Noncovalent associations in fluorous fluids

Perfluorocarbons (PFCs) are emerging as a new type of liquid phase in which molecular recognition processes can effectively take place. The combination of perfluorocarbons (PFCs) and noncovalent associations, mostly hydrogen bonds, ion pairing, halogen bonds or coordination bonds, has already been successfully exploited for applications in organic synthesis (catalyst recycling, by-product removal), electrochemical sensing, selective extraction/titration processes or to prepare gels. Due to the extreme solvophobic effect in PFCs, the least polar existing fluids, noncovalent associations tend to be enhanced. For instance, quantitative data on the increase in association strength occurring in PFCs have recently been reported for ion-pairing interactions or encapsulation processes. Moreover, several examples show that confining a receptor in a fluorous phase leads to recognition processes with improved selectivity.     

CuZnAl记忆合金有序转变的固体电子论分析

应用固体经验电子理论,并联系 G.Inden 的有序转变温度与原子间作用能的关系式,计算了 CuZnAl 记忆合金的 A_2到 B_2,B_2到 DO_3两种有序转变温度随合金元素变化的规律。计算得出的变化趋势与实验结果符合得相当好,表明所采用的理论模型可以说明 CuZnAl 合金的记忆性能和用来指导探索新的记忆合金。     

丝氨酸蛋白酶中催化三元组内氢键的作用

为了探究丝氨酸蛋白酶催化效率的来源,本文分别研究了丝氨酸酶催化水解多肽CI2、MCTI-A和六肽(SUB)的过程中催化三元组内的氢键所起的作用. 首先采用QM/MM-MD方法计算了在酶-底物复合物和过渡态下组氨酸和天冬氨酸之间质子转移的自由能曲线. 结果表明低能垒氢键仅在CI2酰化反应的过渡态区域形成,而在MCTI-A和SUB酰化反应中均是正常氢键. 与MCTI-A相比,CI2和SUB体系中氢键强度在过渡态时显著增强,因此相应的酰化反应能垒明显降低. 过渡态区域形成的低能垒氢键显然有助于加速酰化反应,同时研究也表明正常氢键也有可能降低能垒. 氢键降低能垒的关键则在于过渡态下氢键强度的增加程度,而不是其是否生成了低能垒氢键. 本文为研究催化三元组间的氢键在丝氨酸蛋白酶中的作用提供了新思路,并有助于理解丝氨酸蛋白酶中催化三元组的催化机制.     

Insight into the chemomechanical coupling mechanism of kinesin molecular motors

Kinesin is a two-headed biological molecular motor that can walk processively on microtubule via consumption of ATP molecules. The central issue for the molecular motor is how the chemical energy released from ATP hydrolysis is converted to the kinetic energy of the mechanical motion, namely the mechanism of chemomechanical coupling. To address the issue, diverse experimental methods have been employed and a lot of models have been proposed. This review focuses on the proposed models as well as the qualitative and quantitative comparisons between the results derived from the models and those from the structural, biochemical and single-molecule experimental studies.     

Complementary relation between quantum entanglement and entropic uncertainty

Quantum entanglement is regarded as one of the core concepts,which is used to describe the nonclassical correlation between subsystems,and entropic uncertainty relation plays a vital role in quantum precision measurement.It is well known that entanglement of formation can be expressed by von Neumann entropy of subsystems for arbitrary pure states.An interesting question is naturally raised:is there any intrinsic correlation between the entropic uncertainty relation and quantum entanglement?Or if the relation can be applied to estimate the entanglement.In this work,we focus on exploring the complementary relation between quantum entanglement and the entropic uncertainty relation.The results show that there exists an inequality relation between both of them for an arbitrary two-qubit system,and specifically the larger uncertainty will induce the weaker entanglement of the probed system,and vice versa.Besides,we use randomly generated states as illustrations to verify our results.Therefore,we claim that our observations might offer and support the validity of using the entropy uncertainty relation to estimate quantum entanglement.     

Synthesizing Red Fluorescent Carbon Dots from Rigid Polycyclic Conjugated Molecules: Dual-Mode Sensing and Bioimaging in Biochemical Applications

Red fluorescent carbon dots (R-CDs) are special desirable for biochemical analysis due to good biological compatibility and deep penetration; however, they remain as bottlenecks due to difficulties in expanding the sp² domain, especially those are fused from rigid polycyclic conjugated molecules (RPCMs) with heteroatom substituents due to huge steric hindrance and heteroatom blockage toward graphic lattice. Here, an RPCM with heteroatom substituents, 1,5-diamino-4,8-dihydroxyanthraquinone (DDAQ), based self-doped R-CDs with PL emission at 635 nm is reported. Further investigations reveal that the expanding, hybrid sp² domain with indanthrone tannin structure from DDAQ is mainly responsible for the obtained red fluorescence of R-CDs. Taking advantage of optical properties, R-CDs are considered to construct a colorimetric/fluorescent dual mode sensing array for quantifying trace levels of Fe³⁺ and glyphosate based on the static quenching, and a biomarker for cell imaging. The CD-based sensors exhibit outstanding recovery, high selectivity, and sensitivity, also facilitated dual-mode detection with the naked-eye. The R-CDs have low cytotoxicity, good cell membrane penetration for rapid cell entry, and high resolution, demonstrating their potential for biolabeling and bioanalytic applications.     

盐酸四环素中可交换氢和氢键的核磁共振波谱研究

四环素类抗生素是一类广谱抗生素,对革兰氏阳性菌、革兰氏阴性菌、支原体、衣原体和立克次体感染均具有抗菌活性.本文运用一维（1D）和二维（2D）核磁共振（NMR）技术对盐酸四环素中可交换氢和氢键进行研究,并将研究结果与RNA和蛋白质结合的四环素以及游离药物的晶体结构进行比较,进一步讨论了药物中的氢键构架与药物活性的相关性.最后对盐酸四环素及其同系物的¹H和¹³C NMR信号进行了全归属和分析,并对文献归属结果进行了细微校正.这些结果有助于进一步探索该类药物在更复杂的生物或环境系统中的构效关系.     

On molecular topological properties of hex‐derived networks

Topological indices are numerical parameters of a molecular graph, which characterize its topology and are usually graph invariant. In quantitative structure–activity relationship/quantitative structure–property relationship study, physico‐chemical properties and topological indices such as Randić, atom–bond connectivity (ABC), and geometric–arithmetic (GA) index are used to predict the bioactivity of chemical compounds. Graph theory has found a considerable use in this area of research. In this paper, we study hex‐derived networks HDN1(n) and HDN2(n), which are generated by hexagonal network of dimension n and derive analytical closed results of general Randić index R_α(G) for different values of α, for these networks of dimension n. We also compute the general first Zagreb, ABC, GA, ABC₄, and GA₅ indices for these hex‐derived networks for the first time and give closed formulae of these degree‐based indices for hex‐derived networks. Copyright © 2016 John Wiley & Sons, Ltd.     

Geometrical structure and nonlinear response variations of metal (M = Ni2+, Pd2+, Pt2+) octaphyrin complex derivatives: A DFT study

Nonlinear optical response of designed organometallic complexes of Ni²⁺, Pd²⁺, and Pt²⁺ metal ions with octaphyrin (OP) as ligand were explored by using DFT at CAM-B3LYP/6–311G++(d, p)/LANL2DZ/DEF2SV level of theory. The geometries of these organometallic complexes were studied in terms of effect on molecular framework by metal ion and substituent groups. The optimized geometry of free ligand displays that one of the four pyrrole rings orients out of plane to reduce the steric hindrance. The effect of the substituents on the geometry was found more prominent in the Ni²⁺-OP complexes. The calculations reveal enhancement in the values of dipole moment and hyperpolarizability on introducing electron withdrawing and electron donating groups in ligand framework with maximum enhancement in case of Pt²⁺-OP derivatives. In this study no regular trend was observed for the HOMO and LUMO energies with the second-order hyperpolarizability of M²⁺-OP complexes. However, we have observed that the excited-state properties calculated by using TD-DFT correlate well with the second-order hyperpolarizability values and the dependence was rationalized in terms of two-level model. Thus, from overall calculations we have observed that the designed organometallic complexes display higher polarizability and hyperpolarizability values and can be effective candidates for nonlinear response.     

Synthesis of N‐alkyl‐N′‐aryl or Alkenylpiperazines: A Copper‐Catalyzed C–N Cross‐Coupling in the Presence of Aryl and Alkenyl Triflates and DABCO

Unsymmetrical piperazines are key constituents of many pharmaceuticals. Given that the selective introduction of an aryl and alkyl motif onto the piperazine is not always straightforward, direct arylation and alkenylation of 1,4‐diaza‐bicyclo[2.2.2]octane would obviate the inefficiencies associated with the preparation of these target molecules. We have utilized alkyl halides, aryl or alkenyl triflates, and 1,4‐diaza‐bicyclo[2.2.2]octane for the synthesis of N‐alkyl‐N ′‐aryl or alkenylpiperazines. The optimum conditions are developed using CuCl, t‐BuOL i in NMP . Alkenyl triflates requires N ,N ′‐dimethylethylenediamine and higher temperature to afford the desired cross‐coupled product. Substrates bearing electron‐deficient and electron‐rich groups were successfully coupled under the optimum reaction conditions.