不同防老剂对天然橡胶复合材料P-V-T关系的影响

采用PVT膨胀仪测试了添加不同防老剂的天然橡胶(NR)复合材料的压力-体积-温度(P-V-T)属性,通过最小二乘法拟合得到Tait方程参数,预测了体系的热膨胀系数(α)和等温压缩系数(β),结果表明,Tait状态方程可用来预测该复合材料体系的P-V-T行为,NR复合材料的α值随着压力的增大而减小,随温度变化不明显;β值随压力的增大而减小,且随着温度的升高而升高.分子模拟结果观察了体系凝聚态结构在不同温度下的变化,表明其变化原因是升温使体系自由体积增大,分子链的活动性增强,同时观察到单独加入防老剂4010NA或防老剂RD的体系α和β的值较大,说明其尺寸稳定性差,而当同时加入4010NA和RD进行防老剂并用时,体系的α和β值均较小,表明此复合材料体系不容易产生变形;通过分子动力学模拟手段计算了NR复合材料的内聚能密度(CED)随温度的变化规律,对于2种防老剂并用的体系,其CED比较大,说明分子间相互作用力较强,从而体系尺寸稳定性好,受温度和压力的影响小.     

Palladium‐Catalyzed Decarboxylative Cycloaddition of Vinylethylene Carbonates with Formaldehyde: Enantioselective Construction of Tertiary Vinylglycols

An efficient method for the enantioselective construction of tertiary vinylglycols through a palladium‐catalyzed asymmetric decarboxylative cycloaddition of vinylethylene carbonates with formaldehyde was developed. By using a palladium complex generated in situ from [Pd₂(dba)₃]?CHCl₃ and a phosphoramidite ligand as a catalyst under mild reaction conditions, the process allows conversion of racemic 4‐substituted 4‐vinyl‐1,3‐dioxolan‐2‐ones into the corresponding 1,3‐dioxolanes, as methylene acetal protected tertiary vinylglycols, in high yields with good to excellent enantioselectivities.     

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.     

Highly Enantioselective Kinetic Resolution of Axially Chiral BINAM Derivatives Catalyzed by a Brønsted Acid

A highly efficient strategy for the kinetic resolution of axially chiral BINAM derivatives involving a chiral Brønsted acid‐catalyzed imine formation and transfer hydrogenation cascade process was developed. The kinetic resolution provides a convenient route to chiral BINAM derivatives in high yields with excellent enantioselectivities.     

An MRI‐Sensitive,Non‐Photobleachable Porphysome Photothermal Agent

Photothermal therapy makes use of photothermal sensitizers and laser light to thermally ablate diseased tissues. Porphysome nanoparticles offer a nontoxic alternative to inorganic nanocrystals for the efficient conversion of light into heat. Mn³⁺ ions were incorporated directly into the building blocks of our porphysome nanoparticles, thus imparting MRI sensitivity while simultaneously improving photostability and maintaining high photothermal efficiency. Mn porphysomes are as photothermally effective as free‐base porphysomes and can rival gadolinium diethylenetriaminepentaacetate (Gd‐DTPA) for MRI contrast generation. Their MRI contrast generation, photothermal efficiency, and photostability are unprecedented for an all‐organic nanoparticle composed of a single functional component.     

Manganese‐Catalyzed Dehydrogenative [4+2] Annulation of NH Imines and Alkynes by CH/NH Activation

Described herein is a manganese‐catalyzed dehydrogenative [4+2] annulation of N? H imines and alkynes, a reaction providing highly atom‐economical access to diverse isoquinolines. This transformation represents the first example of manganese‐catalyzed C? H activation of imines; the stoichiometric variant of the cyclomanganation was reported in 1971. The redox neutral reaction produces H₂ as the major byproduct and eliminates the need for any oxidants, external ligands, or additives, thus standing out from known isoquinoline synthesis by transition‐metal‐catalyzed C? H activation. Mechanistic studies revealed the five‐membered manganacycle and manganese hydride species as key reaction intermediates in the catalytic cycle.     

Gold‐Catalyzed Diastereoselective Cycloisomerization of Alkylidene‐Cyclopropane‐Bearing 1,6‐Diynes

An unprecedented gold‐catalyzed diastereoselective cycloisomerization of 1,6‐diynes bearing an alkylidene cyclopropane moiety has been developed. This methodology enables rapid access to a variety of 1,2‐trimethylenenorbornanes, which are important building blocks in the preparations of abiotic and sesquiterpene core structures.     

Restraint of the Differentiation of Mesenchymal Stem Cells by a Nonfouling Zwitterionic Hydrogel

The success of human mesenchymal stem cell (hMSC) therapies is largely dependent on the ability to maintain the multipotency of cells and control their differentiation. External biochemical and biophysical cues can readily trigger hMSCs to spontaneously differentiate, thus resulting in a rapid decrease in the multipotent cell population and compromising their regenerative capacity. Herein, we demonstrate that nonfouling hydrogels composed of pure poly(carboxybetaine) (PCB) enable hMSCs to retain their stem‐cell phenotype and multipotency, independent of differentiation‐promoting media, cytoskeletal‐manipulation agents, and the stiffness of the hydrogel matrix. Moreover, encapsulated hMSCs can be specifically induced to differentiate down osteogenic or adipogenic pathways by controlling the content of fouling moieties in the PCB hydrogel. This study examines the critical role of nonspecific interactions in stem‐cell differentiation and highlights the importance of materials chemistry in maintaining stem‐cell multipotency and controlling differentiation.     

β‐Functionalization of Carboxylic Anhydrides with β‐Alkyl Substituents through Carbene Organocatalysis

The first NHC‐catalyzed functionalization of carboxylic anhydrides is described. In this reaction, the β carbon behaves as a nucleophilic carbon and undergoes asymmetric reactions with electrophiles. Anhydrides with challenging β‐alkyl substituents work effectively.     

Synthesis,thermal, and photophysical properties of polymethylmethacryalte (PMMA) doped with ternary deuterated Eu(III) complexes

Two Eu(III) ternary luminescent complexes, Eu(tpb-H)₃(Tppo)₂ and Eu(tpb-H)₃(Topo)₂ (Tppo: triphenylphosphine oxide, Topo: trioctylphosphine oxide, tpb: 4,4,4-trifluoro-1-phenyl-1,3-butanedione) were synthesized using β-diketonates and phosphine oxides as ligands. Luminescent polymers were fabricated by incorporating the deuterated Eu(III) complexes in a PMMA matrix. Luminescent PMMA containing Eu(tpb-D)₃(Tppo)₂ exhibited relatively higher quantum yield, faster radiation rate, sharper red emission and larger stimulated emission cross-section and the results indicated prepared luminescent polymers including Eu(tpb-D)₃(Tppo)₂ showed promising results for applications in novel organic Eu(III) devices. Additionally, the Eu(III) complexes and luminescent PMMA showed good thermostabilization.