三接触弯曲构型的蓝移氢键CH3…Y的理论研究

运用量子化学从头算方法, 在MP2/6-311＋＋G(d,p), MP2/6-311＋＋G(2df,2p), MP2/6-311＋＋G(3df,3pd)和QCISD/6-311＋＋G(d,p)水平上, 研究了CH₃F, CH₃Cl和CH₃Br作为质子给体与Cl^－, Br^－作为质子接受体形成的氢键CH₃…Y. 计算结果表明: 6种复合物中C—H键收缩, 伸缩振动频率增大, 形成蓝移氢键. 分子中原子(Atoms in Molecules, AIM)分析表明, 这些复合物的电子密度拓扑性质与普通氢键有着本质的不同, 在Y…H之间不存在键临界点, 而在Y与C之间存在键临界点, 因此这些相互作用严格地不能称为氢键. 自然键轨道(Natural bond orbital, NBO)分析表明, 在这些复合物中弯曲的CH…Y的特殊结构使得分子间超共轭n(Y)®σ*(C—H)减小到可以忽略; 质子接受体的电子密度没有转移到σ*(C—H)上, 而是转移到了σ*(C—X) (X＝F, Cl, Br)上; 存在一定程度的重杂化; 分子内超共轭相互作用减小使得σ*(C—H)的电子密度减少. 这些因素共同导致C—H伸缩振动频率的蓝移.     

Characterization of the supermolecular structure of cellulose in wood pulp fibres

The hierarchic organization of cellulose fibrils (microfibrils) was investigated in holocellulose, sulphite pulp and kraft pulp using TEM, XRD, ED and FTIR. There were remarkable differences in both the fibril structure and fibril aggregation between the samples. TEM observations revealed more intimately associated fibrils in the kraft pulp compared to the sulphite pulp and the holocellulose, results in agreement with previous CP/MAS ¹³C-NMR data [Hult E.-L. et al. (2002) Holzforschung 56: 231–234]. Furthermore, the cellulose crystallinity was higher in the kraft pulp sample. With respect to the cellulose I and I allomorphs, these samples were controversial when different analytical techniques were applied. Due to the small fibril size and the low degree of order of cellulose in these samples, the concept of crystalline triclinic and monoclinic components as determined by diffraction analysis may not be adequate. Instead the fibril can be regarded to have different degrees of lateral order (including paracrystalline ordering) that can be reoriented to I type conformation and packing upon pulping.     

Studies on Aggregation Interaction between Reduced Denatured Egg White Lysozymes during Refolding Procedure in Urea Solution

The aggregation interaction between reduced-denatured egg white lysozymes during refolding procedure in urea solution was studied by means of reducing and non-reducing protein electrophoreses. Results of non-reducing sodium dodecyl sulphate polyacrylamide gel electrophoresis （SDS-PAGE） of the supernatant and aggregate precipitate formed in refolding process show that except being refolded to native egg white lysozymes, the reduced-denatured lysozymes can also form the aggregates with molecular weights （MW） being separately about 30.0 and 35.0 kD, while the reducing SDS-PAGE and the refolding results in the presence of sodium dodecyl sulphate show that these aggregates are formed chiefly through the misconnection of disulfide bonds between the reduced-denatured lysozymes, and the aggregate precipitates are formed through the non-covalent interactions between the aggregates with molecular weight being about 30.0 kD. From the results of electrophoresis and size-exclusion chromatographic analyses, it can be inferred that the aggregates with molecular weights being about 30.0 and 35.0 kD are bi-molecular and tri-molecular egg white lysozyme aggregates, respectively. And finally, a suggested refolding mechanism of reduced-denatured egg white lysozymes in urea solution was presented.     

Filtering germs: Groupoids associated to inverse semigroups

We investigate various groupoids associated to an arbitrary inverse semigroup with zero. We show that the groupoid of filters with respect to the natural partial order is isomorphic to the groupoid of germs arising from the standard action of the inverse semigroup on the space of idempotent filters. We also investigate the restriction of this isomorphism to the groupoid of tight filters and to the groupoid of ultrafilters.     

Sampling Consensus of 2nd-Order Multi-Agent Systems Based on Time-Varying Topology北大核心CSCD

基于速度一致位移差保持不变的一致性概念,研究了二阶多智能体系统在时变拓扑下的采样一致性问题。首先,引入虚拟领导者,将具有时变拓扑结构的多智能体系统的采样一致性问题转换为误差系统的采样控制稳定性问题。其次,通过预估采样误差,研究采样误差对系统达到一致性的影响。最后,应用Lyapunov稳定性理论,分析所构造的误差系统的稳定性,并给出该误差系统最终稳定的充分条件。数值仿真结果验证了理论分析的有效性和正确性。     

Rational choice based on vague preferences

This paper studies vague preferences. In contrast to the concept of fuzzy preferences, the more general notion of vague preferences does not entail the assumption that the different degrees of preference are completely ordered. It is shown that the more general concept of a vague preference order arises very naturally in the context of aggregating a set of (exact) weak orders. Furthermore, necessary and sufficient conditions for the rationalizability of an exact choice function by means of a vague preference order are given. It turns out that in the general case these conditions are weaker than in the case where the degrees of preference are completely ordered. Consequently, there exist choice functions which are rationalizable by a general vague preference order but which are not rationalizable by a fuzzy preference order, or more generally by any vague preference order which induces a complete ranking of the degrees of preference. Examples of such choice functions are provided.This is a revised version of a discussion paper which was written at the University of Karlsruhe. I am grateful to Georg Bol and an anonymous referee for valuable comments. The research has been made possible by a fellowship of the DFG (Deutsche Forschungsgemeinschaft) which is also gratefully acknowledged.     

基于改进3D UNet的前列腺MR图像分割

针对前列腺磁共振 (magnetic resonance, MR)图像边缘模糊、对比度较低,灰度值分布不均衡而导致分割精度较差的问题,提出了一种结合双路径注意力(dual path attention,DPA) 和多尺度特征聚合(multi-scale feature aggregation,MFA) 模块的改进3D UNet网络模型。首先,对数据集进行重采样和裁剪处理以适应模型输入。然后,在3D UNet网络的编码器各层引入DPA 并添加残差连接,加强特征的 编码能力。同时,在网络解码器中加入MFA模块,以充分利用空间上下文信息,增强语义信息。最后,在公开数据集PROMISE12上进行验证,所提出的模型的Dice系数为89.90%,Hausdorff 距离为9.37 mm。相比较于其他模型,所提出模型的分割结果更优,且参数量和运算量更少。     

In Situ Deformation Topology of COFs with Shortened Channels and High Redox Properties for Li–S Batteries

Covalent organic frameworks (COFs) with various topologies are typically synthesized by selecting and designing connecting units with rich shapes. However, this process is time-consuming and labour-intensive. Besides, the tight stacking of COFs layers greatly restrict their structural advantages. It is crucial to effectively exploit the high porosity and active sites of COFs by topological design. Herein, for the first time, inducing in situ topological changes in sub-chemometric COFs by adding graphene oxide (GO) without replacing the monomer, is proposed. Surprisingly, GO can slow down the intermolecular stacking and induce rearrangement of COFs nanosheets. The channels of D- [4+3] COFs are significantly altered while the stacking of periodically expanded framework is weakened. This not only maximizes the exposure of pore area and polar groups, but also shortens the channels and increases the redox activity, which enables high loading while enhancing host-guest interactions. This topological transformation to exhibit the structural features of COFs for efficient application is an innovative molecular design strategy.     

太赫兹网络中基于中继协作转发的高效双信道MAC协议

针对现有多输入多输出(Multiple-Input Multiple-Output, MIMO)太赫兹通信网络双信道MAC协议存在波束重叠干扰和冗余控制开销等问题,提出了一种太赫兹网络中基于中继协作转发的双信道MAC协议(High Efficiency Dual channel MAC Protocol Based on Relay Cooperative Forwarding in Terahertz Networks, HE-RCFMAC)。HE-RCFMAC协议包含动态帧聚合、基于位置信息自适应协作转发和精简RTS(Request To Send)/CTS(Clear To Send)帧三种机制。经三种机制处理后,可有效提升信道利用率,同时减小控制开销,提高数据传输成功率和整体网络吞吐量。仿真结果表明,所提协议与现有的MIMO太赫兹双信道MAC协议相比,MAC层吞吐量、数据传输成功率和信道利用率分别提升了12.82%、12.28%和8.73%,证明了所提协议的有效性。     

M2OVQA: Multi-space signal characterization and multi-channel information aggregation for quality assessment of compressed omnidirectional videos

Considering the high requirements for omnidirectional video compression, we propose an objective quality evaluation method to assess quality loss in encoding omnidirectional videos. According to characteristics of 360° videos, we consider multi-space signal characterization (MSSC) to fully characterize the distortions of video signals from spatial/image domains to frequency domains and from image content to motion information, and further consider multi-channel information aggregation (MCIA) to fuse scores from multiple projection planes and temporal divided groups. The main innovation of our method is to establish a universal framework in bridging the connection between typical quality assessment and 360° quality assessment to measure 360° video quality effectively and efficiently. Experimental results show that our method outperforms state-of-the-art 2D quality metrics and quality metrics for omnidirectional images.