Tuning Electrical- and Photo-Conductivity by Cation Exchange within a Redox-Active Tetrathiafulvalene-Based Metal–Organic Framework

To activate electronic and optical functions of the redox-active metal–organic framework, (Me₂NH₂)[In^III(TTFTB)]⋅0.7 C₂H₅OH⋅DMF (Me₂NH₂@ 1 , TTFTB=tetrathiafulvalene-tetrabenzoate, DMF=N,N-dimethylformamide), has been exchanged by tetrathiafulvalenium (TTF^.+) and N,N′-dimethyl-4,4′-bipyridinium (MV²⁺). These cations provide electron carriers and photosensitivity. The exchange retains the crystallinity allowing single-crystal to single-crystal post-synthetic transformation to TTF@ 1 and MV@ 1 . Both TTF^.+ and MV²⁺ enhance the electrical conductivity by a factor of 10² and the visible light induced photocurrent by 4 and 28 times, respectively. EPR evidences synergetic effect involving charge transfer between the framework redox-active TTFTB bridges and MV²⁺. The results demonstrate that functionalization of MOF by cation exchange without perturbing the crystallinity extends possibilities to achieve switchable materials.     

Green synthesis,characterization, and biological activities of saffron leaf extract-mediated zinc oxide nanoparticles: A sustainable approach to reuse an agricultural waste

To increase the profitability and sustainability of agricultural waste, a facile green approach was established to synthesize zinc oxide nanoparticles (ZnO NPs) using saffron leaf extract as a reducing and stabilizing agent. Structural characteristics of NPs were investigated by X-ray diffraction (XRD), Fourier-transform infrared (FTIR), field emission scanning electron microscopy (FESEM), and UV–Visible (UV–Vis) spectroscopy. Characterization results revealed that ZnO NPs is highly crystalline with a hexagonal wurtzite structure and spherical particles with diameter less than 50 nm, as confirmed by XRD and FESEM techniques. UV–Vis absorption spectra depicted an absorption peak at 370 nm, which confirms the formation of ZnO NPs. FTIR spectral analysis confirmed the presence of functional groups and metal oxygen groups. The biological activities of ZnO NPs were also investigated. The antibacterial effect of ZnO NPs was investigated against selected food pathogens (Salmonella Typhimurium, Listeria monocytogenes, and Enterococcus faecalis). The study results prove that the green synthesized ZnO NPs show enhanced antibacterial activity against S. Typhimurium when compared with other strains. A dose-dependent free radical scavenging activity was observed for ZnO NPs in both 2,2-diphenyl-1-picryl-hydrazyl-hydrate (DPPH) and fluorescence recovery after photobleaching (FRAP) assays. The ZnO NPs were evaluated for their photocatalytic activity during the degradation of methylene blue (MB) dye in aqueous solutions. The maximum removal of MB achieved was 64% with an initial ZnO NP concentration of 12 mg/mL under UV light. The present study revealed that the agricultural waste (saffron leaf) provides a simple and eco-friendly option to sustainably synthesize ZnO NPs for use as a photocatalyst. In addition, this is the first report on saffron leaf-mediated synthesis of ZnO NPs.     

Synthesis of Honeycomb-Structured Beryllium Oxide via Graphene Liquid Cells

Using high-resolution transmission electron microscopy and electron energy-loss spectroscopy, we show that beryllium oxide crystallizes in the planar hexagonal structure in a graphene liquid cell by a wet-chemistry approach. These liquid cells can feature van-der-Waals pressures up to 1 GPa, producing a miniaturized high-pressure container for the crystallization in solution. The thickness of as-received crystals is beyond the thermodynamic ultra-thin limit above which the wurtzite phase is energetically more favorable according to the theoretical prediction. The crystallization of the planar phase is ascribed to the near-free-standing condition afforded by the graphene surface. Our calculations show that the energy barrier of the phase transition is responsible for the observed thickness beyond the previously predicted limit. These findings open a new door for exploring aqueous-solution approaches of more metal-oxide semiconductors with exotic phase structures and properties in graphene-encapsulated confined cells.     

新型共价交联纳米胶囊的构筑、调控与功能

利用共价自组装的方法，将刚性组装基元与柔性链在一定条件下进行横向交联，可以方便地制备出单层高分子纳米胶囊.相比于传统的非共价超分子囊泡，这种新型的共价纳米胶囊具有结构稳定、尺度可控且分散性优异等诸多优点.因此，如何利用化学合成的手段来制备新型的纳米胶囊，并进一步实现对其结构调控和性能的探究具有十分重要的意义.针对这些问题，分别发展了功能化的柱[5]芳烃、四苯乙烯、卟啉、三嗪、苯硼酸酐等不同类型构筑基元，并使之与两端具有活性位点的柔性烷基链在适当的溶剂中进行聚合反应，最终获得了一系列的共价纳米胶囊.通过对其结构的修饰和调控，发现这些功能化的高分子纳米胶囊在光捕获、人工酶、抗菌材料以及药物载体等领域具有诸多潜在应用价值.未来，新型共价高分子纳米胶囊的开发、功能化以及应用有望得到进一步的拓展.     

Solubilization of silica nanoparticles in alkanes and poly(α-olefin)s by functionalized polyisobutylene oligomers

Covalent and noncovalent chemical methods that use oligomeric lipophilic agents to solubilize silica nanoparticles in heptane and poly(α-olefin) (EPAO) solvents are described. While only modest solubilization efficiencies are seen with an octadecyl group, a variety of terminally functionalized polyisobutylene (PIB) derivatives are more efficient. Both covalent and noncovalent chemistry was found to be effective. Covalent modification solubilized up to 34 wt% of silica nanoparticles (SiNPs) as stable solutions in heptane or PAOs. Noncovalent modification was however more effective, solubilizing up to 70% of SiNPs in heptane or PAOs. The most successful covalent approach used PIB oligomers containing terminal triethoxysilane groups to covalently modify SiNPs. Alternatively, SiNPs that were first functionalized with amine groups could be solubilized in heptane or PAOs with polyisobutylene containing sulfonic acid groups using acid–base chemistry. Studies of these and other solubilization chemistry was also carried out using fluorescent labels, studies that confirmed the gravimetric analyses of the heptane-solubilized SiNPs. Transmission electron microscopy of a PAO solution of these solutions showed that these SiNPs were present as small aggregates dispersed in the PAOs.     

Efficient synthesis of branched poly(acrylic acid) derivatives via postpolymerization modification

The utility of pentafluorophenyl esters for the selective introduction of functional units and branch points in well-defined poly(acrylic acid) (PAA) derivatives is demonstrated using a combination of controlled radical polymerization and postpolymerization modification. Reversible addition-fragmentation chain transfer enables the synthesis of well-defined copolymers—poly(pentafluorophenyl acrylate-co-tert-butyl acrylate)—with the active ester repeat units serving as attachment points for reaction with primary amines, specifically tris(2-(t-butoxycarbonyl)ethyl)methyl amine (Behera's amine). Deprotection using trifluoroacetic acid removes both the backbone and side chain t-butyl esters to give a series of branched PAA derivatives containing novel tricarboxylic acid side chains that are well suited to complexation and multidentate interactions. Surprisingly, the active ester homopolymer is shown to have the highest reactivity with Behera's amine when compared to copolymers with lower incorporation of pentafluorophenyl esters, suggesting an intriguing interplay of neighboring group effects and steric interactions. The ability to tune the efficiency of postpolymerization modification gives a library of PAA derivatives.     

A Facile Method for the Separation of Methionine Sulfoxide Diastereomers,Structural Assignment,and DFT Analysis

Methionine (Met) oxidation is an important biological redox node, with hundreds if not thousands of protein targets. The process yields methionine oxide (MetO). It renders the sulfur chiral, producing two distinct, diastereomerically related products. Despite the biological significance of Met oxidation, a reliable protocol to separate the resultant MetO diastereomers is currently lacking. This hampers our ability to make peptides and proteins that contain stereochemically defined MetO to then study their structural and functional properties. We have developed a facile method that uses supercritical CO₂ chromatography and allows obtaining both diastereomers in purities exceeding 99 %. ¹H NMR spectra were correlated with X-ray structural information. The stereochemical interconversion barrier at sulfur was calculated as 45.2 kcal mol⁻¹, highlighting the remarkable stereochemical stability of MetO sulfur chirality. Our protocol should open the road to synthesis and study of a wide variety of stereochemically defined MetO-containing proteins and peptides.     

The ABC of Insulin: The Organic Chemistry of a Small Protein

Insulin is a small protein crucial for regulating the blood glucose level in all animals. Since 1922 it has been used for the treatment of patients with diabetes. Despite consisting of just 51 amino acids, insulin contains 17 of the proteinogenic amino acids, A- and B-chains, three disulfide bridges, and it folds with 3 α-helices and a short β-sheet segment. Insulin associates into dimers and further into hexamers with stabilization by Zn²⁺ and phenolic ligands. Selective chemical modification of proteins is at the forefront of developments in chemical biology and biopharmaceuticals. Insulin's structure has made it amenable to organic and inorganic chemical reactions. This Review provides a synthetic organic chemistry perspective on this small protein. It gives an overview of key chemical and physico-chemical aspects of the insulin molecule, with a focus on chemoselective reactions. This includes N-acylations at the N-termini or at Lys^B29 by pH control, introduction of protecting groups on insulin, binding of metal ions, ligands to control the nano-scale assembly of insulin, and more.     

Conformational Studies of Oligosaccharides

The conformation of a molecule strongly affects its function, as demonstrated for peptides and nucleic acids. This correlation is much less established for carbohydrates, the most abundant organic materials in nature. Recent advances in synthetic and analytical techniques have enabled the study of carbohydrates at the molecular level. Recurrent structural features were identified as responsible for particular biological activities or material properties. In this Minireview, recent achievements in the structural characterization of carbohydrates, enabled by systematic studies of chemically defined oligosaccharides, are discussed. These findings can guide the development of more potent glycomimetics. Synthetic carbohydrate materials by design can be envisioned.