6.2 Hybridization of Thiol–Ene Chemistry Hydrogels for Biomedical Applications

Light-triggered thiol–ene polymerization is a powerful tool for synthesizing hydrogels that are aimed to be applied in situ or used as 3D scaffolds. Thiol–ene reactions are a class of click transformations that involve free-radical-mediated addition of electron-rich thiol groups to electron-poor carbon–carbon double bonds. When tuned with homopolymerization of the carbon–carbon double bonds, the resultant hydrogel properties can be finely adjusted. In this review, commonly used methods for modifying polymers with thiol groups or double bonds are discussed, and strategies to overcome flaws in thiol–ene hydrogels are provided. Emphasis is given to the application and outlook of thiol–ene cross-linked hydrogels.

Triglyceride Saturation in Patients at Risk of NASH and NAFLD: A Cross-Sectional Study

Chemical shift magnetic resonance imaging (MRI) is commonly used to estimate the amount of fat in tissues, namely the proton density fat fraction (PDFF). In addition to PDFF, the type of fat can be inferred and characterized in terms of the number of double bonds (NDB), number of methylene-interrupted double bonds (NMIDB) and the chain length (CL) of the fatty acid chains. The saturation index is potentially a marker for metabolic disorders. This study assesses the feasibility of estimating these parameters independently or in a constrained manner. Correlations with spectroscopy were measured in 109 subjects’ subcutaneous and visceral fat depots (p = 2 × 10−28), and with the NAFLD Activity Score (NAS) from histological evaluation of biopsies. The findings indicate that imaging estimates are comparable to spectroscopy (p = 0.0002), but there is no significant association of NDB with NAS (p = 0.1).

Reductive Hydroformylation of Isosorbide Diallyl Ether

Isosorbide and its functionalized derivatives have numerous applications as bio-sourced building blocks. In this context, the synthesis of diols from isosorbide diallyl ether by hydrohydroxymethylation reaction is of extreme interest. This hydrohydroxymethylation, which consists of carbon-carbon double bonds converting into primary alcohol functions, can be obtained by a hydroformylation reaction followed by a hydrogenation reaction. In this study, reductive hydroformylation was achieved using isosorbide diallyl ether as a substrate in a rhodium/amine catalytic system. The highest yield in bis-primary alcohols obtained was equal to 79%.

Betaine formation from the reactions of N-heterocyclic carbenes with polarized alkenes

N-heterocyclic carbenes [1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene 1a (IMes) or 1,3-bis(2,6-di-iso-propylphenyl)imidazolidene 1b (SIPr)] react with the polarized alkenes 2 and 4 to form the crystalline betaines 3a, 3b and 5a. Furthermore, a one-pot reaction between an aldehyde, malonitrile, and an imidazolium salt of an N-heterocyclic carbene has been developed for the efficient preparation of betaine 5a without isolation of the free carbene. Full characterization data, including X-ray crystal structures, is reported for the three synthesized betaines. The structures of the betaines 3a, 3b and 5a shed new light on the initial products formed in the reactions between N-heterocyclic carbenes and compounds containing polarized double bonds.

KINETICS OF FORMATION AND PROPERTIES OF PHOTOCURED SIMULTANEOUS EPOXY-ACRYLATE IPNS WITH THE PREVAILING CONTENT OF AN EPOXY COMPONENT

The distinct features of UV induced polymerization of epoxy-acrylate blends leading to the formation of simultaneous interpenetrating polymer networks (IPNs) have been studied. Different ratios of components within a prevailing content of an epoxy one have been used for the synthesis. Such a content of epoxy monomer is required to create a barrier preventing oxygen diffusion into a curing sample. It allows retardation of the well-known oxygen-inhibition effect, which acrylate monomers are susceptible to. Hence, the conduction of their polymerization in open-air conditions is possible. The proceeding of the polymerization reactions of acrylate (TEGDM) via free radical mechanism and of epoxy (UP-650D) via cationic one have been monitored by FTIR-spectroscopy. Namely, the conversion degrees have been calculated for double bonds of TEGDM and for epoxy groups of UP-650D respectively. A mixture of triphenylsulfonium hexafluorophosphate salts, which is capable of generating both free radical and cationic reactive species, have been used as a single photoinitiator for the formulations being investigated. Almost complete conversion of acrylate double bonds was reached after 60 min of UV irradiation irrespective of epoxy content. On the contrary, conversion of epoxy groups of aliphatic epoxy, which is known to be rather unreactive towards cationic photopolymerization, when mixed may be either higher or lower compared to the neat epoxy network. Such results are attributed to dual influence of acrylate network on the formation of epoxy one. Firstly, cationic polymerization of epoxy component is sensitized by acrylate macroradicals in terms of free radical promoted cationic polymerization. On the other hand, the mobility of epoxy macrocations is restricted by the rapid build-up of acrylate network. At the weight ratio of UP-650D and TEGDM 70/30 the sensitizing effect of acrylate is revealed to be dominant, so the given composition may be considered as optimal. Regardless of low conversion of epoxy groups, the content of the estimated gel fraction is high, and the epoxy component is found not to be leached in the process of extraction in acetone. Furthermore, physicomechanical properties of obtained UV-cured IPNs have been investigated. The results of the measurements, namely, impact resistance by the Gardner test, crosshatch adhesion test to different substrates (including silicon), and accelerated weathering test in a climatic chamber, show that all the samples exhibit good operational properties essential for effective protecting coatings of outdoor exposure.

Catalytic, contra-Thermodynamic Alkene Isomerization

The positional isomerization of C–C double bonds is a powerful strategy for the interconversion of alkene regioisomers. However, existing methods provide access to thermodynamically more stable isomers from less stable starting materials. Here we report the discovery of a dual catalyst system that promotes contra-thermodynamic positional alkene isomerization under photochemical irradiation, providing access to terminal alkene isomers directly from conjugated, internal alkene starting materials. The utility of the method is demonstrated in the deconjugation of diverse electron rich/poor alkenes and through strategic application to natural product synthesis. Mechanistic studies are consistent with a regiospecific bimolecular homolytic substitution (SH2') mechanism proceeding through an allyl-cobaloxime intermediate.

Evaluation and improvement of the oxidative stability of leather fatliquors

Fatliquor oxidation may give leather unpleasant odor, and excessive amounts of Cr(VI) and volatile organic compounds. The accurate evaluation and improvement of the oxidative stability of fatliquors are of great significance to high-quality leather manufacturing. We proposed a set of practical methods for evaluating the oxidative stability of fatliquors on the basis of oxidation induction time, change in iodine value (∆ IV), and change in acid value (∆ AV) under accelerated oxidation conditions (at 100 °C with 10 L/h of air). Oxidation induction time is a highly sensitive marker for quantifying the oxidative stability of fatliquors, and ∆ IV and ∆ AV that are low cost and easy to operate are useful in evaluating the oxidative stability of fatliquors when the oxidation induction time is less than 22 h. The number of double bonds in fatliquors is an important factor affecting oxidative stability. The sulfation modification of fatliquors that greatly reduces double bonds and the addition of antioxidants, especially butylated hydroxyanisole and butylated hydroxytoluene, markedly improve oxidative stability of fatliquors.

Visible Light Promoted Metal Free Sustainable Reduction of Activated Carbon-Carbon Double Bonds Without Any External Reductant

Visible light promoted chemo-selective metal free hydrogenation of activated double bond has been achieved via photoredox catalysis. Eosin Y has proved to an efficient catalyst for the effective reduction of C-C double bonds of isatins, oxindoles and maleimides under visible light. The method worked efficiently without the aid of any external reductants. Commercially viable DIPEA has been employed as a sacrificial electron donor and it’s in-situ generated cationic radical acts as reductant in this transformation. The method proved to be practical as a broad range of substrates containing activated double bond were easily reduced. The method proved to be scalable on a gram scale and the reduced product has been utilized successfully for the further synthetic application. The systematic and detailed mechanistic studies reveal the reductive quenching of the photocatalyst by the activated double bond.

Can Spectrophotometry Be Used to Quantify Zingiberene Sesquiterpenoids in Tomato Leaflet Extracts?

The presence of 7-epi zingiberene in wild tomatoes has been associated with arthropod resistance. Consequently, tomato breeders are attempting to introgress 7-epi zingiberene from wild to cultivated tomato requiring quantification of zingiberene. 7-Epi zingiberene likely absorbs UV light due to its conjugated double bonds and others have claimed that measurement of absorbance at 270 nm of tomato leaflet washes can be used to quantify zingiberene. However, this claim has never been critically evaluated. We initially evaluated this claim in an interspecific hybrid tomato generation that was segregating widely for zingiberene. Results indicated that the method does not obey the Beer–Lambert law. Consequently, we examined in detail aspects of the UV-absorbance of isolated zingiberenoids and leaflet washes obtained from parents and interspecific generations that were segregating for 7-epi zingiberene. Results indicated that isolated zingiberenoids, as well as leaflet washes containing zingiberenoids, have broad absorbance spectra with a λmax of 264 nm. For isolated zingiberenoids, the relationship between abundance and absorbance at 264 nm did obey the Beer–Lambert law. Average absorbance spectra for leaflet washes from interspecific generation plants showed subtle λmax shifts. Furthermore, the relationship between absorbance at 264 nm and zingiberenoid content of these generations did not obey the Beer–Lambert law. The use of multiple wavelengths for estimation of zingiberenoids in these breeding generations was explored and the inclusion of additional absorbances at one or two wavelengths always improved estimates. However, identified wavelength(s) differed among generations. Taken together, the results indicate that measurement of absorbance of tomato leaflet washes at a single wavelength is not a reliable quantitative estimate of zingiberenoids in leaflet washes. Estimates can be improved by utilizing absorbance at multiple wavelengths, but the particular wavelengths will vary among generations. Lastly, measurement of absorbance may be useful for identifying those relatively rare individuals in a generation that is widely segregating for zingiberenoid content. However, even in this situation, the determination of the actual 7-epi zingiberene content would need to be backstopped by a valid quantitative method.