A μ3-OH- bridged two-dimensional zinc(Ⅱ) coordination polymer based on an anthryl ligand：Synthesis, characterization and luminescent properties

A two-dimensional (2D) 3,3,3,4,5,5,6-connected ZnⅡ coordination compound [Zn5(L)2(OH)6]∞ (L=9,10-dioxo-9,10-dihydroanthracene-1,8-dicarboxylate) has been synthesized and characterized by IR, elemental analysis, X-ray powder diffraction and single crystal X-ray diffraction analysis. Moreover, the luminescent properties of the ligand and corresponding compound have been briefly investigated.     

Nonlinear optical metal-organic frameworks for ratiometric temperature sensing in physiological range

The precise and real-time sensing of the temperature within the physiological range is of great significance in biology and medicine. Here, a Zn-based metal-organic framework (MOF) named Zn-TCOMA is synthesized with good SHG performance due to its unique structure of the ligand and 3D frameworks. By encapsulating the two-photon fluorescent dye DMASE into the pores of Zn-TCOMA, the composite Zn-TCOMA?DMASE is obtained and simultaneously exhibits SHG response and two-photon fluorescence. Utilizing the intensity ratio between two-photon fluorescence of DMASE and SHG signal of Zn-TCOMA, Zn-TCOMA?DMASE exhibits ratiometric temperature sensing property at physiological temperature region of 20～60 °C with high sensitivity. This MOF thermometer also shows excellent repeatability, good biocompatibility, and high temperature resolution of 0.018 °C, opening a new avenue to develop diverse optical thermometric or thermographic applications in biotechnology or other areas.     

From Distinct Metallopeptoids to Self-Assembled Supramolecular Architectures

The construction of synthetic protein mimics is a central goal in chemistry. A known approach for achieving this goal is the self-assembly of synthetic biomimetic sequences into supramolecular structures. Obtaining different 3D structures via a simple sequence modification, however, is still challenging. Herein we present the design and synthesis of biomimetic architectures, via the self-assembly of distinct copper-peptoid duplexes. We demonstrate that changing only one non-coordinating side-chain within the peptoids—sequence-specific N-substituted glycine oligomers—leads to different supramolecular structures. Four peptoid trimers incorporating 2,2’-bipyridine and pyridine ligands, and a non-coordinating but rather a structure-directed bulky group were synthesized, and their solutions were treated with Cu²⁺ in a 1:1 ratio. Single-crystal X-ray analysis of the products revealed the self-assembly of each peptoid into a metallopeptoid duplex, followed by the self-assembly of multiple duplexes and their packing into a three-dimensional supramolecular architecture via hydrogen bonding and π–π interactions. Tuning the non-coordinating side-chain enables to regulate both the final structure being either a tightly packed helical rod or a nano-channel, and the pore width of the nano-channels. Importantly, all the metallopeptoids structures are stable in aqueous solution as verified by cryo-TEM measurements and supported by UV/Vis and EPR spectroscopies and by ESI-MS analysis. Thus, we could also demonstrate the selective recognition abilities of the nano-channels towards glycerol.     

A Porphyrin-Based Covalent Organic Framework for Metal-Free Photocatalytic Aerobic Oxidative Coupling of Amines

Imines are important intermediates in drug synthesis. Photocatalytic aerobic oxidative coupling of amines has been considered as a clean and promising way to produce imines and has attracted great attention. Herein, we designed and synthesized a novel two-dimensional porphyrin-based covalent organic framework (Por-BC-COF) which adopts an AA stacking mode with excellent crystallinity, high Brunauer–Emmett–Teller surface areas (1200 m² g⁻¹), wide light absorption range (200–1300 nm) and good stability in a variety of organic solvents. Por-BC-COF can be used as a metal-free heterogeneous photocatalyst for the photocatalytic oxidation of amines to imines under visible light and red light with a high yield (97 %). This work presents a novel and efficient COF photocatalyst in the application of light-driven organic synthesis.     

‘New mathematics’ and teaching

Inside the scientific world it is not always understood that the mood of mathematics, which is a product and a part of culture, can change with time. This is partly why many have been surprised by the coming of the so‐called new mathematics.

In the truly creative mathematical mind two opposite tendencies coexist: the logical and the imaginative. Apparently it seems that new mathematics can be reduced to a purely logical machinery. In fact it contains as much imaginative contributions as classical mathematics. But it is difficult to show simultaneously the logical sequence of propositions and the clumsy progression of research itself. Mathematical exposition does not always follow the ‘ most natural slopes’ of the mind. Unfamiliar presentations often give an impression of ‘ abstraction ‘, more familiar ones an impression of concreteness ‘.

So it appears that difficulties with new mathematics are mostly of psychological origin. Misuses of it can easily raise up intolerance reactions and emotional blocks. Perhaps insisting upon the fact that, here as elsewhere, it is important to be able to guess, to realize that intuition and imagination are essential, could help to make new mathematics better understood, more useful and more able to be considered as a unifing element among sciences.     

Chaos in social learning with multiple true states

Most existing social learning models assume that there is only one underlying true state. In this work, we consider a social learning model with multiple true states, in which agents in different groups receive different signal sequences generated by their corresponding underlying true states. Each agent updates his belief by combining his rational self-adjustment based on the external signals he received and the influence of his neighbors according to their communication. We observe chaotic oscillation in the belief evolution, which implies that neither true state could be learnt correctly by calculating the largest Lyapunov exponents and Hurst exponents.     

中学生学习自我效能感、学习策略与学业成就的关系

以学习自我效能感和学习策略量表为工具,通过方差分析、相关分析和路径分析等方法,重点考察了学习自我效能感和学习策略这两个因素对学业成就的影响路径以及相互间的关系.发现中学生的学习自我效能感与学习策略间存在着显著的相关关系;学习自我效能感和学习策略对初中生的学业成就有显著回归效应,而学习策略对高中生的学业成就有显著回归效应;学习自我效能感可通过影响学习策略来间接影响学业成就.     

Quantum chemical electron impact mass spectrum prediction for de novo structure elucidation: Assessment against experimental reference data and comparison to competitive fragmentation modeling

We investigate the success of the quantum chemical electron impact mass spectrum (QCEIMS) method in predicting the electron impact mass spectra of a diverse test set of 61 small molecules selected to be representative of common fragmentations and reactions in electron impact mass spectra. Comparison with experimental spectra is performed using the standard matching algorithms, and the relative ranking position of the actual molecule matching the spectra within the NIST‐11 library is examined. We find that the correct spectrum is ranked in the top two matches from structural isomers in more than 50% of the cases. QCEIMS, thus, reproduces the distribution of peaks sufficiently well to identify the compounds, with the RMSD and mean absolute difference between appropriately normalized predicted and experimental spectra being at most 9% and 3% respectively, even though the most intense peaks are often qualitatively poorly reproduced. We also compare the QCEIMS method to competitive fragmentation modeling for electron ionization, a training‐based mass spectrum prediction method, and remarkably we find the QCEIMS performs equivalently or better. We conclude that QCEIMS will be very useful for those who wish to identify new compounds which are not well represented in the mass spectral databases.     

A 3D Luminescent Metal‐organic Framework Constructed from Cu4I4 Cubane Clusters and Triangular Imidazole Ligand

Abstract . The solvothermal reaction between cuprous iodide and the rigid triangular imidazole ligand in mixed N,N′‐dimethylacetamide (DMA)‐acetonitrile solvent leads to the isolation of the 3D metal‐organic framework [(Cu₄I₄)₃(TIPA)₄] · 7DMA ( 1 ) [TIPA = tri(4‐imidazolylphenyl) amine], which was characterized by elemental analysis, IR spectroscopy, powder X‐ray diffraction, and single‐crystal X‐ray diffraction. Topologically, the structure of 1 is an unprecedented 3,3,4,4‐connected net with a point symbol of {4.8.10}₂{4.8²}₂{4².8².10²}₂{8⁴.12²}. Compound 1 exhibits orange‐red photoluminescence with an emission maximum at 622 nm at room temperature.