On the Fundamental Polymer Chemistry of Inverse Vulcanization for Statistical and Segmented Copolymers from Elemental Sulfur

In this concept review, the fundamental and polymerization chemistry of inverse vulcanization for the preparation of statistical and segmented sulfur copolymers, which have been actively developed and advanced in various applications over the past decade is discussed. This concept review delves into a discussion of step-growth polymerization constructs to describe the inverse vulcanization process and discuss prepolymer approaches for the synthesis of segmented sulfur polyurethanes. Furthermore, this concept review discusses the advantages of inverse vulcanization in conjunction with dynamic covalent polymerization and post-polymerization modifications to prepare segmented block copolymers with enhanced thermomechanical and flame retardant properties of these materials.     

从知识传授到育人:高职“生活中的化学”教学实践*

深挖高职院校公选课“生活中的化学”的育人元素,精心设计教学内容,运用课堂主题辩论、趣味生活实验的设计与展示、探秘生活中的化学等理论知识传授与课内外实践相结合的教学方式,实现全过程育人,充分展现了公选课在立德树人方面的价值。     

Regularity of optimal sets for some functional involving eigenvalues of an operator in divergence form

In this paper we consider minimizers of the functional$\min \{{\lambda }_1(\mathrm{\Omega })+\cdots +{\lambda }_k(\mathrm{\Omega })+\mathrm{\Lambda }|\mathrm{\Omega }|,:\mathrm{\Omega }\subset D\text{ open}\}$ where $D\subset {\mathbb{R}}^d$ is a bounded open set and where $0<{\lambda }_1(\mathrm{\Omega })\le \cdots \le {\lambda }_k(\mathrm{\Omega })$ are the first k eigenvalues on Ω of an operator in divergence form with Dirichlet boundary condition and with Hölder continuous coefficients. We prove that the optimal sets ${\mathrm{\Omega }}^{⁎}$ have finite perimeter and that their free boundary $\partial {\mathrm{\Omega }}^{⁎}\cap D$ is composed of a regular part, which is locally the graph of a $C^{1,\alpha }$-regular function, and a singular part, which is empty if $d<d^{⁎}$, discrete if $d=d^{⁎}$ and of Hausdorff dimension at most $d-d^{⁎}$ if $d>d^{⁎}$, for some $d^{⁎}\in \{5,6,7\}$.     

Visible light-driven acridone catalysis for atom transfer radical polymerization

Acridone as a new kind of visible light photocatalyst has been developed to catalyze metal free atom transfer radical polymerization (ATRP). The photocatalyst possess low excited state potential as can undergo an oxidative quenching pathway to initiate ATRP of vinyl monomers. Kinetic study and light on/off reaction demonstrate the “living”/controlled nature of the polymerization by light. Block copolymers can be achieved by using PMMA as macroinitiator to reinitiate polymerization of other vinyl monomers, which shows highly preserved Br chain-end functionality in the synthesized polymers. Moreover, the polymerization can be conducted under air atmosphere as most photocatalysts need anaerobic condition, which may give inspiration of further application of this kind of photocatalyst.     

Hydrophobic Monomers Recognize Microenvironments in Hydrogel Microspheres during Free-Radical-Seeded Emulsion Polymerization

The three-dimensional structure of nanocomposite microgels was precisely determined by cryo-electron micrography. Several nanocomposite microgels that differ with respect to their nanocomposite structure, which were obtained from seeded emulsion polymerization in the presence of microgels, were used as model nanocomposite materials for cryo-electron micrography. The obtained three-dimensional segmentation images of these nanocomposite microgels provide important insights into the interactions between the hydrophobic monomers and the microgels, that is, hydrophobic styrene monomers recognize molecular-scale differences in polarity within the microgels during the emulsion polymerization. This result led to the formation of unprecedented multi-layered nanocomposite microgels, which promise substantial potential in colloidal applications.     

A Far-Red Emitting Fluorescent Chemogenetic Reporter for In Vivo Molecular Imaging

Far-red emitting fluorescent labels are highly desirable for spectral multiplexing and deep tissue imaging. Here, we describe the generation of frFAST (far-red Fluorescence Activating and absorption Shifting Tag), a 14-kDa monomeric protein that forms a bright far-red fluorescent assembly with (4-hydroxy-3-methoxy-phenyl)allylidene rhodanine (HPAR-3OM). As HPAR-3OM is essentially non-fluorescent in solution and in cells, frFAST can be imaged with high contrast in presence of free HPAR-3OM, which allowed the rapid and efficient imaging of frFAST fusions in live cells, zebrafish embryo/larvae, and chicken embryos. Beyond enabling the genetic encoding of far-red fluorescence, frFAST allowed the design of a far-red chemogenetic reporter of protein–protein interactions, demonstrating its great potential for the design of innovative far-red emitting biosensors.     

Malononitrile-involved Michael addition polymerization: An efficient and facile route for cyano-rich polyesters with programmable thermal and mechanical properties

An efficient, atom-economic, oxygen-tolerant, and water-tolerant strategy has been established to synthesize cyano-rich polyesters. Four kinds of organic bases, 1,1,3,3-tetramethylguanidine (TMG), 4-dimethylaminopyridine, triethylamine, and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) were explored for accelerating Michael addition polymerization of malononitrile and 1,4-butandiol diacrylate. TMG can promote the polymerization efficiently under mild conditions to quantitatively afford polyester with high-molecular weight and moderate polydispersity. The comparison of the kinetic studies of TMG and TBD reveals that TMG shows better catalytic performance, while the catalysis of TBD brings about oligomers in spite of the higher efficiency at early age of the polymerization. Moreover, other diacrylate compounds could also be quantitatively polymerized to afford polyesters with high molecular weight. When dimethacrylate is chose as the monomer, the polymerization becomes sluggish. All the afforded polyesters display programmable thermal and mechanical properties that are closely related to their chemical structures.     

Mechanistic Aspects of a Highly Active Dinuclear Zinc Catalyst for the Co‐polymerization of Epoxides and CO2

The dinuclear zinc complex reported by us is to date the most active zinc catalyst for the co‐polymerization of cyclohexene oxide (CHO) and carbon dioxide. However, co‐polymerization experiments with propylene oxide (PO) and CO₂ revealed surprisingly low conversions. Within this work, we focused on clarification of this behavior through experimental results and quantum chemical studies. The combination of both results indicated the formation of an energetically highly stable intermediate in the presence of propylene oxide and carbon dioxide. A similar species in the case of cyclohexene oxide/CO₂ co‐polymerization was not stable enough to deactivate the catalyst due to steric repulsion.     

Computational Design of Novel Allosteric Inhibitors for Plasmodium falciparum DegP

The serine protease, DegP exhibits proteolytic and chaperone activities, essential for cellular protein quality control and normal cell development in eukaryotes. The P. falciparum DegP is essential for the parasite survival and required to combat the oscillating thermal stress conditions during the infection, protein quality checks and protein homeostasis in the extra-cytoplasmic compartments, thereby establishing it as a potential target for drug development against malaria. Previous studies have shown that diisopropyl fluorophosphate (DFP) and the peptide SPMFKGV inhibit E. coli DegP protease activity. To identify novel potential inhibitors specific to PfDegP allosteric and the catalytic binding sites, we performed a high throughput in silico screening using Malaria Box, Pathogen Box, Maybridge library, ChEMBL library and the library of FDA approved compounds. The screening helped identify five best binders that showed high affinity to PfDegP allosteric (T0873, T2823, T2801, {"type":"entrez-protein","attrs":{"text":"RJC02337","term_id":"1480409465","term_text":"RJC02337"}}RJC02337, CD00811) and the catalytic binding site (T0078L, T1524, T2328, BTB11534 and 552691). Further, molecular dynamics simulation analysis revealed {"type":"entrez-protein","attrs":{"text":"RJC02337","term_id":"1480409465","term_text":"RJC02337"}}RJC02337, BTB11534 as the best hits forming a stable complex. WaterMap and electrostatic complementarity were used to evaluate the novel bio-isosteric chemotypes of {"type":"entrez-protein","attrs":{"text":"RJC02337","term_id":"1480409465","term_text":"RJC02337"}}RJC02337, that led to the identification of 231 chemotypes that exhibited better binding affinity. Further analysis of the top 5 chemotypes, based on better binding affinity, revealed that the addition of electron donors like nitrogen and sulphur to the side chains of butanoate group are more favoured than the backbone of butanoate group. In a nutshell, the present study helps identify novel, potent and Plasmodium specific inhibitors, using high throughput in silico screening and bio-isosteric replacement, which may be experimentally validated.