Cellulose as recyclable organocatalyst for ipso-hydroxylation of arylboronic acids

Cellulose catalyzed oxidative hydroxylation of aryl and hetero-arylboronic acids to the corresponding phenols under metal and base free strategy has been demonstrated. The sustainable ipso-hydroxylation takes place using hydrogen peroxide as an oxidant in water under mild condition in shorter period of time. Interestingly, easy recovery and reusability of heterogeneous catalyst without significant loss in catalytic yield makes the protocol environmentally benign.     

Miktoarm star‐shaped poly(lactic acid) copolymer: Synthesis and stereocomplex crystallization behavior

The miktoarm star‐shaped poly(lactic acid) (PLA) copolymer, (PLLA)₂‐core‐(PDLA)₂, was synthesized via stepwise ring‐opening polymerization of lactide with dibromoneopentyl glycol as the starting material. ¹H NMR and FTIR spectroscopy proved the feasibility of synthetic route and the successful preparation of star‐shaped PLA copolymers. The results of FTIR spectroscopy and XRD showed that the stereocomplex structure of the copolymer could be more perfect after solvent dissolution treatment. Effect of chain architectures on crystallization was investigated by studying the nonisothermal and isothermal crystallization of the miktoarm star‐shaped PLA copolymer and other stereocomplexes. Nonisothermal differential scanning calorimetry and polarizing optical microscopy tests indicated that (PLLA)₂‐core‐(PDLA)₂ exhibited the fastest formation of a stereocomplex in a dynamic test due to its special structure. In isothermal crystallization tests, the copolymer exhibited the fast crystal growth rate and the most perfect crystal morphology. The results reveal that the unique molecular structure has an important influence on the crystallization of the miktoarm star‐shaped PLA copolymer. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 814–826     

Fast,Facile and Solvent-Free Dry-Melt Synthesis of Oxovanadium(IV) Complexes: Simple Design with High Potency towards Cancerous Cells

A range of oxobis(phenyl-1,3-butanedione) vanadium(IV) complexes have been successfully synthesized from cheap starting materials and a simple and solvent-free one-pot dry-melt reaction. This direct, straightforward, fast and alternative approach to inorganic synthesis has the potential for a wide range of applications. Analytical studies confirm their successful synthesis, purity and solid-state coordination, and we report the use of such complexes as potential drug candidates for the treatment of cancer. After a 24 hour incubation of A549 lung carcinoma cells with the compounds, they reveal cytotoxicity values elevenfold greater than cisplatin and remain non-toxic towards normal cell types. Additionally, the complexes are stable over a range of physiological pH values and show the potential for interactions with bovine serum albumin.     

High-Throughput Synthesis and Characterization of Aryl Silicones by Using the Piers–Rubinsztajn Reaction

Arylsilicones are widely exploited for their thermal and optical properties. The creation of phenylsilicone elastomers with specific physical properties is typically done by a “one-off” formulation and test process. Herein, it is demonstrated that high-throughput synthesis methods can be used to rapidly prepare a series of arylsilicone elastomers and then the relative impact of different aryl groups on their physical properties is assessed. Aromatic groups were incorporated into polydimethylsiloxane (PDMS) elastomers by exploiting the relative reactivity of different functional groups in the Piers–Rubinsztajn reaction. To analyze trends in the silicone mechanical properties as a function of increasing aryl concentration—structure/property relationships—libraries of elastomers were both quickly synthesized and characterized by using high-throughput suites starting from low viscosity silicone oils/monomers in 96-well plates. Liquid handling parameters were optimized to effectively work with the silicones. Incorporating aryl instead of alkyl crosslinkers into the PDMS backbone increased the silicone elastomer modulus by approximately 50 % (at a crosslink density of 6 %); elastomers prepared with an aromatic crosslinker with three contact points led to much higher moduli compared with those with one contact point at the same crosslink density. When located at precise rather than random points on the silicone chains, diphenylsilicones had lower moduli than analogous monophenylsilicones.     

Total Synthesis of Callyspongiolide,Part 2: The Ynoate Metathesis/cis-Reduction Strategy

The macrocyclic core of the cytotoxic marine natural product callyspongiolide ( 1 ) was forged by ring-closing alkyne metathesis (RCAM) of an ynoate precursor using a molybdenum alkylidyne complex endowed with triarylsilanolate ligands as the catalyst. This result is remarkable in view of the failed attempts documented in the literature at converting electron deficient alkynes with the aid of more classical catalysts. The subsequent Z-selective semi-reduction of the resulting cycloalkyne by hydrogenation over nickel boride required careful optimization in order to minimize overreduction and competing dehalogenation of the compound's alkenyl iodide terminus as needed for final attachment of the side chain of 1 by Sonogashira coupling. The required cyclization precursor itself was prepared via Kocienski olefination.     

Exploring the Phase-Selective,Green, Hydrothermal Synthesis of Upconverting Doped Sodium Yttrium Fluoride: Effects of Temperature,Time, and Precursors

The aim of this work was i) to develop a hydrothermal, low-temperature synthesis protocol affording the upconverting hexagonal phase NaYF₄ with suitable dopants while adhering to the “green chemistry” standards and ii) to explore the effect that different parameters have on the products. In optimizing the synthesis protocol, short reaction times and low temperatures (below 150 °C) were considered. Yb³⁺ and Er³⁺ ions were chosen as dopants for the NaYF₄ material. Within the context of the second goal, parameters including nature of the precursors, treatment temperature, and treatment time were investigated to afford a pure hexagonal crystalline phase, both in the doped and undoped materials. To fully explore the synthesis results, the prepared materials were characterized from a structural (XRD), compositional (XPS, ICP-MS), and morphological (SEM) point of view. The upconverting properties of the compounds were confirmed by photoluminescence measurements.     

Introducing the Petasis Reaction for Late‐Stage Multicomponent Diversification,Labeling, and Stapling of Peptides

For the first time, the Petasis (borono‐Mannich) reaction is employed for the multicomponent labeling and stapling of peptides. The report includes the solid‐phase derivatization of peptides at the N‐terminus, Lys, and N^?‐MeLys side‐chains by an on‐resin Petasis reaction with variation of the carbonyl and boronic acid components. Peptides were simultaneously functionalized with aryl/vinyl substituents bearing fluorescent/affinity tags and oxo components such as dihydroxyacetone, glyceraldehyde, glyoxylic acid, and aldoses, thus encompassing a powerful complexity‐generating approach without changing the charge of the peptides. The multicomponent stapling was conducted in solution by linking N^?‐MeLys or Orn side‐chains, positioned at i, i+7 and i, i+4, with aryl tethers, while hydroxy carbonyl moieties were introduced as exocyclic fragments. The good efficiency and diversity oriented character of these methods show prospects for peptide drug discovery and chemical biology.     

原位合成Bi3O4Br/Bi12O17Br2光催化剂及其对磺胺甲噁唑降解性能

Bi_xO_yBr_z光催化剂在有机药物废水处理领域有着非常广阔的潜在应用价值,但因光生电子和空穴的快速复合而表现出较低的光催化效率,进而限制了其应用范围。通过简易的水解-焙烧法原位制得一种新型的Bi₃O₄Br/Bi₁₂O₁₇Br₂复合光催化剂,并以磺胺甲噁唑(SMX)为模拟药物污染物进行了光催化性能测试,对所制催化剂进行了X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电子显微镜(SEM)、紫外可见漫反射光谱(UV-Vis DRS)、电化学阻抗(EIS)、光致发光光谱(PL)等表征。结果表明所制备的Bi₃O₄Br/Bi₁₂O₁₇Br₂复合光催化剂具有较强的光生载流子分离率、较低的界面电荷转移电阻,进而展示出优异的光催化降解SMX性能,在模拟太阳光下照射30 min,SMX降解率达到87%,相较于纯的Bi₃O₄Br和Bi₁₂O₁₇Br₂催化剂,降解率分别提升了30%和24%。最后基于自由基捕获实验和催化剂能带结构分析了所制催化剂的降解机理。     

Rh(III)-Catalyzed One-Step Synthesis of ortho-Alkynylated Perylene Imide Dyes: Optical and Electrochemical Properties of New Derivatives

A one-step Rh-catalyzed site-selective ortho-C−H alkynylation of perylene as well as naphthalene mono- and diimides is reported. A single step regioselective access to ortho-C−H alkynylated derivatives of these ryleneimides not only increases the step economy of the ortho-functionalization on these dyes but also provides a quick access route towards highly functionalized dyes that have potential optoelectronic applications. Increased solubility of tetra(triisopropylsilyl)acetylenyl PDIs in organic solvents greatly enhances their utility for further derivatization.     

Metal–Organic Framework (MOF)-Derived Carbon-Mediated Interfacial Reaction for the Synthesis of CeO2−MnO2 Catalysts

CeO₂-based catalysts are widely studied in catalysis fields. Developing one novel synthetic approach to increase the intimate contact between CeO₂ and secondary species is of particular importance for enhancing catalytic activities. Herein, an interfacial reaction between metal–organic framework (MOF)-derived carbon and KMnO₄ to synthesize CeO₂−MnO₂, in which carbon is derived from the pyrolysis of Ce-MOFs under an inert atmosphere, is described. The MOF-derived carbon is found to restrain the growth of CeO₂ crystallites under a high calcination temperature and, more importantly, intimate contact within CeO₂/C is conveyed to CeO₂/MnO₂ after the interfacial reaction; this is responsible for the high catalytic activity of CeO₂−MnO₂ towards CO oxidation.