Effect of the Secondary Reduction on the Enantioselectivity and Function of Additives in the Chiral Oxazaborolidine‐Catalyzed Asymmetric Borane Reduction of Ketones

The secondary reduction in the direct and oxazaborolidine‐catalyzed asymmetric borane reduction of ketones was investigated by the use of GC/MS tracing titration and control experiments. The results indicate that the secondary reduction affects the enantioselectivity only in noncoordinated solvents at low temperature and not under the usual catalytic reduction conditions because the intermediate alkoxyborane is unstable and quickly converts to borane and dialkoxyborane. The function of an alcohol additive in the asymmetric borane reduction of ketones is to consume excess borane in the reduction system thus inhibiting noncatalytic reduction, which leads to increased enantioselectivity in the catalytic reduction.     

DNA electrochemistry through the base pairs not the sugar-phosphate backbone

Using intercalated, covalently bound daunomycin as a redox probe, ground state charge transport in DNA films with a perturbation in base pair stacking was examined in comparison with breaks in the sugar-phosphate backbone. While the introduction of one or even two nicks in the sugar-phosphate backbone yields no detectable effect on electron transfer, a CA mismatch significantly attenuates the electron transfer yield. These results confirm that the base pair stack is the pathway for DNA-mediated charge transfer, not the sugar-phosphate backbone.     

A new strategy for the synthesis of α,β-diaroylpropionates promoted by samarium metal in DMF

When promoted by samarium in DMF, aroyl chlorides react readily with acrylates to afford α,β-diaroylpropionates in good to excellent yields without pretreating or activating the metallic samarium.     

二甲基甲酰胺中四种钕盐的电导

通过电导测量研究了四种钕盐：Nd(CF3SO3)3、Nd(ClO4)3、Nd(NO3)3和NdCl3在极性非质子溶剂DMF中的电导性质.利用线性拟合方法求得在25 ℃下Nd(CF3SO3)3和Nd(ClO4)3的极限摩尔电导率分别为278.8和 280.7 S•cm2•mol－1.用间接方法求得Nd(NO3)3 与NdCl3 的极限摩尔电导率分别为297.2和287.3 S•cm2 •mol－1.在25～65 ℃温度范围内，Nd(CF3SO3)3和Nd(ClO4)3的电导率随温度呈线性变化. Nd(NO3)3和NdCl3的电导行为表现出明显的离子缔合.     

抚顺烟煤及其抽出物的FTIR光谱结构表征

用富立叶变换红外光谱(FTIR)对抚顺烟煤的有机组分进行了测定。通过对谱图的解析,指出抚顺烟煤及其吡啶抽出物和抽提残煤在结构上的异同。以及抽出物各色谱馏分中存在的官能团和官能团之间极性的差异,对原煤整体结构提供了精细的结构信息。     

在涂层TiO2改性铜催化剂上甲醇脱氢制甲酸甲酯

在常压和２５０℃下，考察了涂层ＴｉＯ２改性铜催化剂上甲醇脱氢生成甲酸甲酯的活性和选择性以及催化剂的稳定性。结果表明，涂层ＴｉＯ２明显提高了铜催化剂的活性和稳定性。在所考察的铜催化剂中，以Ｃｕ／ＴｉＯ２／ＡｌＯ３的催化活性最高，甚至高于离子交换法制备的Ｃｕ（ｅｘ）／ＳｉＯ２催化剂。ＸＰＳ分析表明，Ｃｕ／ＴｉＯ２／ＡｌＯ３中存在着两种化学环境不同的ＣＵ（０），即负载在ｒ－ＡＬＯ３和ＴｉＯ２－Ａｌ２Ｏ３     

Stereoselective synthesis of unnatural α-amino acid derivatives through photoredox catalysis

A protocol for stereoselective C-radical addition to a chiral glyoxylate-derived N-sulfinyl imine was developed through visible light-promoted photoredox catalysis, providing a convenient method for the synthesis of unnatural α-amino acids. The developed protocol allows the use of ubiquitous carboxylic acids as radical precursors without prior derivatization. The protocol utilizes near-stoichiometric amounts of the imine and the acid radical precursor in combination with a catalytic amount of an organic acridinium-based photocatalyst. Alternative mechanisms for the developed transformation are discussed and corroborated by experimental and computational studies.

A protocol for stereoselective C-radical addition to a chiral glyoxylate-derived N-sulfinyl imine was developed through visible light-promoted photoredox catalysis, providing a convenient method for the synthesis of unnatural α-amino acids.     

Multifunctional peptide-assembled micelles for simultaneously reducing amyloid-β and reactive oxygen species

The excessive production and deposition of amyloid-β (Aβ) is one of the most important etiologies of Alzheimer''s disease (AD). The interaction between Aβ and metal ions produces aberrant reactive oxygen species (ROS), which induce oxidative stress and accelerate the progression of AD. To reduce Aβ plaques and ROS to maintain their homeostasis is an emerging and ingenious strategy for effective treatment of AD. Herein, we report the rational design of multifunctional micelles (MPGLT) based on a polymer-grafted peptide to simultaneously clear Aβ and ROS for AD therapy. The MPGLT integrating three functional peptides as a ROS scavenger (tk-GSH), β-sheet breaker (LP) and an autophagy activator (TK) respectively, could capture and degrade Aβ. Meanwhile, the tk-GSH on the surface of MPGLT effectively scavenges the intracellular ROS. Consequently, MPGLT reduced the cytotoxicity of Aβ and ROS. In vivo animal studies using an AD mouse model further showed that MPGLT could transport across the blood–brain barrier for decreasing the Aβ plaque and eliminating ROS in vivo. This peptide micelle-based synergistic strategy may provide novel insight for AD therapy.

Multifunctional micelles based on a peptide–polymer for simultaneously targeting Aβ degradation and ROS scavenging for AD therapy.     

Mechanism and kinetics of the 2,2′-bipyridyl catalysis of the chromium(VI) oxidation of malic acid

A spectrophotometric study of the kinetics and mechanism of the oxidation of malic acid (Mal) by chromium(VI) catalyzed by 2,2′-bipyridyl (bpy) in aqueous acidic medium was conducted in a temperature range of ～298 to 313 K. This reaction was found to be pseudo-first order with respect to Cr(VI) and first order with respect to malic acid. Under the conditions of the pseudo-first order ([Mal]_o ? [Cr(VI)]_o), the observed rate constant (k _obs) increased with the increase in [H⁺] and [bpy]. There was a weak negative salt effect. Based on the experimental results, a possible reaction mechanism for this oxidation catalyzed by bpy is proposed. The rate equation derived from this mechanism can explain all the experimental phenomena.     

Morphology control of soap-free seeded P(St-EA-AA) latex particles

Soap-free poly(styrene-ethyl acrylate-acrylic acid) latex particles with narrow size distribution and with surface carboxyl groups were synthesized by semicontinuous emulsion polymerization, and the particles with homogeneous multihollow structure were obtained after alkali posttreatment. Effects of treatment conditions and crosslinking agents on particle morphology were investigated. Results showed that the multihollow structure can be formed inside the uncrosslinked particles only when the treatment temperature exceeded 50 °C, the pH was higher than 10.0, the amount of 2-butanone was more than 3.0 ml and the treatment time was longer than 30 min. Furthermore, the volume expansion of the particles increased with the temperature increased to 90 °C, the pH to 12.5 or the amount of 2-butanone to 7.0 ml, and this value increased first and then decreased with the treatment time prolonged. Fine pores can be generated in the shell of particles crosslinked by 0.2 g of ethyl glycol dimethylacrylate (EGDMA), while no hollow structure formed inside particles when 0.4 g of EGDMA or 0.2 g of divinyl benzene was used.