One-Pot Synthesis of Nanovesicles via Surface-Initiated Polymerization-Induced Self-Assembly of Polychloroprene-Grafted Silica

One-Pot Synthesis of Nanovesicles via Surface-Initiated Polymerization-Induced Self-Assembly of Polychloroprene-Grafted Silica | 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 One-Pot Synthesis of Nanovesicles via Surface-Initiated Polymerization-Induced Self-Assembly of Polychloroprene-Grafted Silica Zaid M. Abbas, Fatma A. Khazaal, Ammar Ferman Abbood, Mohammad N. AL-Baiati This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-8861776/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract This study presents the first instance of polychloroprene-grafted inorganic nanoparticles self-assembling into single-walled vesicles by surface-initiated polymerization. Initially, a solvent-miscible brush was used to attach 15-nm silica nanoparticles. A second brush that was soluble in solvent was then polymerized to stimulate self-assembly. On-site self-assembly took place while the second brush was being surface-initiated polymerization. This method enables the production of nanovesicles at a comparatively high concentration of NPs and eliminates the need for post-polymerization processing. Additionally, this technique helped us better understand how the surface-grafted polymer controls NP vesicular assembly, enabling us to observe how well-dispersed NPs formed into nanovesicles. RAFT polymerization Nanocomposites Polychloroprene Self-assembly Surface-initiated polymerization Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Introduction Rubber, one of the most important biosynthesized polymers with exceptional chemical and physical properties, finds widespread application in various industries. 1 – 6 Medical equipment, including gloves, condoms, blood transfusion tubing, catheters, injector closures, and safety bags, has been made from rubber due to its remarkable elasticity, flexibility, resistance to viral penetration, superior formability, and biodegradability. 7–10 Like any other polymer, its macromolecular backbone contains unsaturated bonds, making it vulnerable to heat or oxidative deterioration, especially when it forms thin films. 11 – 13 Other significant problems with rubbery products include low tensile strength and poor tear resistance, particularly in applications such as condoms and medical gloves. Attempts have been made to strengthen dry rubber using silica, carbon black, and modified metal oxides. These conventional reinforcing materials, however, are not particularly effective in enhancing the finished structure. Therefore, finding innovative ways to enhance the mechanical properties and resistance to aging of rubber goods is crucial. 5 , 14 – 17 Polymer graft inorganic nanocomposites, an alternative to conventional-filled polymers or polymer blends, combine the benefits of polymers, such as flexibility, toughness, and ease of processing, with those of inorganic phases, including hardness, durability, and thermal stability. 18 – 20 This improvement in composite characteristics is particularly notable at modest loading levels of nanoparticle fillers, which do not significantly increase the compound's density or reduce light transmission. Recently, there has been considerable interest in incorporating inorganic nanofillers into rubber matrices to address the issues with nanocomposites. It was found that the organically modified nanocomposite, loaded with a respectable weight percent, exhibited substantial reinforcement on the rubber matrix due to the infusion of NP and the growth of the framework inside the matrix. The rubber matrix's three-dimensional network was also shown to improve its solvent and mechanical resistance significantly. 21 – 23 The exceptional reinforcing effectiveness of layered silicate rubber nanocomposites, even at low loading of layered silicates, is mainly due to the silicate platelets' high aspect ratio and nanoscale dispersion. The properties of rubber might be further improved by directly reinforcing it with fillers that have a larger specific surface area, such as spherical inorganic nanoparticles. This is likely because there is no reliable way to prevent nanoparticles from vigorously self-aggregating. Our previous work used a novel self-assembly nanocomposite approach to manufacture surface-initiated polymerization-induced self-assembly (SI-PISA). We found a straightforward and efficient way to induce inorganic NPs to self-assemble into single-layer nanovesicles via surface-initiated polymerization. The SI-PISA approach is a new use of PISA that guides the self-assembly of inorganic nanoparticles by forming polymer chains from NP surfaces. 24 , 25 One possible method for creating new, valuable materials is the capacity of inorganic nanoparticles to self-assemble into hierarchical structures. 24 – 30 Among all the self-assembled structures (strings, tubes, spheres, vesicles, etc.), nanovesicles are especially significant due to their hollow topologies, which enable uses in cancer treatment, drug delivery, catalysis, and bioimaging. 31 – 33 Recent studies have shown that inorganic NPs were coated with polymers or amphiphilic ligands to create these vesicles. 24 , 25 , 30 , 34 – 37 Thin-layer vesicles for polymer-directed self-assembly have been successfully constructed using block copolymer tethered NPs and mixed brush-grafted NPs. 38 , 39 Typically, each component's polymer-grafted NPs were made using an appropriate solvent, and any free polymers were eliminated using purification methods. 40 The self-assembly process commenced with adding a specific solvent or through film rehydration, necessitating several sample preparation steps and constrained by low nanoparticle concentration. 41 , 42 Previous research employed solvent switching to examine the impact of concentration on the self-assembly of PEG-b-PCL tethered gold nanoparticles. 24 , 25 , 43 When particle concentrations exceeded 250 µg/ml, they found that giant nanoscale vesicles that could form were massive submicron-sized assemblies. 44 The consistent dispersion of silica nanoparticles and the robust interactions between silica and polymer matrixes are primarily responsible for the improved characteristics. We recently synthesized rubber/SiO2 nanocomposites using this self-assembly approach and provided a brief report on their preparation and thermal characteristics. This work will methodically cover the self-assembly mechanism of silica nanoparticles and polychloroprene. Additionally, the shape of the nanocomposite and the microstructure of silica nanoclusters will be seen using DLS and TEM, and the effects of particles will be examined. Materials 3,4-Dichloro-1-butene (TCI America) was dehydrochlorinated to yield chloroprene monomer following a standard procedure. The chain transfer agent (CTA), 2-Methyl-2-[(dodecylsulfanylthiocarbonyl) sulfanyl]propanoic acid (MDSS, 97%), was obtained from Strem Chemicals and used as received. Spherical silica nanoparticles (SiO₂, MT–ST, 10–15 nm diameter) were purchased from Nissan Chemical Co. Aminopropyldimethylethoxysilane (APS, 95%) was supplied by Gelest and used without further purification. 2,2'-Azobisisobutyronitrile (AIBN) was acquired from Fisher, recrystallized from methanol, and dissolved in tetrahydrofuran (THF) to prepare a 10 mM stock solution. HPLC-grade THF, methanol, and hexanes were used as received. Characterization Techniques Fourier-transform infrared (FTIR) spectra were acquired using a Richmond Scientific FTIR Spectrophotometer to confirm the chemical modifications at each stage of the synthesis. Spectra were collected in the range of 4000 to 400 cm⁻¹ with a resolution of 4 cm⁻¹ and were averaged over 32 scans to ensure a high signal-to-noise ratio. Samples were analyzed as solid films deposited on the crystal surface of a single-reflection Diamond ATR (Attenuated Total Reflectance) accessory. This method allowed for the direct analysis of the functionalized nanoparticles without the need for KBr pellet preparation. Nuclear Magnetic Resonance (NMR) spectroscopy was conducted on a Bruker Avance III HD 400 MHz spectrometer. Samples were dissolved in deuterated chloroform (CDCl₃) with tetramethylsilane (TMS) as an internal standard. Gel Permeation Chromatography (GPC) was used to determine the molecular weight and dispersity (Ð) of the cleaved polymers against polystyrene standards. Dynamic Light Scattering (DLS) and Zeta Potential measurements were performed on a Malvern Zetasizer Nano ZS to monitor nanoparticle size and surface charge during the polymerization. Transmission Electron Microscopy (TEM) images were obtained using a JEOL JEM-1400Plus microscope operating at 120 kV. Samples were prepared by depositing a dilute droplet of the dispersion onto a carbon-coated copper grid and allowing it to dr y under ambient conditions. X-ray Diffraction (XRD) patterns were collected on a Bruker D8 Advance diffractometer using Cu Kα radiation (λ = 1.5406 Å) over a 2θ range of 10–80°. Synthesis of Amine-Functionalized Silica Nanoparticles (SiO₂-NH₂) A solution of silica nanoparticles (10 mL, 30 wt% in methanol) was added to a round-bottom flask containing 15 mL of THF. To this, 3-aminopropyldimethylethoxysilane (APS, 0.3 mL, 1.59 mmol) was added. The mixture was refluxed at 75°C under a nitrogen atmosphere for 3 hours. After cooling to room temperature, the product was precipitated into 120 mL of hexanes. The particles were collected via centrifugation, redispersed in THF via sonication, and reprecipitated in hexanes. This purification cycle was repeated twice. The final amine-functionalized particles were dissolved in 40 mL of THF for subsequent reactions. Grafting of the RAFT Agent (MDSS-g-SiO₂) A solution of the amine-functionalized SiO₂ nanoparticles (40 mL, ~ 6 g) in THF was placed in a round-bottom flask. A solution of the NHS-activated MDSS RAFT agent (0.2 g, 0.4 mmol) in THF was added dropwise at room temperature. The reaction mixture was stirred for 12 hours. The resulting MDSS-grafted particles were precipitated into 400 mL of hexanes, collected by centrifugation (3000 rpm, 8 min), and redispersed in 30 mL of THF. The dissolution-precipitation process was repeated until the supernatant was colorless, indicating the complete removal of unbound RAFT agent. The grafting density of the CTA was determined by UV-Vis spectroscopy using a calibration curve constructed from standard solutions of free MDSS and was found to be 0.2 chains/nm². The synthesis pathway is illustrated in Scheme 1 . Surface-Initiated RAFT Polymerization of Chloroprene (PCP-g-SiO₂) In a typical procedure, chloroprene monomer (1 g) and MDSS-g-SiO₂ RAFT agent (0.22 g) were combined in a Schlenk tube. AIBN initiator (114 µL from a 10 mM stock solution in THF) and methanol (3 mL) were added. The mixture was subjected to three freeze-pump-thaw cycles to remove oxygen and back-filled with nitrogen. The Schlenk flask was then immersed in an oil bath at 60°C to initiate polymerization. Aliquots were withdrawn at specific time intervals to monitor kinetics and assembly. The polymerization was quenched by cooling in an ice bath. The resultant PCP-grafted silica particles (PCP-g-SiO₂) were purified by precipitation into a large excess of methanol, followed by centrifugation (8000 rpm, 10 min), and were subsequently redispersed in THF. Cleavage of Grafted Polymer for Characterization To characterize the grafted polymer cleaved from the silica surface, PCP-g-SiO₂ particles (20 mg) were dissolved in THF (2 mL). Aqueous hydrofluoric acid (HF, 49%, 0.2 mL) was added to etch the silica core, and the mixture was stirred overnight at room temperature. The solution was transferred to a PTFE dish, and the volatiles were allowed to evaporate in a fume hood. The recovered polymer was analyzed by GPC and ¹H NMR spectroscopy. In Situ Assembly Monitoring The formation of vesicles during the polymerization was monitored by observing the increase in turbidity of the reaction mixture. Aliquots were extracted at timed intervals (0, 60, 90, 120 min) and analyzed immediately by DLS and TEM to track the evolution of the self-assembled structures. The formation of assemblies during polymerization could be observed from the turbidity changes of the reaction solution. A small sample was withdrawn from the reaction flask periodically throughout polymerization, and each sample's visual appearance is shown in Fig. 1 . Results and Discussion The work effectively illustrated the formation of single-walled vesicles from polychloroprene-grafted silica nanoparticles (SiO₂) via surface-initiated polymerization-induced self-assembly (SI-PISA). A second brush that was soluble in the solvent-induced self-assembly was then polymerized after a solvent-miscible brush was affixed to 15 nm silica nanoparticles. Post-polymerization processing was unnecessary since self-assembly occurred in situ during the polymerization process. As shown in Fig. 2 , the DLS data demonstrated the progression of the assemblies over time, confirming the production of vesicles through the observed increase in particle size as polymerization proceeded. Figure 3 A presents the ln(M₀/Mₜ) vs time plot for surface-initiated polymerization in methanol, showing first-order kinetics, while Fig. 3 B displays the Mn vs. monomer conversion plots, confirming controlled polymerization behavior. These kinetic analyses were crucial for understanding the growth mechanism of polychloroprene grafts. Transmission electron microscopy (TEM) provided direct visualization of the morphological evolution, as evidenced in Fig. 4 , which shows representative TEM images of the assemblies at different polymerization times: 0 min (A), 60 min (B), 90 min (C), and 120 min (D). The images clearly showed the creation of distinct vesicles at various phases of polymerization, complementing the DLS data in Fig. 2 . Representative TEM images of the assemblies at different polymerization times are shown in Fig. 4 : (A) 0 min, (B) 60 min, (C) 90 min, and (D) 120 min. The XRD analysis of chloroprene-grafted silica nanovesicles (Shown in Fig. 5 ) at different polymerization times reveals a clear progression of structural development that correlates well with TEM observations. The XRD patterns show a dominant amorphous halo centered at approximately 22° 2θ, characteristic of silica nanoparticles, with superimposed sharper crystalline peaks at 19.2°, 23.5°, 40.1°, and 58.3° 2θ corresponding to the developing polychloroprene crystalline domains. As polymerization progressed from 0 to 120 minutes, these polymer-related peaks showed a significant increase in intensity and sharpness, indicating enhanced crystallinity and structural ordering. The calculated crystallite size increased from 1.70 nm at 0 minutes to 2.40 nm at 120 minutes, while the full width at half maximum (FWHM) of the main peak decreased from 4.8° to 3.4°, confirming the growth of more defined crystalline regions. These XRD findings directly complement the TEM results, which showed the evolution from dispersed nanoparticles at 0 minutes to well-defined vesicular structures at 120 minutes. The increasing crystallinity observed by XRD corresponds to the improved organizational integrity of the nanovesicles visualized by TEM, demonstrating that the in situ polymerization not only drives self-assembly but also enhances the structural perfection of the resulting hybrid materials. The combined XRD and TEM data provide compelling evidence that the SI-PISA process facilitates simultaneous vesicle formation and crystallinity development, offering a unique approach to creating well-organized nanocomposites with controlled structural properties. The SI-PISA method described in this work is a new and effective technique for creating nanovesicles at high nanoparticle concentrations. The self-assembly process may be precisely tuned by adjusting the polymer chains' molecular weight and grafting density on the silica nanoparticles, as demonstrated by the kinetic data in Fig. 3 . The findings imply that the surface-grafted polymer is essential for guiding nanoparticle self-assembly into vesicles. The grafted polymer's amphiphilic character, which encourages the organizing of nanoparticles into hollow structures, is probably what drives the production of vesicles. The study also emphasizes how crucial solvent selection and polymerization parameters are to optimal self-assembly. The results are consistent with earlier studies on polymer-directed nanoparticle self-assembly. Nevertheless, this work contributes to the field by showing that polychloroprene-grafted silica nanoparticles that self-assemble into vesicles may be produced utilizing SI-PISA. One major benefit is that these structures may be produced without the need for further purification procedures or solvent switching, which streamlines the procedure and lowers the possibility of nanoparticle aggregation. These nanovesicles have a wide range of potential uses, especially in industries where hollow nanostructures are highly desired, such medication delivery, catalysis, and bioimaging. Additionally, the work sheds light on the basic processes of nanoparticle self-assembly, which may help designers create future nanocomposites with specific characteristics. Conclusion This study on the in situ self-assembly of chloroprene-grafted silica nanoparticles signifies a substantial advancement in materials science, having extensive ramifications across several sectors. This research presents a solvent-free, one-step approach to produce reinforced nanocomposites and functional nanovesicles, tackling significant issues in rubber reinforcing, drug delivery, and innovative materials. The medical sector might gain significantly, since these materials may result in more resilient gloves, safer catheters, and sophisticated drug delivery devices; nonetheless, biocompatibility testing and sterilization validation are critical obstacles before practical use. In industrial applications, these nanocomposites' superior mechanical characteristics and thermal resistance provide alternatives for automobile seals, vibration dampers, and corrosion-resistant coatings, possibly supplanting conventional carbon black reinforcements. The distinctive hollow nanostructures facilitate catalytic applications and environmental technologies, as their adjustable porosity may enhance chemical processes and pollutant cleanup. Nonetheless, transitioning from laboratory innovation to commercial viability necessitates the resolution of specific pragmatic issues. The scalability of the synthesis process, long-term stability assessment, and cost-effectiveness relative to current materials require meticulous consideration. Future endeavors should establish industrial collaborations to evaluate real-world efficacy, optimize manufacturing methods for large-scale production, and investigate bio-based alternatives to enhance sustainability. The intrinsic value of this study is in its adaptability; by offering both foundational understanding of nanoparticle self-assembly and pragmatic pathways to improved materials, it fosters prospects for innovation in healthcare, transportation, energy, and environmental domains. As these advancements unfold, they possess the capacity to enhance scientific comprehension and yield significant enhancements in product efficacy, manufacturing productivity, and patient outcomes, ultimately illustrating how innovative nanotechnology can address practical challenges. Declarations Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. Funding No funding was received for this research. Author Contribution Author Contributions:• Zaid M. Abbas: Conceptualization, Methodology, Lab work, Supervision, Writing – original draft, Writing – review & editing, Project administration• Fatma A. Khazaal: Investigation, Formal analysis, Lab work, Data curation, Validation, Visualization• Ammar Ferman Abbood: Investigation, Methodology, Lab work, Formal analysis, Data curation, Visualization• Mohammad N. 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Supplementary Files SI.docx floatimage1.png Scheme 1 Synthesis of SiO 2 -g-(polychloroprene) Cite Share Download PDF Status: Posted Version 1 posted 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. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. 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Abbas","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA6UlEQVRIiWNgGAWjYFACHjYgYQNhJ4CIA2BEUEsaVEsC8VoOMyCsIaCeQb797LEHP/6cT+yXSH784eEPBjm+GwmMB97g0cLYk5du2Nt2O3HmjDQzCaDDjCVvJDAcnINHCzNDjpkEb8PtxA23E8xAfkncANRymAePFjb+N2aSf/6cA2pJ//wBqKWeoBYeiRwzaR62A0AtOQYghyUYENIiIfEu3Vi2Ldl45vw3ZRIJaRKGM888bMDrF/n+3GMP3/yxk+3nOb754w8bG3m+48mHP+ALMQxbgZixgQGfw3AAMrSMglEwCkbB8AUAbqRTqiHhz+4AAAAASUVORK5CYII=","orcid":"","institution":"University of Wasit","correspondingAuthor":true,"prefix":"","firstName":"Zaid","middleName":"M.","lastName":"Abbas","suffix":""},{"id":619363323,"identity":"b3779613-ad9a-4f36-85fa-7aeb6c19bf21","order_by":1,"name":"Fatma A. Khazaal","email":"","orcid":"","institution":"University of Wasit","correspondingAuthor":false,"prefix":"","firstName":"Fatma","middleName":"A.","lastName":"Khazaal","suffix":""},{"id":619363326,"identity":"80397538-5ab1-4c5f-92d5-a14dcad6fef3","order_by":2,"name":"Ammar Ferman Abbood","email":"","orcid":"","institution":"University of Wasit","correspondingAuthor":false,"prefix":"","firstName":"Ammar","middleName":"Ferman","lastName":"Abbood","suffix":""},{"id":619363327,"identity":"93a21b00-3b04-46a7-bf44-c6c48089500b","order_by":3,"name":"Mohammad N. AL-Baiati","email":"","orcid":"","institution":"University of Karbala","correspondingAuthor":false,"prefix":"","firstName":"Mohammad","middleName":"N.","lastName":"AL-Baiati","suffix":""}],"badges":[],"createdAt":"2026-02-12 11:54:03","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-8861776/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-8861776/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":106557454,"identity":"d6c46175-1615-4f53-92fd-0702ce98870e","added_by":"auto","created_at":"2026-04-09 20:34:40","extension":"jpg","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":16384,"visible":true,"origin":"","legend":"\u003cp\u003eVisual appearance of each sample withdrawn during polymerization.\u003c/p\u003e","description":"","filename":"Picture1.jpg","url":"https://assets-eu.researchsquare.com/files/rs-8861776/v1/f626bea19c8ef5a978e1d9e6.jpg"},{"id":106725645,"identity":"0e301016-e941-49c4-b301-a10038fb0257","added_by":"auto","created_at":"2026-04-12 18:33:21","extension":"jpg","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":53169,"visible":true,"origin":"","legend":"\u003cp\u003eDLS of each sample withdrawn during polymerization.\u003c/p\u003e","description":"","filename":"Picture2.jpg","url":"https://assets-eu.researchsquare.com/files/rs-8861776/v1/1072a731c1bd98ddae8a6df7.jpg"},{"id":106727322,"identity":"3c3d0030-e310-4d2c-a74c-3703d0be1104","added_by":"auto","created_at":"2026-04-12 18:38:41","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":41194,"visible":true,"origin":"","legend":"\u003cp\u003e(A) ln(M0/Mt) vs time plot for surface-initiated polymerization in methanol. (B) Mn vs. monomer conversion plots for surface-initiated polymerization in methanol.\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-8861776/v1/8215cdcc2f930f3132042fe6.png"},{"id":106557459,"identity":"51aa6510-52c7-4422-86ac-ce86139a646f","added_by":"auto","created_at":"2026-04-09 20:34:40","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":621825,"visible":true,"origin":"","legend":"\u003cp\u003eRepresentative TEM images of the assemblies at different polymerization times: 0 min (A), 60 min (B), 90 min (C), 120 min (D).\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-8861776/v1/9413b20e878a87d5843803b3.png"},{"id":106557460,"identity":"3fd22fd7-7911-48aa-8526-64e0f5aa804a","added_by":"auto","created_at":"2026-04-09 20:34:41","extension":"jpg","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":105796,"visible":true,"origin":"","legend":"\u003cp\u003eXRD Patterns of Chloroprene-Grafted Silica Nanovesicles at Different Polymerization Times.\u003c/p\u003e","description":"","filename":"5.jpg","url":"https://assets-eu.researchsquare.com/files/rs-8861776/v1/b90d8c413ca7841fa642f744.jpg"},{"id":107867919,"identity":"a3f67873-b1e0-4612-94f1-a0af13399ec3","added_by":"auto","created_at":"2026-04-27 07:05:24","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1053361,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-8861776/v1/5e4e7b71-e4d8-4da2-a9e2-db5e4597eb22.pdf"},{"id":106725081,"identity":"d1c8da70-510c-4505-a043-099aa9d8a728","added_by":"auto","created_at":"2026-04-12 18:31:18","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":723183,"visible":true,"origin":"","legend":"","description":"","filename":"SI.docx","url":"https://assets-eu.researchsquare.com/files/rs-8861776/v1/398179ac81dd9357c12a83f3.docx"},{"id":106557457,"identity":"4d60639e-1a14-4a3b-b125-8d372392aec4","added_by":"auto","created_at":"2026-04-09 20:34:40","extension":"png","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":249604,"visible":true,"origin":"","legend":"\u003cp\u003eScheme 1 Synthesis of SiO\u003csub\u003e2\u003c/sub\u003e-g-(polychloroprene)\u003c/p\u003e","description":"","filename":"floatimage1.png","url":"https://assets-eu.researchsquare.com/files/rs-8861776/v1/5d27b9a97b11afa29200997d.png"}],"financialInterests":"No competing interests reported.","formattedTitle":"One-Pot Synthesis of Nanovesicles via Surface-Initiated Polymerization-Induced Self-Assembly of Polychloroprene-Grafted Silica","fulltext":[{"header":"Introduction","content":"\u003cp\u003eRubber, one of the most important biosynthesized polymers with exceptional chemical and physical properties, finds widespread application in various industries.\u003csup\u003e\u003cspan additionalcitationids=\"CR2 CR3 CR4 CR5\" citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e\u003c/sup\u003e Medical equipment, including gloves, condoms, blood transfusion tubing, catheters, injector closures, and safety bags, has been made from rubber due to its remarkable elasticity, flexibility, resistance to viral penetration, superior formability, and biodegradability. \u003csup\u003e7\u0026ndash;10\u003c/sup\u003e Like any other polymer, its macromolecular backbone contains unsaturated bonds, making it vulnerable to heat or oxidative deterioration, especially when it forms thin films.\u003csup\u003e\u003cspan additionalcitationids=\"CR12\" citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e\u003c/sup\u003e Other significant problems with rubbery products include low tensile strength and poor tear resistance, particularly in applications such as condoms and medical gloves. Attempts have been made to strengthen dry rubber using silica, carbon black, and modified metal oxides. These conventional reinforcing materials, however, are not particularly effective in enhancing the finished structure. Therefore, finding innovative ways to enhance the mechanical properties and resistance to aging of rubber goods is crucial.\u003csup\u003e\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e,\u003cspan additionalcitationids=\"CR15 CR16\" citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e\u003c/sup\u003e Polymer graft inorganic nanocomposites, an alternative to conventional-filled polymers or polymer blends, combine the benefits of polymers, such as flexibility, toughness, and ease of processing, with those of inorganic phases, including hardness, durability, and thermal stability.\u003csup\u003e\u003cspan additionalcitationids=\"CR19\" citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e\u003c/sup\u003e This improvement in composite characteristics is particularly notable at modest loading levels of nanoparticle fillers, which do not significantly increase the compound's density or reduce light transmission. Recently, there has been considerable interest in incorporating inorganic nanofillers into rubber matrices to address the issues with nanocomposites. It was found that the organically modified nanocomposite, loaded with a respectable weight percent, exhibited substantial reinforcement on the rubber matrix due to the infusion of NP and the growth of the framework inside the matrix. The rubber matrix's three-dimensional network was also shown to improve its solvent and mechanical resistance significantly.\u003csup\u003e\u003cspan additionalcitationids=\"CR22\" citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e\u003c/sup\u003e The exceptional reinforcing effectiveness of layered silicate rubber nanocomposites, even at low loading of layered silicates, is mainly due to the silicate platelets' high aspect ratio and nanoscale dispersion. The properties of rubber might be further improved by directly reinforcing it with fillers that have a larger specific surface area, such as spherical inorganic nanoparticles. This is likely because there is no reliable way to prevent nanoparticles from vigorously self-aggregating. Our previous work used a novel self-assembly nanocomposite approach to manufacture surface-initiated polymerization-induced self-assembly (SI-PISA). We found a straightforward and efficient way to induce inorganic NPs to self-assemble into single-layer nanovesicles via surface-initiated polymerization. The SI-PISA approach is a new use of PISA that guides the self-assembly of inorganic nanoparticles by forming polymer chains from NP surfaces.\u003csup\u003e\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e,\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e\u003c/sup\u003e One possible method for creating new, valuable materials is the capacity of inorganic nanoparticles to self-assemble into hierarchical structures.\u003csup\u003e\u003cspan additionalcitationids=\"CR25 CR26 CR27 CR28 CR29\" citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e\u003c/sup\u003e Among all the self-assembled structures (strings, tubes, spheres, vesicles, etc.), nanovesicles are especially significant due to their hollow topologies, which enable uses in cancer treatment, drug delivery, catalysis, and bioimaging.\u003csup\u003e\u003cspan additionalcitationids=\"CR32\" citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e\u003c/sup\u003e Recent studies have shown that inorganic NPs were coated with polymers or amphiphilic ligands to create these vesicles.\u003csup\u003e\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e,\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e,\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e,\u003cspan additionalcitationids=\"CR35 CR36\" citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e\u003c/sup\u003e Thin-layer vesicles for polymer-directed self-assembly have been successfully constructed using block copolymer tethered NPs and mixed brush-grafted NPs.\u003csup\u003e\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e,\u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e\u003c/sup\u003e Typically, each component's polymer-grafted NPs were made using an appropriate solvent, and any free polymers were eliminated using purification methods.\u003csup\u003e\u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e40\u003c/span\u003e\u003c/sup\u003e The self-assembly process commenced with adding a specific solvent or through film rehydration, necessitating several sample preparation steps and constrained by low nanoparticle concentration.\u003csup\u003e\u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e41\u003c/span\u003e,\u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e42\u003c/span\u003e\u003c/sup\u003e Previous research employed solvent switching to examine the impact of concentration on the self-assembly of PEG-b-PCL tethered gold nanoparticles.\u003csup\u003e\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e,\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e,\u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e43\u003c/span\u003e\u003c/sup\u003e When particle concentrations exceeded 250 \u0026micro;g/ml, they found that giant nanoscale vesicles that could form were massive submicron-sized assemblies.\u003csup\u003e\u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e44\u003c/span\u003e\u003c/sup\u003e The consistent dispersion of silica nanoparticles and the robust interactions between silica and polymer matrixes are primarily responsible for the improved characteristics. We recently synthesized rubber/SiO2 nanocomposites using this self-assembly approach and provided a brief report on their preparation and thermal characteristics. This work will methodically cover the self-assembly mechanism of silica nanoparticles and polychloroprene. Additionally, the shape of the nanocomposite and the microstructure of silica nanoclusters will be seen using DLS and TEM, and the effects of particles will be examined.\u003c/p\u003e "},{"header":"Materials","content":" \u003cp\u003e3,4-Dichloro-1-butene (TCI America) was dehydrochlorinated to yield chloroprene monomer following a standard procedure. The chain transfer agent (CTA), 2-Methyl-2-[(dodecylsulfanylthiocarbonyl) sulfanyl]propanoic acid (MDSS, 97%), was obtained from Strem Chemicals and used as received. Spherical silica nanoparticles (SiO₂, MT\u0026ndash;ST, 10\u0026ndash;15 nm diameter) were purchased from Nissan Chemical Co. Aminopropyldimethylethoxysilane (APS, 95%) was supplied by Gelest and used without further purification. 2,2'-Azobisisobutyronitrile (AIBN) was acquired from Fisher, recrystallized from methanol, and dissolved in tetrahydrofuran (THF) to prepare a 10 mM stock solution. HPLC-grade THF, methanol, and hexanes were used as received.\u003c/p\u003e \u003cp\u003eCharacterization Techniques\u003c/p\u003e \u003cp\u003eFourier-transform infrared (FTIR) spectra were acquired using a Richmond Scientific FTIR Spectrophotometer to confirm the chemical modifications at each stage of the synthesis. Spectra were collected in the range of 4000 to 400 cm⁻\u0026sup1; with a resolution of 4 cm⁻\u0026sup1; and were averaged over 32 scans to ensure a high signal-to-noise ratio. Samples were analyzed as solid films deposited on the crystal surface of a single-reflection Diamond ATR (Attenuated Total Reflectance) accessory. This method allowed for the direct analysis of the functionalized nanoparticles without the need for KBr pellet preparation. Nuclear Magnetic Resonance (NMR) spectroscopy was conducted on a Bruker Avance III HD 400 MHz spectrometer. Samples were dissolved in deuterated chloroform (CDCl₃) with tetramethylsilane (TMS) as an internal standard. Gel Permeation Chromatography (GPC) was used to determine the molecular weight and dispersity (\u0026ETH;) of the cleaved polymers against polystyrene standards. Dynamic Light Scattering (DLS) and Zeta Potential measurements were performed on a Malvern Zetasizer Nano ZS to monitor nanoparticle size and surface charge during the polymerization. Transmission Electron Microscopy (TEM) images were obtained using a JEOL JEM-1400Plus microscope operating at 120 kV. Samples were prepared by depositing a dilute droplet of the dispersion onto a carbon-coated copper grid and allowing it to dr y under ambient conditions. X-ray Diffraction (XRD) patterns were collected on a Bruker D8 Advance diffractometer using Cu Kα radiation (λ\u0026thinsp;=\u0026thinsp;1.5406 \u0026Aring;) over a 2θ range of 10\u0026ndash;80\u0026deg;.\u003c/p\u003e \u003cp\u003eSynthesis of Amine-Functionalized Silica Nanoparticles (SiO₂-NH₂)\u003c/p\u003e \u003cp\u003eA solution of silica nanoparticles (10 mL, 30 wt% in methanol) was added to a round-bottom flask containing 15 mL of THF. To this, 3-aminopropyldimethylethoxysilane (APS, 0.3 mL, 1.59 mmol) was added. The mixture was refluxed at 75\u0026deg;C under a nitrogen atmosphere for 3 hours. After cooling to room temperature, the product was precipitated into 120 mL of hexanes. The particles were collected via centrifugation, redispersed in THF via sonication, and reprecipitated in hexanes. This purification cycle was repeated twice. The final amine-functionalized particles were dissolved in 40 mL of THF for subsequent reactions.\u003c/p\u003e \u003cp\u003eGrafting of the RAFT Agent (MDSS-g-SiO₂)\u003c/p\u003e \u003cp\u003eA solution of the amine-functionalized SiO₂ nanoparticles (40 mL, ~\u0026thinsp;6 g) in THF was placed in a round-bottom flask. A solution of the NHS-activated MDSS RAFT agent (0.2 g, 0.4 mmol) in THF was added dropwise at room temperature. The reaction mixture was stirred for 12 hours. The resulting MDSS-grafted particles were precipitated into 400 mL of hexanes, collected by centrifugation (3000 rpm, 8 min), and redispersed in 30 mL of THF. The dissolution-precipitation process was repeated until the supernatant was colorless, indicating the complete removal of unbound RAFT agent. The grafting density of the CTA was determined by UV-Vis spectroscopy using a calibration curve constructed from standard solutions of free MDSS and was found to be 0.2 chains/nm\u0026sup2;. The synthesis pathway is illustrated in Scheme \u003cspan refid=\"Sch1\" class=\"InternalRef\"\u003e1\u003c/span\u003e.\u003c/p\u003e \u003cp\u003eSurface-Initiated RAFT Polymerization of Chloroprene (PCP-g-SiO₂)\u003c/p\u003e \u003cp\u003eIn a typical procedure, chloroprene monomer (1 g) and MDSS-g-SiO₂ RAFT agent (0.22 g) were combined in a Schlenk tube. AIBN initiator (114 \u0026micro;L from a 10 mM stock solution in THF) and methanol (3 mL) were added. The mixture was subjected to three freeze-pump-thaw cycles to remove oxygen and back-filled with nitrogen. The Schlenk flask was then immersed in an oil bath at 60\u0026deg;C to initiate polymerization. Aliquots were withdrawn at specific time intervals to monitor kinetics and assembly. The polymerization was quenched by cooling in an ice bath. The resultant PCP-grafted silica particles (PCP-g-SiO₂) were purified by precipitation into a large excess of methanol, followed by centrifugation (8000 rpm, 10 min), and were subsequently redispersed in THF.\u003c/p\u003e \u003cp\u003eCleavage of Grafted Polymer for Characterization\u003c/p\u003e \u003cp\u003eTo characterize the grafted polymer cleaved from the silica surface, PCP-g-SiO₂ particles (20 mg) were dissolved in THF (2 mL). Aqueous hydrofluoric acid (HF, 49%, 0.2 mL) was added to etch the silica core, and the mixture was stirred overnight at room temperature. The solution was transferred to a PTFE dish, and the volatiles were allowed to evaporate in a fume hood. The recovered polymer was analyzed by GPC and \u0026sup1;H NMR spectroscopy.\u003c/p\u003e \u003cp\u003eIn Situ Assembly Monitoring\u003c/p\u003e \u003cp\u003eThe formation of vesicles during the polymerization was monitored by observing the increase in turbidity of the reaction mixture. Aliquots were extracted at timed intervals (0, 60, 90, 120 min) and analyzed immediately by DLS and TEM to track the evolution of the self-assembled structures.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe formation of assemblies during polymerization could be observed from the turbidity changes of the reaction solution. A small sample was withdrawn from the reaction flask periodically throughout polymerization, and each sample's visual appearance is shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e.\u003c/p\u003e"},{"header":"Results and Discussion","content":"\u003cp\u003eThe work effectively illustrated the formation of single-walled vesicles from polychloroprene-grafted silica nanoparticles (SiO₂) via surface-initiated polymerization-induced self-assembly (SI-PISA). A second brush that was soluble in the solvent-induced self-assembly was then polymerized after a solvent-miscible brush was affixed to 15 nm silica nanoparticles. Post-polymerization processing was unnecessary since self-assembly occurred in situ during the polymerization process.\u003c/p\u003e \u003cp\u003eAs shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e, the DLS data demonstrated the progression of the assemblies over time, confirming the production of vesicles through the observed increase in particle size as polymerization proceeded. Figure\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eA presents the ln(M₀/Mₜ) vs time plot for surface-initiated polymerization in methanol, showing first-order kinetics, while Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eB displays the Mn vs. monomer conversion plots, confirming controlled polymerization behavior. These kinetic analyses were crucial for understanding the growth mechanism of polychloroprene grafts.\u003c/p\u003e \u003cp\u003eTransmission electron microscopy (TEM) provided direct visualization of the morphological evolution, as evidenced in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e, which shows representative TEM images of the assemblies at different polymerization times: 0 min (A), 60 min (B), 90 min (C), and 120 min (D). The images clearly showed the creation of distinct vesicles at various phases of polymerization, complementing the DLS data in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e. Representative TEM images of the assemblies at different polymerization times are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e: (A) 0 min, (B) 60 min, (C) 90 min, and (D) 120 min.\u003c/p\u003e \u003cp\u003eThe XRD analysis of chloroprene-grafted silica nanovesicles (Shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e) at different polymerization times reveals a clear progression of structural development that correlates well with TEM observations. The XRD patterns show a dominant amorphous halo centered at approximately 22\u0026deg; 2θ, characteristic of silica nanoparticles, with superimposed sharper crystalline peaks at 19.2\u0026deg;, 23.5\u0026deg;, 40.1\u0026deg;, and 58.3\u0026deg; 2θ corresponding to the developing polychloroprene crystalline domains. As polymerization progressed from 0 to 120 minutes, these polymer-related peaks showed a significant increase in intensity and sharpness, indicating enhanced crystallinity and structural ordering. The calculated crystallite size increased from 1.70 nm at 0 minutes to 2.40 nm at 120 minutes, while the full width at half maximum (FWHM) of the main peak decreased from 4.8\u0026deg; to 3.4\u0026deg;, confirming the growth of more defined crystalline regions. These XRD findings directly complement the TEM results, which showed the evolution from dispersed nanoparticles at 0 minutes to well-defined vesicular structures at 120 minutes. The increasing crystallinity observed by XRD corresponds to the improved organizational integrity of the nanovesicles visualized by TEM, demonstrating that the in situ polymerization not only drives self-assembly but also enhances the structural perfection of the resulting hybrid materials. The combined XRD and TEM data provide compelling evidence that the SI-PISA process facilitates simultaneous vesicle formation and crystallinity development, offering a unique approach to creating well-organized nanocomposites with controlled structural properties.\u003c/p\u003e \u003cp\u003eThe SI-PISA method described in this work is a new and effective technique for creating nanovesicles at high nanoparticle concentrations. The self-assembly process may be precisely tuned by adjusting the polymer chains' molecular weight and grafting density on the silica nanoparticles, as demonstrated by the kinetic data in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e. The findings imply that the surface-grafted polymer is essential for guiding nanoparticle self-assembly into vesicles. The grafted polymer's amphiphilic character, which encourages the organizing of nanoparticles into hollow structures, is probably what drives the production of vesicles. The study also emphasizes how crucial solvent selection and polymerization parameters are to optimal self-assembly.\u003c/p\u003e \u003cp\u003eThe results are consistent with earlier studies on polymer-directed nanoparticle self-assembly. Nevertheless, this work contributes to the field by showing that polychloroprene-grafted silica nanoparticles that self-assemble into vesicles may be produced utilizing SI-PISA. One major benefit is that these structures may be produced without the need for further purification procedures or solvent switching, which streamlines the procedure and lowers the possibility of nanoparticle aggregation.\u003c/p\u003e \u003cp\u003eThese nanovesicles have a wide range of potential uses, especially in industries where hollow nanostructures are highly desired, such medication delivery, catalysis, and bioimaging. Additionally, the work sheds light on the basic processes of nanoparticle self-assembly, which may help designers create future nanocomposites with specific characteristics.\u003c/p\u003e"},{"header":"Conclusion","content":"\u003cp\u003eThis study on the in situ self-assembly of chloroprene-grafted silica nanoparticles signifies a substantial advancement in materials science, having extensive ramifications across several sectors. This research presents a solvent-free, one-step approach to produce reinforced nanocomposites and functional nanovesicles, tackling significant issues in rubber reinforcing, drug delivery, and innovative materials. The medical sector might gain significantly, since these materials may result in more resilient gloves, safer catheters, and sophisticated drug delivery devices; nonetheless, biocompatibility testing and sterilization validation are critical obstacles before practical use. In industrial applications, these nanocomposites' superior mechanical characteristics and thermal resistance provide alternatives for automobile seals, vibration dampers, and corrosion-resistant coatings, possibly supplanting conventional carbon black reinforcements. The distinctive hollow nanostructures facilitate catalytic applications and environmental technologies, as their adjustable porosity may enhance chemical processes and pollutant cleanup.\u003c/p\u003e \u003cp\u003eNonetheless, transitioning from laboratory innovation to commercial viability necessitates the resolution of specific pragmatic issues. The scalability of the synthesis process, long-term stability assessment, and cost-effectiveness relative to current materials require meticulous consideration. Future endeavors should establish industrial collaborations to evaluate real-world efficacy, optimize manufacturing methods for large-scale production, and investigate bio-based alternatives to enhance sustainability. The intrinsic value of this study is in its adaptability; by offering both foundational understanding of nanoparticle self-assembly and pragmatic pathways to improved materials, it fosters prospects for innovation in healthcare, transportation, energy, and environmental domains. As these advancements unfold, they possess the capacity to enhance scientific comprehension and yield significant enhancements in product efficacy, manufacturing productivity, and patient outcomes, ultimately illustrating how innovative nanotechnology can address practical challenges.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e \u003ch2\u003eDeclaration of Competing Interest\u003c/h2\u003e \u003cp\u003eThe authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.\u003c/p\u003e \u003c/p\u003e\u003ch2\u003eFunding\u003c/h2\u003e \u003cp\u003eNo funding was received for this research.\u003c/p\u003e\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003eAuthor Contributions:\u0026bull; Zaid M. 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Angewandte Chemie - Int Ed 52(52):13958\u0026ndash;13964. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1002/anie.201308986\u003c/span\u003e\u003cspan address=\"10.1002/anie.201308986\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"},{"header":"Scheme ","content":"\u003cp\u003eScheme 1 is available in the Supplementary Files section.\u003c/p\u003e\n"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"RAFT polymerization, Nanocomposites, Polychloroprene, Self-assembly, Surface-initiated polymerization","lastPublishedDoi":"10.21203/rs.3.rs-8861776/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-8861776/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThis study presents the first instance of polychloroprene-grafted inorganic nanoparticles self-assembling into single-walled vesicles by surface-initiated polymerization. Initially, a solvent-miscible brush was used to attach 15-nm silica nanoparticles. A second brush that was soluble in solvent was then polymerized to stimulate self-assembly. On-site self-assembly took place while the second brush was being surface-initiated polymerization. This method enables the production of nanovesicles at a comparatively high concentration of NPs and eliminates the need for post-polymerization processing. Additionally, this technique helped us better understand how the surface-grafted polymer controls NP vesicular assembly, enabling us to observe how well-dispersed NPs formed into nanovesicles.\u003c/p\u003e","manuscriptTitle":"One-Pot Synthesis of Nanovesicles via Surface-Initiated Polymerization-Induced Self-Assembly of Polychloroprene-Grafted Silica","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2026-04-09 20:34:30","doi":"10.21203/rs.3.rs-8861776/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"20b84f2d-a93c-435b-a309-f7afba00e015","owner":[],"postedDate":"April 9th, 2026","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2026-05-07T17:38:43+00:00","versionOfRecord":[],"versionCreatedAt":"2026-04-09 20:34:30","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-8861776","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-8861776","identity":"rs-8861776","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}