"hasAnyPriority\":false,\"hideJournal\":false,\"highlight\":\"\",\"institution\":\"\",\"isAcceptedByJournal\":true,\"isAuthorSuppliedPdf\":false,\"isDeskRejected\":\"\",\"isHiddenFromSearch\":false,\"isInQc\":false,\"isInWorkflow\":false,\"isPdf\":false,\"isPdfUpToDate\":true,\"isWithdrawnOrRetracted\":false,\"journal\":{\"display\":true,\"email\":\"info@researchsquare.com\",\"identity\":\"adsorption\",\"isNatureJournal\":false,\"hasQc\":true,\"allowDirectSubmit\":false,\"externalIdentity\":\"adso\",\"sideBox\":\"Learn more about [Adsorption](http://link.springer.com/journal/10450)\",\"snPcode\":\"10450\",\"submissionUrl\":\"https://submission.nature.com/new-submission/10450/3\",\"title\":\"Adsorption\",\"twitterHandle\":\"\",\"acdcEnabled\":true,\"dfaEnabled\":true,\"editorialSystem\":\"em\",\"reportingPortfolio\":\"Springer Hybrid\",\"inReviewEnabled\":true,\"inReviewRevisionsEnabled\":false},\"keywords\":\"chiral metal-organic frameworks, helical pores, adsorption isotherms, enantioselectivity\",\"lastPublishedDoi\":\"10.21203/rs.3.rs-7470067/v1\",\"lastPublishedDoiUrl\":\"https://doi.org/10.21203/rs.3.rs-7470067/v1\",\"license\":{\"name\":\"CC BY 4.0\",\"url\":\"https://creativecommons.org/licenses/by/4.0/\"},\"manuscriptAbstract\":\"\\u003cp\\u003eChiral metal-organic frameworks (CMOFs) are promising materials for catalysis, chromatography, and sensor applications. Typically, chirality in such frameworks is achieved by using chiral ligands. However, there are rare examples of CMOFs that form without any chiral source, usually via spontaneous symmetry breaking, resulting in supramolecular chirality. Germanium oxide framework SU-MB exhibits a unique mechanism of chirality emergence: during synthesis, only micropores of one handedness are selectively filled. This paper investigates the adsorption of limonene and α-pinene enantiomers on SU-MB. The framework demonstrated consistent enantioselectivity for both pairs of enantiomers, with a higher selectivity coefficient observed for α-pinenes than for limonenes. This difference arises from distinct trends in the isosteric heats of adsorption (Q\\u003csub\\u003est\\u003c/sub\\u003e): for limonenes and (\\u0026minus;)-α-pinene, Q\\u003csub\\u003est\\u003c/sub\\u003e approaches the heat of liquefaction with increasing adsorption, whereas for (+)-α-pinene, Q\\u003csub\\u003est\\u003c/sub\\u003e remains unchanged. These findings show that even a non-chiral crystal without chiral centers can exhibit enantioselectivity in adsorption processes, because of helical pores of one handedness.\\u003c/p\\u003e\",\"manuscriptTitle\":\"Enantioselective adsorption of limonenes and α-pinenes on germanium oxide metal-organic framework\",\"msid\":\"\",\"msnumber\":\"\",\"nonDraftVersions\":[{\"code\":1,\"date\":\"2025-09-22 09:10:36\",\"doi\":\"10.21203/rs.3.rs-7470067/v1\",\"editorialEvents\":[{\"type\":\"communityComments\",\"content\":0},{\"type\":\"decision\",\"content\":\"Revision requested\",\"date\":\"2025-11-03T21:21:09+00:00\",\"index\":\"\",\"fulltext\":\"\"},{\"type\":\"editorInvitedReview\",\"content\":\"\",\"date\":\"2025-09-24T01:52:06+00:00\",\"index\":\"hide\",\"fulltext\":\"\"},{\"type\":\"editorInvitedReview\",\"content\":\"\",\"date\":\"2025-09-18T21:26:37+00:00\",\"index\":\"hide\",\"fulltext\":\"\"},{\"type\":\"reviewerAgreed\",\"content\":\"303244525380492792556307439386184031265\",\"date\":\"2025-09-15T01:39:50+00:00\",\"index\":\"hide\",\"fulltext\":\"\"},{\"type\":\"reviewerAgreed\",\"content\":\"146198391707444904473960537665385526248\",\"date\":\"2025-09-15T00:48:01+00:00\",\"index\":\"hide\",\"fulltext\":\"\"},{\"type\":\"reviewersInvited\",\"content\":\"\",\"date\":\"2025-09-15T00:19:25+00:00\",\"index\":\"\",\"fulltext\":\"\"},{\"type\":\"editorAssigned\",\"content\":\"\",\"date\":\"2025-08-29T05:06:23+00:00\",\"index\":\"\",\"fulltext\":\"\"},{\"type\":\"checksComplete\",\"content\":\"\",\"date\":\"2025-08-29T05:05:31+00:00\",\"index\":\"\",\"fulltext\":\"\"},{\"type\":\"submitted\",\"content\":\"Adsorption\",\"date\":\"2025-08-27T09:20:31+00:00\",\"index\":\"\",\"fulltext\":\"\"}],\"status\":\"published\",\"journal\":{\"display\":true,\"email\":\"info@researchsquare.com\",\"identity\":\"adsorption\",\"isNatureJournal\":false,\"hasQc\":true,\"allowDirectSubmit\":false,\"externalIdentity\":\"adso\",\"sideBox\":\"Learn more about [Adsorption](http://link.springer.com/journal/10450)\",\"snPcode\":\"10450\",\"submissionUrl\":\"https://submission.nature.com/new-submission/10450/3\",\"title\":\"Adsorption\",\"twitterHandle\":\"\",\"acdcEnabled\":true,\"dfaEnabled\":true,\"editorialSystem\":\"em\",\"reportingPortfolio\":\"Springer Hybrid\",\"inReviewEnabled\":true,\"inReviewRevisionsEnabled\":false}}],\"origin\":\"\",\"ownerIdentity\":\"8d485873-5859-44a2-95f6-03bd76576904\",\"owner\":[],\"postedDate\":\"September 22nd, 2025\",\"published\":true,\"recentEditorialEvents\":[],\"rejectedJournal\":[],\"revision\":\"\",\"amendment\":\"\",\"status\":\"published-in-journal\",\"subjectAreas\":[],\"tags\":[],\"updatedAt\":\"2026-02-23T16:09:46+00:00\",\"versionOfRecord\":{\"articleIdentity\":\"rs-7470067\",\"link\":\"https://doi.org/10.1007/s10450-026-00676-1\",\"journal\":{\"identity\":\"adsorption\",\"isVorOnly\":false,\"title\":\"Adsorption\"},\"publishedOn\":\"2026-02-20 15:58:01\",\"publishedOnDateReadable\":\"February 20th, 2026\"},\"versionCreatedAt\":\"2025-09-22 09:10:36\",\"video\":\"\",\"vorDoi\":\"10.1007/s10450-026-00676-1\",\"vorDoiUrl\":\"https://doi.org/10.1007/s10450-026-00676-1\",\"workflowStages\":[]},\"version\":\"v1\",\"identity\":\"rs-7470067\",\"journalConfig\":\"researchsquare\"},\"__N_SSP\":true},\"page\":\"/article/[identity]/[[...version]]\",\"query\":{\"redirect\":\"/article/rs-7470067\",\"identity\":\"rs-7470067\",\"version\":[\"v1\"]},\"buildId\":\"XKTyCvWXoU3ODBz1xrDgd\",\"isFallback\":false,\"isExperimentalCompile\":false,\"dynamicIds\":[84888],\"gssp\":true,\"scriptLoader\":[]}","source_license":"CC-BY-4.0","license_restricted":false}