三维网状的4-羧基苯氧乙酸锶(Ⅱ)配位聚合物[Sr2(4-CPOA)2(H2O)5]n的合成、结构与热稳定性研究

A novel coordination polymer of [Sr₂(4-CPOA)₂(H₂O)₅]_n (where 4-CPOA^2- is 4-carboxylphenoxyacetate) has been synthesized and characterized by elemental analysis, IR, TG and single crystal X-ray diffraction. The title complex belongs to monoclinic system with space group C2/c, a=2.563 9(5) nm, b=1.162 7(2) nm, c=0.742 96(15) nm, β=99.64(3)°. V=2.183 5(7) nm³, Z=4, M_r=653.60, D_c=1.988 g·cm^-3, R=0.027 8, wR=0.058 1. The strontium atom has a bicapped triangular prismatic coordination geometry, involving four oxoacetate oxygen atoms, one ether oxygen atom from different 4-CPOA^2- ligands and three water molecules. The strontium(Ⅱ) ions are linked by 4-CPOA^2- ligands and water molecules to form a 3D network structure. CCDC: 223313.     

一维链状柔性羧酸镉配位聚合物[Cd(p-BDOA)·2H2O]n的合成、结构与性质研究(英)

A novel 1-D Cd(Ⅱ) coordination polymer, [Cd(p-BDOA)·2H₂O]_n(I) ( p-BDOA^2-=benzene-1,4-dioxyacetate dianion) has been synthesized and characterized by elemental analysis, IR, PL, TG and X-ray single crystal diffraction. The Crystal crystallizes in monoclinic system, the space group is C2/c, with the crystal cell parameters a=1.175 1(1) nm, b=0.551 0(1) nm, c=1.827 7(2) nm, β=96.14(2)°, and V=1.176 6(3) nm^3,, M_r=372.60, R=0.045 9, wR=0.127 9. The Cd(Ⅱ) ion has a trigonal prism coordination configuration that defined by four carboxyl O atoms from two different p-BDOA^2- ligands and two water molecules. Adjacent Cd(Ⅱ) ions are linked by carboxylate groups with the bidentate coordination mode, giving rise to a chain structure with the adjacent Cd…Cd distance of 1.526 3(5) nm. Furthermore, such chains are linked by hydrogen bonds to form supramolecular network. The results of PL and TG show that the complex exhibits intense fluorescent emissions and its chain skeleton is thermally stable up to 419 K. CCDC: 220443.     

闪电AR谱的多重分形特性分析及放电类型的识别

对闪电时域波形的分形研究由于忽略了其频率特性,致使复杂多变的闪电过程的全部特性无法得到充分表征。针对此问题,本文将多重分形理论引入到现代谱估计中,提出了一种基于AR(auto-regressive)谱的闪电电场信号的多重分形特性分析及放电类型的识别方法。首先基于AR模型谱估计法获得闪电电场信号的功率谱,然后,通过多重分形去趋势波动分析(multifractal detrended fluctuation analysis,MF-DFA) 法验证了闪电AR谱序列具有多重分形特性,并进一步对AR谱序列的Hurst指数以及多重分形谱进行了讨论,最后将相关参数作为闪电信号的有效特征值输入支持向量机进行了云闪(intracloud lightning) 和地闪(cloud-to-ground lightning,CG) 不同放电类型的识别。实验结果表明,本文方法对云、地闪信号的有效识别率达到了94%以上,该研究成果对闪电的特性研究与自动化识别技术均具有一定的参考价值。     

Sufficient Utilization of Mn2+/Mn3+/Mn4+ Redox in NASICON Phosphate Cathodes towards High-Energy Na-Ions Batteries

Na superionic conductor of Na₃MnTi(PO₄)₃ only containing high earth-abundance elements is regarded as one of the most promising cathodes for the applicable Na-ion batteries due to its desirable cycling stability and high safety. However, the voltage hysteresis caused by Mn²⁺ ions resided in Na⁺ vacancies has led to significant capacity loss associated with Mn reaction centers between 2.5–4.2 V. Herein, the sodium excess strategy based on charge compensation is applied to suppress the undesirable voltage hysteresis, thereby achieving sufficient utilization of the Mn²⁺/Mn³⁺ and Mn³⁺/Mn⁴⁺ redox couples. These findings indicate that the sodium excess Na_3.5MnTi_0.5Ti_0.5(PO₄)₃ cathode with Ti⁴⁺ reduction has a lowest Mn²⁺ occupation on the Na⁺ vacancies in its initial composition, which can improve the kinetics properties, finally contributing to a suppressed voltage hysteresis. Based on these findings, it is further applied the sodium excess route on a Mn-richer phosphate cathode, which enables the suppressed voltage hysteresis and more reversible capacity. Consequently, this developed Na_3.6Mn_1.15Ti_0.85(PO₄)₃ cathode achieved a high energy density over 380 Wh kg⁻¹ (based on active substance mass of cathode) in full-cell configurations, which is not only superior to most of the phosphate cathodes, but also delivers more application potential than the typical oxides cathodes for Na-ion batteries.     

A New Method to Investigate the Clustering Phenomena in Supercritical Fluids

EstimationoflocaldensityofsolventaboutthesoluteSolvatochromicbehaviorsofspectroscopicprobesarewidelyusedtoestimatethesol-ventstrengthofsupercriticalfluids(SCF,).i-3lnthiswork,thesolvatochrondcshiftofthen-n*transitionbandforacetone(O.o37mo1.L-')insupercrihcal(SC)CO2wasde-terminedbyUVspectroscopytostUdythesolvationeffect.TheMcRae-BaylissexpressionbasedonthedielectriccontinUUInmodelgivestherelahonshipbetWeenso1vatochromicshiftandpo1arizabilityofnonPolarsolvents4-5asfollows:wherevisthewave…     

A MATHEMATICAL STUDY OF THE SEVEN GRAPTOLITE BIOZONES OF THE LOWER SILURIAN LONGMAXIAN STAGE IN CHINA

With the aid of matrix theory and computer a series of data can be obtained such as the total number of localities in which r species of graptolites appears, the common number of localities in which both i and j species of graptolites appear, the total number of species of graptolites in one locality, the common number of species of graptolites found in both i and j localities, the total number of zones in which r species of graptolites appears, the common number of zones in which both i and j species appear, the total number of species of graptolites found in one zone, the common number of species of graptolites found in both i and j zones. Based on these data a common problem in biostratigraphy may be solved, that is, in the absence of the zonal graptolite which species of graptolites can be chosen to replace the zonal graptolite, or how to detect the zonal graptolite of a graptolite biozone. The result of matrix treatment not only detects the graptolite biozone but is useful to infer the paleo-biogeo     

Synthesis, Crystal Structure and Properties of [Co(1,3- bdoaH)_2·4H_2O]·4H_2O with Benzene-1,3-dioxyacetate Ligand

1INTRODUCTIONTheorganicaromaticcarboxylatemetalcom-plexeshavearousedmuchattentionandbeenwidelyinvestigated.However,thestrategyofdesignandsynthesisofthesecomplexesismostlyfocusedonrigidligands,suchasterephthalicacidandbenzenetricarboxylicacid,etc.[1～5].Theassemblyofcom-plexesbyusingflexiblearomaticcarboxylateli-gandsisfarlessdeveloped[6,.Phenylenedioxydia-7]ceticacids(bdoaH2)withbiologicalactivitiesandwideapplicationsinagriculture[8]areafamilyofmultidentateflexibleligandswithversatilebind…     

Synthesis and Crystal Structure of a 1-D Chain Zinc（Ⅱ） Coordinated Polymer with N-p-Tolysulfonyl-glutamine

A novel coordination polymer {[Zn(ts-gln)(bipy)]3H2O}n (ts-glnH2=N-p-toly-sulfonyl-glutamine,bipy=2,2-bipyridine) has been prepared and structurally characterized by X-ray diffraction method. It crystallizes in orthorhombic,space group P212121 with a=8.2622(5),b=16.6244(10),c=18.2807(10) ,V=2510.9(3) 3,C22H28N4O8SZn,Mr=573.91,Z=4,Dc= 1.518 g/cm3,μ(MoKa)=1.115 mm-1,F(000)=1192,the final R=0.0262 and wR=0.0662 for 5691 independent reflections with Rint=0.0240. The zinc(Ⅱ) atom is coordinated by N(3) and N(4) atoms of a bipy molecule,two carboxylate O(1) and O(2A) and amino N(1) atoms of ts-gln ligands,resulting in a square-pyramidal geometry. The title complex consists of an infinite zigzag chain of zinc(Ⅱ) ions linked by the carboxylate of N-p-tolysulfonyl-glutamine.     

C60-吡咯烷衍生物的合成及非线性光学性质的研究

通过富勒烯C₆₀与肌氨酸和有机醛化合物的1,3-偶极环加成反应, 获得了九种含不同有机功能基团的C₆₀吡咯烷衍生物1～9, 用¹H NMR, ¹³C NMR, FTIR, UV-vis和FAB-MS进行了结构表征; 利用皮秒激光光源, 采用z扫描技术测定了分子的三阶非线性超极化率γ⁽³⁾, 结果显示: 化合物3 (γ⁽³⁾＝4.14×10^－33 esu)具有最大的三阶非线性光学系数, 说明增加噻吩共轭链的长度, 使三阶非线性活性增加; 对具有相同共轭链的C₆₀-噻吩吡咯烷衍生物(2, 5, 1和4), 吸电子取代基减小了三阶光学非线性活性, 给电子基增大了三阶光学非线性活性; 同时发现喹啉环2-位键联(7)比4-位(8)有更好的三阶光学非线性活性.     

逐步增长聚合的研究进展

逐步增长聚合应用面广,且聚合物分子量是逐步增加的,近来利用逐步增长聚合可以合成新型高分子材料日益引人注目。按照逐步增长聚合的不同类型,对近年来逐步增长聚合研究的新进展,特别是对合成聚酯等的缩聚反应,以及利用二异氰酸酯和Click反应的逐步加成聚合等进行了综述。为了进一步获得性能优良、分子量可控、结构理想且制备方法简便的高分子材料,加强逐步增长聚合理论研究、开发新型结构的单体,并充分开发相应的聚合新技术,是今后逐步增长聚合研究的重点。