Controlled Synthesis and Degradation of Poly(N‐(isobutoxymethyl) acrylamide) Homopolymers and Block Copolymers

The homopolymerization of the water‐insoluble N‐(isobutoxymethyl)acrylamide (IBMA) is investigated for the first time by nitroxide‐mediated polymerization. The homopolymerization is characterized by a linear increase in number average molecular weight (M_n) versus conversion (X) to X > 0.80 while maintaining dispersities of M_w/M_n < 1.30. A strong Arrhenius relationship correlates the apparent rate constants and the homopolymerization temperatures between 105 and 120 °C. All poly(IBMA) homopolymers are then successfully chain‐extended with styrene (S) to form well‐defined block copolymers of poly(IBMA)‐b‐poly(S) suggesting a high degree of livingness of the poly(IBMA) macroinitiators. Thermogravimetric analysis and differential scanning calorimetry are both used to characterize the thermal properties of the homopolymers and block copolymers and identify possible unique degradation of the poly(IBMA) block through imide formation at elevated temperatures.

     

and Au6 clusters: Superatomic molecules bearing an SP3‐hybrid Au6 core

The octahedral Au₆ core is explored for the formation of novel SP³‐hybrid superatomic molecules by considering and Au₆ clusters (X= F, Cl, Br, I). The bonding between the four capping atoms and the Au₆ core requires a combination of 1S and 1P shells of the core leading to a set of four equivalent hybrid orbitals. Thus, combining the superatom concept with both the Lewis structure model and VSEPR theory contributes to the rationalization of structure and bonding in metal clusters. For example, our results consider the Au₆ clusters as analogues of the simplest perhalogenated hydrocarbon, CX₄.     

Chemical applications of topology and group theory

The 60 even permutations of the ligands in the five-coordinate complexes, ML ₅, form the alternating group A ₅, which is isomorphic with the icosahedral pure rotation group I. Using this idea, it is shown how a regular icosahedron can be used as a topological representation for isomerizations of the five-coordinate complexes, ML ₅, involving only even permutations if the five ligands L correspond either to the five nested octahedra with vertices located at the midpoints of the 30 edges of the icosahedron or to the five regular tetrahedra with vertices located at the midpoints of the 20 faces of the icosahedron. However, the 120 total permutations of the ligands in five-coordinate complexes ML ₅ cannot be analogously represented by operations in the full icosahedral point group I _h, since I _his the direct product I×C₂ whereas the symmetric group S ₅ is only the semi-direct product A ₅S₂. In connection with previously used topological representations on isomerism in five-coordinate complexes, it is noted that the automorphism groups of the Petersen graph and the Desargues-Levi graph are isomorphic to the symmetric group S ₅ and to the direct product S ₅×S ₂, respectively. Applications to various fields of chemistry are briefly outlined.     

Segregation of tetracarbon units in low-energy tetracarbindane structures: Major differences from their aluminum and gallium analogs

The structures and energetics of the tetracarbindanes C₄In_n−4Me_n (n = 6-14) have been determined by density functional theory. In contrast to their aluminum and gallium analogs, the lowest energy tetracarbindanes typically have all four carbon atoms segregated into a single C₄ unit. Thus, linear C₄ units resembling butadiene are found in the lowest energy C₄In_n−4Me_n structures. In addition, some higher energy tetracarbindane structures have a structural feature not found in any of the corresponding tetracarbalanes and tetracarbagallanes, namely closed trapezoidal C₄ units resembling cyclobutene. Such trapezoidal C₄ units bind to the In_n−4 subcluster with the CC edge bonding to a single indium atoms as an olefin-metal or 3-center 2-electron bond. These differences may be attributed to the larger size of indium atoms (1.42 Å covalent radius) relative to gallium atoms (1.22 Å covalent radius).     

Measurement of adenosine, inosine and hypoxanthine in human term placenta by reversed-phase high-performance liquid chromatography

An analytical method was developed for measuring adenosine, inosine and hypoxanthine in freshly delivered human term placentas. Representative freeze-clamped samples were taken from the sub-maternal surface of each placenta. Acid-soluble extracts of the samples were analyzed by reversed-phase high-performance liquid chromatography on columns packed with 10-micron porous octadecylsilica, using gradient elution with a linear increase in methanol concentration in ammonium phosphate buffer. Resolution of hypoxanthine from xanthine and adenosine from adenine, and quantitation of hypoxanthine and adenosine were achieved using 0.05 M ammonium dihydrogen phosphate, pH 6.5, as the low-strength eluent. Resolution of inosine from a prominent peak of beta-NAD was optimized using 0.02 M ammonium dihydrogen phosphate, pH 5.6, as low-strength eluent. Recovery of standards was greater than 90%. Mean contents (+/- S.D.) of the analytes in placentas from seven normal deliveries were, adenosine 30.6 +/- 11.5 nmol/g, inosine 68.0 +/- 25.8 nmol/g and hypoxanthine 217 +/- 127.5 nmol/g.     

Thermal analysis of PMMA/gel silica glass composites

Thermal analysis of poly-methylmethacrylate (PMMA) impregnated porous gel silica glasses confirms that the PMMA chains form hydrogen bonds with the pore surface silanol groups. The adopted conditions for the insitu polymerisation result in about 4% of residual monomers trapped in the polymer, most of them in the amorphous structure. The polymer and monomer mixture takes up the whole of the free pore volume. Most of the residual monomer polymerises during the DSC scans above the glass transition temperature providing an excellent probe for the weak glass transition. Polymerisation in the gel silica glass medium affects the glass transition temperature, the length of polymer chains, and the degree of polymerisation.     

Bi4V2O11/石墨烯异质结光催化剂的制备及其在降解抗体污染物中应用

发展和设计高效、廉价和稳定的光催化剂用于抗生素污染物降解仍然存在巨大的挑战。 本文通过一种便捷的水热方法制备了Bi₄V₂O₁₁/石墨烯复合材料并用于可见光下抗生素污染物光催化降解。 通过自由基追踪实验,确认了光催化降解过程中活性物质为h⁺和·OH基团。 根据实验结果,提出了相应的反应机理。 石墨烯的引入可以有效地促进光生电子-空穴对的分离,从而增强光催化活性。 该复合催化剂展现出良好的活性和稳定性。 该方法以石墨烯为载体制备了光催化降解材料,为高性能光催化剂的制备提供了参考。     

Total Synthesis of Tambromycin by Combining Chemocatalytic and Biocatalytic C−H Functionalization

A combination of genomic and metabolomic approaches recently resulted in the identification of a nonribosomal tetrapeptide tambromycin, which possesses promising antiproliferative activity and several unusual structural features, including a densely substituted indole, a methyloxazoline ring, and an unusual pyrrolidine‐containing amino acid called tambroline. In this work, we identify a concise synthetic route to access tambromycin, which relies on the strategic use of biocatalytic and chemocatalytic C?H functionalization methods to prepare two key precursors to the natural product in an efficient and scalable manner. The success of our study highlights the benefits of applying the principles of biocatalytic retrosynthesis as well as C?H functionalization logic to the synthesis of complex molecular scaffolds.     

Terminal Hydride Species in [FeFe]‐Hydrogenases Are Vibrationally Coupled to the Active Site Environment

A combination of nuclear resonance vibrational spectroscopy (NRVS), FTIR spectroscopy, and DFT calculations was used to observe and characterize Fe?H/D bending modes in CrHydA1 [FeFe]‐hydrogenase Cys‐to‐Ser variant C169S. Mutagenesis of cysteine to serine at position 169 changes the functional group adjacent to the H‐cluster from a ‐SH to ‐OH, thus altering the proton transfer pathway. The catalytic activity of C169S is significantly reduced compared to that of native CrHydA1, presumably owing to less efficient proton transfer to the H‐cluster. This mutation enabled effective capture of a hydride/deuteride intermediate and facilitated direct detection of the Fe?H/D normal modes. We observed a significant shift to higher frequency in an Fe?H bending mode of the C169S variant, as compared to previous findings with reconstituted native and oxadithiolate (ODT)‐substituted CrHydA1. On the basis of DFT calculations, we propose that this shift is caused by the stronger interaction of the ‐OH group of C169S with the bridgehead ‐NH‐ moiety of the active site, as compared to that of the ‐SH group of C169 in the native enzyme.     

The configurational dependence of binding free energies: A Poisson–Boltzmann study of Neuraminidase inhibitors

The linear finite difference Poisson-Boltzmann (FDPB) equation is applied to the calculation of the electrostatic binding free energies of a group of inhibitors to the Neuraminidase enzyme. An ensemble of enzyme-inhibitor complex conformations was generated using Monte Carlo simulations and the electrostatic binding free energies of subtly different configurations of the enzyme-inhibitor complexes were calculated. It was seen that the binding free energies calculated using FDPB depend strongly on the configuration of the complex taken from the ensemble. This configurational dependence was investigated in detail in the electrostatic hydration free energies of the inhibitors. Differences in hydration energies of up to 7 kcal mol^–1 were obtained for root mean square (RMS) structural deviations of only 0.5 Å. To verify the result, the grid size and parameter dependence of the calculated hydration free energies were systematically investigated. This showed that the absolute hydration free energies calculated using the FDPB equation were very sensitive to the values of key parameters, but that the configurational dependence of the free energies was independent of the parameters chosen. Thus just as molecular mechanics energies are very sensitive to configuration, and single-structure values are not typically used to score binding free energies, single FDPB energies should be treated with the same caution.