Tailoring 3,3′‐Dihydroxyisorenieratene to Hydroxystilbene: Finding a Resveratrol Analogue with Increased Antiproliferation Activity and Cell Selectivity

Four novel compounds were designed by “tailoring” 3,3′‐dihydroxyisorenieratene (a natural carotenoid) based on an isoprene unit retention truncation strategy. Among them, the smallest molecule 1 (2,3,6,2′,3′,6′‐hexamethyl‐4,4′‐dihydroxy‐trans‐stilbene) was concisely synthesized in a one‐pot Stille–Heck tandem sequence, and surfaced as a promising lead molecule in terms of its selective antiproliferative activity mediated by blocking the NCI‐H460 cell cycle in G1 phase. Additionally, theoretical calculations and cell uptake experiments indicate that the unique polymethylation pattern of compound 1 significantly induces a conformational change shift out of planarity and increases its cell uptake and metabolic stability. The observation should be helpful to rationally design resveratrol‐inspired antiproliferative agents.     

Highly Enantioselective Catalytic System for Asymmetric Copolymerization of Carbon Dioxide and Cyclohexene Oxide

A new ligand can be easily prepared, and its intramolecular dinuclear zinc complexes act as a high performance catalyst for the asymmetric alternating copolymerization of cyclohexene oxide and CO₂ under very mild conditions (1 atm CO₂, room temperature), affording completely alternating polycarbonates with up to 93.8 % enantiomeric excess (ee) and 98 % yield. A high M_n value of 28 600 and a relatively narrow polydispersity (M_w/M_n ratio) of 1.43 were also achieved.     

Well‐Defined Iron Complexes as Efficient Catalysts for “Green” Atom‐Transfer Radical Polymerization of Styrene,Methyl Methacrylate,and Butyl Acrylate with Low Catalyst Loadings and Catalyst Recycling

Environmentally friendly iron(II) catalysts for atom‐transfer radical polymerization (ATRP) were synthesized by careful selection of the nitrogen substituents of N,N,N‐trialkylated‐1,4,9‐triazacyclononane (R₃TACN) ligands. Two types of structures were confirmed by crystallography: “[(R₃TACN)FeX₂]” complexes with relatively small R groups have ionic and dinuclear structures including a [(R₃TACN)Fe(μ‐X)₃Fe(R₃TACN)]⁺ moiety, whereas those with more bulky R groups are neutral and mononuclear. The twelve [(R₃TACN)FeX₂]_n complexes that were synthesized were subjected to bulk ATRP of styrene, methyl methacrylate (MMA), and butyl acrylate (BA). Among the iron complexes examined, [{(cyclopentyl)₃TACN}FeBr₂] ( 4 b ) was the best catalyst for the well‐controlled ATRP of all three monomers. This species allowed easy catalyst separation and recycling, a lowering of the catalyst concentration needed for the reaction, and the absence of additional reducing reagents. The lowest catalyst loading was accomplished in the ATRP of MMA with 4 b (59 ppm of Fe based on the charged monomer). Catalyst recycling in ATRP with low catalyst loadings was also successful. The ATRP of styrene with 4 b (117 ppm Fe atom) was followed by precipitation from methanol to give polystyrene that contained residual iron below the calculated detection limit (0.28 ppm). Mechanisms that involve equilibria between the multinuclear and mononuclear species were also examined.     

Synthesis,characterization and properties of novel cellulose derivatives containing phosphorus: cellulose diphenyl phosphate and its mixed esters

Using ionic liquid 1-allyl-3-methylimidazolium chloride as reaction medium, a series of novel cellulose esters containing phosphorus including cellulose diphenyl phosphate (C-Dp) and cellulose acetate (CA)–diphenyl phosphate mixed esters was synthesized homogeneously. The degree of substitution was well controlled by altering reaction conditions, such as the molar ratio of the acylating reagents/anhydroglucose unit and reaction time. The structure and thermal properties of cellulose esters were characterized by FTIR, NMR, wide-angle X-ray powder diffraction and differential scanning calorimetry. All the products possessed excellent solubility in some common organic solvents, and transparent films of cellulose esters were obtained by solution casting. In contrast to C-Dp, CA–diphenyl phosphate mixed esters showed clear glass transitions. More interestingly, these cellulose mixed esters exhibited thermoplastic behavior and could be processed by traditional melt processing methods.     

Roles of xyloglucan and pectin on the mechanical properties of bacterial cellulose composite films

Xyloglucan and pectin are major non-cellulosic components of most primary plant cell walls. It is believed that xyloglucan and perhaps pectin are functioning as tethers between cellulose microfibrils in the cell walls. In order to understand the role of xyloglucan and pectin in cell wall mechanical properties, model cell wall composites created using Gluconacetobacter xylinus cellulose or cellulose nanowhiskers (CNWs) derived there from with different amounts of xyloglucan and/or pectin have been prepared and measured under extension conditions. Compared with pure CNW films, CNW composites with lower amounts of xyloglucan or pectin did not show significant differences in mechanical behavior. Only when the additives were as high as 60 %, the films exhibited a slightly lower Young’s modulus. However, when cultured with xyloglucan or pectin, the bacterial cellulose (BC) composites produced by G. xylinus showed much lower modulus compared with that of the pure BC films. Xyloglucan was able to further reduce the modulus and extensibility of the film compared to that of pectin. It is proposed that surface coating or tethering of xyloglucan or pectin of cellulose microfibrils does not alone affect the mechanical properties of cell wall materials. The implication from this work is that xyloglucan or pectin alters the mechanical properties of cellulose networks during rather than after the cellulose biosynthesis process, which impacts the nature of the connection between these compounds.     

静电纺丝制备YVO4:Sm3+纳米纤维及其荧光光谱性能

采用静电纺丝技术与高温煅烧工艺相结合,以氧化钐、氧化钇、偏钒酸铵和聚丙烯腈为主要原料,制备稀土离子掺杂的YVO4:Sm3+纳米纤维。利用X射线衍射(XRD)、扫描电子显微镜(SEM)、傅立叶变换红外(FT-IR)、热重-差热(TG-DTA)和荧光光谱(PL)等分析测试手段对所得样品的结构、形貌和荧光光谱性能进行表征。研究结果表明:静电纺丝制备的有机-无机复合纤维的直径在200~250 nm之间,经过900℃热处理后,所得YVO4:Sm3+样品纤维状结构保持完好,直径减至100 nm。掺杂的稀土Sm3+离子在YVO4纤维中显示出特征发射,同时VO3-4和稀土Sm3+离子之间存在能量传递;Sm3+的掺杂浓度为2%(摩尔分数)时发光强度最大。     

石墨烯条带的电子结构与性质:电场及长度效应

在密度泛函理论(DFT)和含时密度泛函理论(TDDFT)的基础上对宽度上含有8个zigzag链的石墨烯条带(8-ZGNR)的基态和激发态的性质进行了理论研究,着重考察了条带长度及电场的影响.B3LYP杂化泛函的计算结果显示:在基态上,8-ZGNR的最低能量态并不具有磁性,随着长度的增加,才会显示出反铁磁的性质.静电场的加入使8-ZGNR显示出反铁磁性和半金属性.在激发态上,诱导电子会随着外激光脉冲的变化而发生移动和变化,但是相比而言,α自旋电子更容易被激发而产生较明显的诱导电子密度,而β自旋电子则更容易脱离外激光场的控制而产生非绝热现象.     

Exceedingly Fast Copper(II)‐Promoted ortho CH Trifluoromethylation of Arenes using TMSCF3

The direct ortho‐trifluoromethylation of arenes, including heteroarenes, with TMSCF₃ has been accomplished by a copper(II)‐promoted C? H activation reaction which completes within 30 minutes. Mechanistic investigations are consistent with the involvement of C? H activation, rather than a simple electrophilic aromatic substitution (S_EAr), as the key step.     

Trinuclear Gold Clusters Supported by Cyclic (alkyl)(amino)carbene Ligands: Mimics for Gold Heterogeneous Catalysts

The synthesis of air‐ and moisture‐stable trinuclear mixed‐valence gold(I)/gold(0) clusters is described. They promote the catalytic carbonylation of amines under relatively mild conditions. The synthetic route leading to the trinuclear clusters involves a simple ligand exchange from the readily available μ³‐oxo‐[(Ph₃PAu)₃O]⁺ complex. This synthetic method paves the way for the preparation of a variety of mixed‐valence gold(I)/gold(0) polynuclear clusters. Moreover, the well‐defined nature of the complexes demonstrates that the catalytic process involves a rare example of a definite change of oxidation state of gold from Au⁰₂Au^I to Au^I₃.     

A Tetrameric Cage with D2h Symmetry through Alkyne Metathesis

Shape‐persistent covalent organic polyhedrons (COPs) with ethynylene linkers are usually prepared through kinetically controlled cross‐coupling reactions. The high‐yielding synthesis of ethynylene‐linked rigid tetrameric cages via one‐step alkyne metathesis from readily accessible triyne precursors is presented. The tetrameric cage contains two macrocyclic panels and exhibits D_2h symmetry. The assembly of such a COP is a thermodynamically controlled process, which involves the initial formation of macrocycles as key intermediates followed by the connection of two macrocycles with ethynylene linkages. With a large internal cavity, the cage exhibits a high binding selectivity toward C₇₀ (K=3.9×10³ L mol^?1) over C₆₀ (no noticeable binding).