Photoinitiated Thiol-ene Click Reaction Research Articles

Rational design and facile preparation of hybrid superhydrophobic epoxy coatings modified by fluorinated silsesquioxane-based giant molecules via photo-initiated thiol-ene click reaction with potential applications

First, several fluorinated silsesquioxane-based giant molecules (G-SQs) were easily prepared by the photo-initiated thiol-ene click reaction of octa(mercaptopropyl)silsesquioxane (SH8-SQ) with monovinyl(heptatrifluoropropyl)silsesquioxane (CF3-SQ) and perfluorohexyl ethylene with varying stoichiometric ratios. Then, G-SQs were used as low surface energy substances to modify epoxy acrylate resin (EA), which allowed adhesion to different substrates to prepare hydrophobic coatings via photo-initiated thiol-ene click reaction. The hybrid coating can impart stable superhydrophobic properties to cotton fabrics, which possess self-cleaning and oil–water separation function. The cotton fabrics coated by G-SQs-EA can perform oil–water separation very well, whose oil–water separation fluxes and efficiencies are 34,000 L m−2 h−1 and 99 %, respectively. The hybrid hydrophobic coating also provides effective corrosion protection for copper and the corrosion protection effect is further improved by increasing coating thickness. The corrosion current density, corrosion rate and impedance (0.01 Hz) reached 1.17*10−2 μA·cm−2, 0.14 μm yr−1 and 1026 kΩ cm−2, respectively. These excellent results indicate that EA coating modified by G-SQs has potential applications in many fields.

Metal-Phenolic Network Directed Coating of Single Probiotic Cell Followed by Photoinitiated Thiol-Ene Click Fortification to Enhance Oral Therapy.

Probiotics-based oral therapy has become a promising way to prevent and treat various diseases, while the application of probiotics is primarily restricted by loss of viability due to adverse conditions in the gastrointestinal (GI) tract during oral delivery. Layer-by-layer (LbL) single-cell encapsulation approaches are widely employed to improve the bioavailability of probiotics. However, they are generally time- and labor-intensive owing to multistep operation. Herein, a simple yet efficient LbL technique is developed to coat a model probiotic named Escherichia coli Nissle 1917 (EcN) through polyphenol-Ca2+ network directed allyl-modified gelatin (GelAGE) adsorption followed by cross-linking of GelAGE via photoinitiated thiol-ene click reaction to protect EcN from harsh microenvironments of GI tract. LbL single-cell encapsulation can be performed within 1h through simple operation. It is revealed that coated EcN exhibits significantly improved viability against acidic gastric fluid and bile salts, and enhanced colonization in the intestinal tract without loss of proliferation capabilities. Furthermore, oral therapy of coated EcN remarkably relieves the pathological symptoms associated with colitis in mice including down-regulating inflammation, repairing epithelial barriers, scavenging reactive oxygen species (ROS), and restoring the homeostasis of gut microbiota. This simplified LbL coating strategy has great potential for various probiotics-mediated biomedical and nutraceutical applications.

Asymmetric Block Extension of Star-Shaped [PEG-SH]4 - toward Poly(dehydroalanine)-Functionalized PEG Hydrogels for Catch and Release of Charged Guest Molecules.

With the incorporation of polyampholytic segments into soft matter, hydrogels can serve as a reservoir for a variety of charged molecules which can be caught and released upon changes in pH value. Asymmetric block extension of one arm for star-shaped poly(ethylene glycol) [PEG26 -SH]4 using short segments of polyampholytic poly(dehydroalanine) (PDha) is herein demonstrated while maintaining the functional thiol end groups for network formation. For subsequent hydrogel synthesis with up to 10wt.% PDha a straightforward and biocompatible photoinitiated thiol-ene click reaction is exploited. The investigation of the swelling properties of the hydrogel revealed responsive behavior toward ionic strength and variations in pH value. Moreover, the reversible adsorption of the model dyes methylene blue (MB) and acid orange 7 (AO7) is investigated by UV-vis measurements and the procedure can be successfully transferred to the adsorption of the adhesion peptide RGDS resulting in an uptake of 1.5 wt% RGDS with regard to the dry weight of the hydrogel.

Strong Binding of C-Glycosylic1,2-Thiodisaccharides to Galectin-3─Enthalpy-Driven Affinity Enhancement by Water-Mediated Hydrogen Bonds.

Galectin-3 is involved in multiple pathways of many diseases, including cancer, fibrosis, and diabetes, and it is a validated pharmaceutical target for the development of novel therapeutic agents to address unmet medical needs. Novel 1,2-thiodisaccharides with a C-glycosylic functionality were synthesized by the photoinitiated thiol-ene click reaction of O-peracylated 1-C-substituted glycals and 1-thio-glycopyranoses. Subsequent global deprotection yielded test compounds, which were studied for their binding to human galectin-3 by fluorescence polarization and isothermal titration calorimetry to show low micromolar Kd values. The best inhibitor displayed a Kd value of 8.0 μM. An analysis of the thermodynamic binding parameters revealed that the binding Gibbs free energy (ΔG) of the new inhibitors was dominated by enthalpy (ΔH). The binding mode of the four most efficient 1,2-thiodisaccharides was also studied by X-ray crystallography that uncovered the unique role of water-mediated hydrogen bonds in conferring enthalpy-driven affinity enhancement for the new inhibitors. This 1,2-thiodisaccharide-type scaffold represents a new lead for galectin-3 inhibitor discovery and offers several possibilities for further development.

Extremely high energy density and long fatigue life of nano-silica/polymethylvinylsiloxane dielectric elastomer generator by interfacial design

Dielectric elastomer generator (DEG) can harvest electrical energy from various movement in nature such as human walking and ocean waves. To achieve high energy harvesting performance of DEG, dielectric elastomer (DE) composite with strong interfacial interaction, and thus high electrical breakdown strength (Eb) and long fatigue life (NFL) at high strain is a key. In this study, nano-silica (SiO2)/polymethylvinylsiloxane (PMVS) DE composite with strong interfacial interaction for DEG with extremely high energy density (w), high power conversion efficiency (PCE) and long NFL was prepared by designing and synthesizing a new polar macromolecule coupling agent (MCA), ester group grafted liquid butadiene rubber using a photoinitiated thiol-ene click reaction. Compared with the common small molecule coupling agent (SCA) modified SiO2 (SCA@SiO2)/PMVS composite, the new MCA modified SiO2 (MCA@SiO2)/PMVS composite shows much stronger interfacial interaction owing to the largely increased co-crosslinking junction and chain entanglement, resulting in the significantly improved elongation at break and Eb at high strain (400%). As a result, MCA@SiO2/PMVS DEG exhibits an up-to-date highest w (92.2 mJ/cm3) and PCE (35.8%) among the previously reported DEG using unprestretched DE film, and its NFL reaches 141000 times, 3.9 times that of SCA@SiO2/PMVS DEG (36000 times). Thus, MCA@SiO2/PMVS DEG shows the highest full-life generating energy density (9710 J/cm3), 4.8 times and 2427 times that of SCA@SiO2/PMVS DEG and commercial VHB DEG, respectively.

Thiolene- and Polycaprolactone Methacrylate-Based Polymerized High Internal Phase Emulsion (PolyHIPE) Scaffolds for Tissue Engineering.

Highly porous emulsion templated polymers (PolyHIPEs) provide a number of potential advantages in the fabrication of scaffolds for tissue engineering and regenerative medicine. Porosity enables cell ingrowth and nutrient diffusion within, as well as waste removal from, the scaffold. The properties offered by emulsion templating alone include the provision of high interconnected porosity, and, in combination with additive manufacturing, the opportunity to introduce controlled multiscale porosity to complex or custom structures. However, the majority of monomer systems reported for PolyHIPE preparation are unsuitable for clinical applications as they are nondegradable. Thiol-ene chemistry is a promising route to produce biodegradable photocurable PolyHIPEs for the fabrication of scaffolds using conventional or additive manufacturing methods; however, relatively little research has been reported on this approach. This study reports the groundwork to fabricate thiol- and polycaprolactone (PCL)-based PolyHIPE materials via a photoinitiated thiolene click reaction. Two different formulations, either three-arm PCL methacrylate (3PCLMA) or four-arm PCL methacrylate (4PCLMA) moieties, were used in the PolyHIPE formulation. Biocompatibility of the PolyHIPEs was investigated using human dermal fibroblasts (HDFs) and human osteosarcoma cell line (MG-63) by DNA quantification assay, and developed PolyHIPEs were shown to be capable of supporting cell attachment and viability.

Fabrication of highly crosslinked and monodispersed silicon-containing polymeric microspheres via photo-initiated polymerization and their application in capillary liquid chromatography

Although inorganic silica-based and polymeric micron-sized spheres have widely been explored as column packing materials in high performance liquid chromatography (HPLC), they are still suffering the problems of either alkali corrosion of silica or polymer swelling. It is still necessary to search simple approaches for fabrication of monodisperse micron-sized hybrid particles as packing materials in HPLC. A novel kind of silicon-containing polyacrylate microspheres was designed and fabricated via two-step swelling and photo-initiated polymerization approach using 3-(allylpropylsilane) propyl acrylate (TAPA) containing both acrylate and vinyl groups and trimethylolpropane triacrylate (TRIM) as precursors. After carefully optimizing the fabrication conditions, the monodisperse micron-sized microspheres could be acquired as chromatographic packing, exhibiting excellent mechanical stability and reproducibility. Due to existence of electron-rich vinyl groups, three kinds of thiols such as octadecanethiol (ODT), dithiothreitol (DTT) and trimethylolpropane tris(3-mercaptopropionate) (TTMP) were facilely anchored onto the surface of microsphere via photo-initiated thiol-ene click reaction. They were applied in the separation of small molecules by cLC-UV and complex biosamples by cLC-MS/MS. A total of 6691 unique peptides from 1771 unique proteins was identified by ODT-modified microsphere, which was higher than those by unmodified and DTT/TTMP-modified poly(TAPA-co-TRIM) microspheres. It was expected this kind of hybrid microspheres can be further modified and widely applied in chromatographic field, offering great potential in commercialization.

Salen-decorated Periodic Mesoporous Organosilica: From Metal-assisted Epoxidation to Metal-free CO2 Insertion.

We clicked a salen ligand onto a thiol-ethane bridged periodic mesoporous organosilica (Salen-PMO) using a photo-initiated thiol-ene click reaction. This process resulted in a covalently bonded salen ligand on the PMO material. The final BET surface area amounts 511 m2 /g and the pore size diameter is approximately 7 nm. The functionalized PMO material showed an excellent carbon dioxide uptake capacity of 1.29 mmol/g at 273 K and 1 bar. More importantly, by coordinating a MoO2 2+ complex onto the Salen-PMO material, we obtained a heterogeneous catalyst with a good catalytic performance for the epoxidation of cyclohexene. The catalyst was highly reusable, as no decrease in its activity was observed for at least four runs (99% conversion). Finally, the metal-free Salen-PMO showed an exceptional catalytic performance in the cycloaddition of CO2 to epoxides. The obtained results clearly demonstrate the versatility of the Salen-PMO material not only as metal-free catalyst but also as a support material to anchor metal complexes for specific catalytic applications. With the same catalytic platform, we were able to firstly create epoxides out of alkenes, and subsequently turn these epoxides into cyclic carbonates, consuming CO2 .

Photo-Cross-Linked Polycarbonate Coating with Surface-Erosion Behavior for Corrosion Resistance and Cytocompatibility Enhancement of Magnesium Alloy.

Absorbable magnesium (Mg) materials are promising for medical implant applications. However, their corrosion rate and potential toxicity remain a challenge. Herein, a photo-cross-linked coating with suitable durability and unique surface-eroding behavior for enhancement of anticorrosion property and cytocompatibility of AZ31 Mg alloy was developed. The biodegradable allyl-functional polycarbonate, poly[(5-methyl-5-allyloxycarbonyl-1,3-propanediol carbonate)-co-(trimethylene carbonate)] [P(MAC-co-TMC), PMT], was first synthesized by ring-opening copolymerization. The PMT copolymer, pentaerythritol tetrakis(3-mercaptopropionate), and a photoinitiator were then applied on AZ31 Mg alloy by dip coating, and these films were cross-linked via the subsequent photoinitiated thiol-ene click reaction. The poly(l-lactide) (PLLA) and poly(1,3-trimethylene carbonate) (PTMC) coatings without cross-linking were prepared and used as control. Our results show that the cross-linked PMT coatings exhibited superior mechanical properties compared with PLLA and PTMC coatings. Meanwhile, the surface-erosion behavior of the cross-linked PMT coatings remained, as confirmed by scanning electron microscopy analysis. As a result, the cross-linked PMT-coated Mg alloy showed lower corrosion rates, better in vitro corrosion resistance, and much lower cytotoxicity, compared with bare Mg and ones coated with PLLA and PTMC coatings. Results indicate that the cross-linked PMT coatings with unique surface-erosion behavior and good cytocompatibility might be promising to improve the safety and success rate of Mg-based devices and implants.

Atomically Precise Structure Determination of Porous Organic Cage from Ab Initio PXRD Structure Analysis: Its Molecular Click Postfunctionalization and CO2 Capture Application.

A novel porous organic cage (POC) was prepared via condensation reaction between 1,3,5-triformylbenzene (TFB) and (1R,2R)-4-cyclohexene-1,2-diamine (CHEDA). This POC could pack in either an amorphous structure or a crystalline one. Atomically precise structure determination of POC was achieved through ab initio powder X-ray diffraction (PXRD) structure analysis in the chiral trigonal space group R3. The same atomically precise structure determination of POC from single-crystal X-ray diffraction (SXRD) structure analysis could be obtained independently with a slight difference in cell parameter, indicating that the refinement method through ab initio PXRD structure analysis is reliable and may serve as an essential method for atomically precise structure determination. The cage could adsorb up to 8 mmol/g CO2 at 298 K and 1 bar. Furthermore, 1-thioglycerol and 1-octadecanethiol were chosen to prove that postmodification of this POC was flexible. After post-synthetic modification (PSM) via highly efficient photoinitiated thiol-ene click reaction, the products still kept porous with relatively higher special surface area (337 m2/g of 5T and 156 m2/g of 5O) than mostly reported cages via the reduced-amine approach.

Fast fabrication and modification of polyoctahedral silsesquioxane-containing monolithic columns via two-step photo-initiated reactions and their application in proteome analysis of tryptic digests

A fast and robust approach was developed to fabricate and modify hybrid monolithic columns via two-step photo-initiated reactions. At first, acrylopropyl polyoctahedral silsesquioxane (acryl-POSS) and 3-(triallyl silyl) propyl acrylate (TAPA) were chosen as precursors to synthesize poly (POSS-co-TAPA) monolithic column (monolith I) via photo-initiated free-radical polymerization within 10 min, which left lots of allyl groups on the surface of monolith. Secondly, two thiol-containing compounds, penicillamine and 1-octadecanethiol (ODT), were introduced to modify the prepared poly (POSS-co-TAPA) column via photo-initiated thiol-ene click reaction within 20 min. Finally, three resulting monolithic columns were applied to separate phenolic, anilines and antibiotics mixtures. These mixtures were baseline-separated on the monolith modified with penicillamine (monolith II), exhibiting better selectivity than both pristine monolith I and that modified with ODT (monolith III). Additionally, these columns were further used for separation of tryptic digest of HeLa cells by cLC-MS/MS. The 5071 unique peptides mapped to 2442 proteins were identified from HeLa cells digest on monolith II, which were superior over those on monolith III, but slightly lower than those on monolith I. These results demonstrated that these POSS-containing columns exhibited great separation ability for complex samples.

Lithium (4-styrenesulfonyl) (trifluoromethanesulfonyl) imide based single-ion polymer electrolyte with superior battery performance

A novel single ion conducting polymer electrolyte is synthesized via a facile and efficient one-step ultraviolet initiated thiol-ene click reaction. The monomers of lithium (4-styrenesulfonyl) (trifluoromethanesulfonyl) imide, pentaerythritol tetrakis (2-mercaptoacetate) and pentaerythritol tetraacrylate are polymerized to be a crosslinked network structured polymer within a polypropylene nonwoven fabric supporting membrane by a photo-initiated thiol-ene click reaction. Upon solvent soaking, the obtained single ion conducting polymer electrolyte exhibits high ionic conductivity (0.84 mS cm−1 at room temperature), very high lithium ion transference number of 0.93, wide electrochemical window up to 5.2 V (vs. Li+/Li) and well compatibility with lithium metal anode. The corresponding LiFePO4/Li cell assembled with the prepared polymer electrolyte shows excellent rate capability and prominent cycling performance with the capacity retention rate of 83% after 400 cycles at 1 C. Therefore, the synthesized single ion conducting polymer electrolyte owns great potential for practical application in lithium ion batteries.

New Generation of Clickable Nucleic Acids: Synthesis and Active Hybridization with DNA.

Due to the ability to generate oligomers of precise sequence, sequential and stepwise solid-phase synthesis has been the dominant method of producing DNA and other oligonucleotide analogues. The requirement for a solid support, however, and the physical restrictions of limited surface area thereon significantly diminish the efficiency and scalability of these syntheses, thus, negatively affecting the practical applications of synthetic polynucleotides and other similarly created molecules. By employing the robust photoinitiated thiol-ene click reaction, we developed a new generation of clickable nucleic acids (CNAs) with a polythioether backbone containing repeat units of six atoms, matching the spacing of the phosphodiester backbone of natural DNA. A simple, inexpensive, and scalable route was utilized to produce CNA monomers in gram-scale, which indicates the potential to dramatically lower the cost of these DNA mimics and thereby expand the scope of these materials. The efficiency of this approach was demonstrated by the completion of CNA polymerization in 30 seconds, as characterized by size-exclusive chromatography (SEC) and infrared (IR) spectroscopy. CNA/DNA hybridization was demonstrated by gel electrophoresis and used in CdS nanoparticle assembly.

Understanding the Mechanism of Star-Block Copolymers as Nanoreactors for Synthesis of Well-Defined Silver Nanoparticles

Facile and large-scale synthesis of well-defined, thermally stable silver nanoparticles protected by polymer brushes for use in practical applications is still a challenge. Recent work has reported a nanoreactor approach that can be used to synthesize these silver nanoparticles. This approach uses amphiphilic star-block copolymers, which have a hydrophilic core surrounded by a hydrophobic exterior. These polymers thus can serve as the nanoreactors. In this study, we hypothesize that the local high concentration of silver ions in the inner hydrophilic cores of these star-block copolymers facilitates the nucleation and subsequent growth of silver nanoparticles. When all silver nanoparticles nucleate from the cores of the star-block copolymers in solution, the particle size can be controlled by the core size of the polymer. To test this hypothesis, a polyisoprene-b-poly(p-tert-butylstyrene) (PI-b-PtBS) star-block copolymer was functionalized with carboxylic acid groups using a high-efficiency, photo-initiated thiol-ene click reaction. We characterized this modified polymer using proton nuclear magnetic resonance spectroscopy, and the results indicated that ~60% of the double bonds in the polyisoprene block were successfully functionalized with carboxylic acid groups. When silver ions were added to a solution of these functionalized star-block copolymers, the negatively charged carboxylic acid groups would attract the positively charged silver ions. Subsequent reduction of these Ag+ by a tert-butylamine-borane complex at room temperature produced nanosized silver particles. However, transmission electron microscopy images showed that a significant amount of relatively large silver nanoparticles grew outside the star-block copolymer nanoreactors.

Cross-linked supramolecular polymers synthesized by photo-initiated thiol-ene click reaction of supramonomers

Supramonomers refer to monomers fabricated via noncovalent interactions and can be polymerized through conventional covalent methods. In this article, we realized the fabrication of cross-linked supramolecular polymers through photo-initiated thiol-ene click reaction of quadruple hydrogen bonded supramonomers. It is found that the cross-linked supramolecular polymer has a higher critical polymerization concentration than the linear supramolecular polymer, because the orientation of the trifunctional monomer leads to cyclize at low concentrations. It is anticipated that this research can enrich the methodology of fabricating cross-linked supramolecular polymers and provide a new phenomenon to understand the self-assembling behavior of cross-linked supramolecular polymers.

Synthesis of a novel sulfur-bearing secondary antioxidant with a high molecular weight and its comparative study on antioxidant behavior in polypropylene with two commercial sulfur-bearing secondary antioxidants having relatively low molecular weight

A novel sulfur-bearing secondary antioxidant with a high molecular weight of 2252 (OS-POSS), successfully synthesized via photoinitiated thiol-ene click reaction, was compared with two commercial sulfur-bearing secondary antioxidants on the stabilization of polypropylene (PP). The results of their oxidation induction time (OIT) via differential scanning calorimeter measurement (DSC) showed that the higher the molecular weight of secondary antioxidant is, the longer the OIT value, whether such sulfur-bearing antioxidant is used singly or in combination with primary antioxidant. The study of their long-term accelerated thermal aging in the air oven at 150 °C displayed that the molecular structure of sulfur-bearing secondary antioxidant, besides molecular weight, is another highly important factor determining the antioxidant efficiency, i.e., physical loss of antioxidants with the relatively low molecular weight may determine antioxidant efficiency, whereas thioether groups having neighboring ester carbonyl moieties may decompose more hydroperoxides with quicker rate.

Synthesis of cyclic, multivalent Arg-Gly-Asp using sequential thiol-ene/thiol-yne photoreactions.

A unique method has been developed for the formation of multivalent cyclic peptides. This procedure exploits on-resin peptide cyclization using a photoinitiated thiol-ene click reaction and subsequent clustering using thiol-yne photochemistry. Both reactions utilize the sulfhydryl group on natural cysteine amino acids to participate in the thiol-mediated reactions.