Towards the synthesis of insulated oligoynes: A ring-closing-metathesis approach to molecular encapsulation

Masked hexayne 18 was prepared in 11 steps from commercially available reagents. The four butenyl substituents contained within the two arylsilane residues in 18 have been used in a double ring-closing-metathesis operation in an attempt to encapsulate the π-conjugated framework. When 18 was treated with Grubbs’ 1st generation metathesis catalyst however, double ring-closing metathesis provided macrocycle 19 as the major product in good yield. Reasons why the macrocycle in 19 crowns, rather than encapsulates, the π-conjugated framework are discussed.     

示差脉冲伏安法测定乳酸脱氢酶活性及纳米微粒生物毒性检测新方法研究

采用示差脉冲伏安法，在乳酸脱氢酶(LDH)酶促体系“丙酮酸盐 + NADH +H⁺ (?) 乳酸盐 + NAD⁺”中，通过检测NAD⁺还原峰电流的变化，测定了不同条件下(不同酶用量、缓冲液pH值以及温度)LDH的活性、酶促体系的米氏常数K_m^NADH以及最大反应速率v_max。并且在最佳实验条件下，通过检测LDH活性的改变，实验考察了3种纳米物质(ZnS，TiO₂(R)和TiO₂(A))对乳酸脱氢酶酶促体系的影响。     

Comparison of triel bonds with different chalcogen electron donors: Its dependence on triel donor and methyl substitution

The complexes between R₃Tr (Tr = B, Al, and Ga; R = H, F, Cl, and Br) and H₂X (X = O, S, and Se) were theoretically studied. The interaction energies of R₃Al⋯H₂X and R₃Ga⋯H₂X are consistent with the electronegativity of the halogen atom R (R ≠ H), but an opposite dependence is found for R₃B⋯H₂X. The triel bond of R₃Tr⋯H₂X is weaker for the heavier chalcogen donor. The dependence of triel bonding strength on the triel atom is complicated, depending on the nature of R and X. The methyl substitution of H₂X causes a substantial increase in the interaction energy from −5.74 kcal/mol to −22.88 kcal/mol, and its effect is relevant to the nature of Tr, X, and R groups. For the S and Se donors, the increased percentage of interaction energy is almost the same due to the methyl substitution, which is larger than that of the O analogue. In most triel-bonded complexes, electrostatic dominates and polarization has comparable contribution. However, polarization plays a dominant role in R₃B⋯ and R₃B⋯ (R = Cl and Br; R′ = H and Me).     

Theoretical studies of mechanisms of cycloaddition reaction between difluoromethylene carbene and acetone

Mechanisms of the cycloaddition reaction between singlet difluoromethylene carbene and acetone have been investigated with the second‐order Møller–Plesset (MP2)/6‐31G* method, including geometry optimization and vibrational analysis. Energies for the involved stationary points on the potential energy surface (PES) are corrected by zero‐point energy (ZPE) and CCSD(T)/6‐31G* single‐point calculations. From the PES obtained with the CCSD(T)//MP2/6‐31G* method for the cycloaddition reaction between singlet difluoromethylene carbene and acetone, it can be predicted that path B of reactions 2 and 3 should be two competitive leading channels of the cycloaddition reaction between difluoromethylene carbene and acetone. The former consists of two steps: (i) the two reactants first form a four‐membered ring intermediate, INT2, which is a barrier‐free exothermic reaction of 97.8 kJ/mol; (ii) the intermediate INT2 isomerizes to a four‐membered product P_2b via a transition state TS2b with an energy barrier of 24.9 kJ/mol, which results from the methyl group transfer. The latter proceeds in three steps: (i) the two reactants first form an intermediate, INT1c, through a barrier‐free exothermic reaction of 199.4 kJ/mol; (ii) the intermediate INT1c further reacts with acetone to form a polycyclic intermediate, INT3, which is also a barrier‐free exothermic reaction of 27.4 kJ/mol; and (iii) INT3 isomerizes to a polycyclic product P₃ via a transition state TS3 with an energy barrier of 25.8 kJ/mol. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

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.     

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.     

Pyrrole-2-carboxylate dimer: a robust supramolecular synthon for crystal engineering

Two pyrrole-2-carboxylates, tris[2-(2-pyrryl-carboxy)ethyl]amine (1) and tetrakis(2-pyrryl-carboxy-methyl)methane (2), were prepared by the treatment of 2-trichloroacetylpyrrole with tri(2-hydroxylethyl)amine and pentaerythritol, respectively. Hexagonal and grid supramolecular structures were obtained from the self-assembly of 1 and 2, respectively. From the assembly structure, a novel supramolecular synthon of the pyrrole-2-carbonyl dimer has been found. The synthon was demonstrated to be robust by our density functional calculation. It is expected to be useful in the self-assembly of crystal engineering.     

吡嗪衍生物在石墨表面上的自组装单层膜结构

利用扫描隧道显微镜研究了荧光液晶分子2, 5-二-[2-(3, 4-二-十二烷氧基-苯基)-乙烯基]-3, 6-二甲基吡嗪(BPDP12)在石墨表面上自组装单层膜的结构. 实验结果表明, 该化合物在石墨表面形成两种自组装结构：一种是稳定的, 分子的共轭中心相互平行, 烷基链相互交错的密排结构；另一种是不稳定的, 分子的共轭中心彼此为烷基链所分隔的非密排结构. 分子之间较强的π-π作用和分子烷基链之间的范德华作用力对分子组装的取向形成竞争, 是产生两种不同组装结构的根本原因.     

(CH_3C_5H_4)_3Ln·THF(Ln=Sm,Ho,Tb,Yb)与环戊二烯生成(C_5H_5)_3Ln·THF的新反应

研究了(CH_3C_5H_4)_3Ln·THF (Ln = Sm,Ho,Tb,Yb)与环戊二烯高产率生成 (C_5H_5)_3Ln·THF的新反应。反应产物经过了元素分析、质谱和X射线的表征。产 物(C_5H_5)_3Ln·THF的特征结构参数,如五元碳环的碳原子与中心金属的平均距 离,五元碳环质心与中心金属距离,配位的四氢呋喃氧原子与中心金属距离,由于 “镧系收缩现象”,随着中心原子序数的增加而减小。     

Synthesis of new polymetallic carbene complexes: Uracil analogs

The easy cycloaddition of ureas with alkynyl alkoxy biscarbene complexes afforded, in fairly good yields, new biscarbene uracil analogs. X-ray structural data is reported for the dimethyluracil biscarbene complex. By changing the reaction conditions, a new non symmetric complex was obtained whose reaction with ethylenediamine afforded a new tetrakis amino carbene complex.