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81.
82.
溶液的光谱研究一直受到化学工作者的关注,但大多研究是以一维光谱技术为主,存在分辨率低,误差较大,重叠峰难以分辨等诸多弊端,无法清晰地给出需要的信息。二维光谱通过对外部扰动下的动态光谱进行相关分析计算,从而得到光谱强度的整体变化信息,显著提高一维光谱的分辨率以及重叠峰的分离度。在判断特定外扰下不同官能团的响应次序以及研究分子间、分子内的弱相互作用上具有独特优势。采用二维相关拉曼光谱和理论计算相结合,对溶液内微观团簇及其变化进行了研究。利用显微共焦激光拉曼光谱仪对目标溶液(纯DMF与0.84 mol·L-1的CuCl2/DMF溶液)进行了升温实验。结果发现在C-N键伸缩振动谱带范围内,由于CuCl2的加入,特征峰强度整体大幅下降,峰宽变大,在1 115 cm-1有新峰产生,随温度升高,伸缩振动峰强度逐渐下降,峰形变缓。为了获得C-N键振动内各特征峰随温度的变化情况,采用移动窗口二维拉曼(MW2D Raman)光谱技术,对光谱数据进行分析。结果表明溶液内不同类别的微观团簇对温度的敏锐程度不同,随温度升高,它们之间存在相互转化,且变化速度不同。为了获取溶液内各微观团簇运动的实质,以温度为外扰,采用二维拉曼(2D Raman)光谱对目标溶液进行分析,通过对二维光谱中特征峰进行归属和变化次序判断,发现金属Cu2+的加入,使得溶液体系变得更加复杂,除存在原溶剂内所含的团簇构型,还存在与Cu2+发生溶剂化的团簇构型,它们之间存在着一定的相互转化。利用密度泛函理论对溶液中可能存在的团簇构型进行结构优化和热力学计算,结果证实了Cu2+与DMF存在相互作用,且由此产生的团簇构型[Cu(DMF)n]2+(n=1~6)的稳定性随n的增大逐渐变差,进一步验证了二维相关光谱分析的可行性与正确性。 相似文献
83.
Absence of magnetic order in dichloro [1,2-bis(diphenylphosphino)ethane] nickel~(2+) single crystal 下载免费PDF全文
《中国物理 B》2021,30(5):57501-057501
Dichloro [1,2-bis(diphenylphosphino) ethane] nickel~(2+)(Ni Cl_2(dppe)) is an organic compound containing C_(26)H_(24)P_2(dppe) molecules and Cl-, Ni~(2+)ions. The large-size Ni Cl_2(dppe) single crystals with longest dimension of4 mm were grown by the method of slow evaporation of organic solution. Single crystal x-ray diffraction spectrum indicates that the single crystal is of high quality. Magnetization results of the Ni Cl_2(dppe) single crystals show an anisotropic paramagnetism behavior and diamagnetic background, which come from Ni~(2+) ions and benzene ring, respectively. However, according to the specific heat results with temperature down to 0.1 K and magnetic field up to 14 T, no expected field-induced quantum phase transition was observed in Ni Cl_2(dppe) single crystals. 相似文献
84.
An asymmetric memristive diode-bridge (MDB) emulator is raised to imitate the asymmetric volt-ampere characteristic of a physical memristor. Then, an asymmetric MDB-based Jerk circuit is built and its state equation is derived, upon which the theoretical analysis, MATLAB-based numerical simulations, and hardware measurements are executed to reveal the asymmetric coexisting bifurcations and the phenomenon of multi-stability. The memristive Jerk circuit has three equilibrium points of a pair nontrivial equilibrium points of asymmetric unstable saddle-foci and a zero equilibrium point of unstable saddle-focus, which leads to the occurrence of asymmetric coexisting bifurcations and asymmetric local attraction basins. The asymmetrical bifurcations are numerically disclosed by 1-D/2-D bifurcation plots, Lyapunov spectrum, and phase plane trajectories. Multi-stability with asymmetric coexisting attractors under two sets of system parameters are demonstrated as examples by local attraction basins and phase plane trajectories. Thereafter, experimental circuit prototype employing discrete components is manually welded and hardware measurements are executed to validate the numerical simulations. 相似文献
85.
Broadband topological valley-projected edge-states transport in composite structure phononic crystal 下载免费PDF全文
Hong-Yong Mao 《中国物理 B》2021,30(8):84302-084302
The topological valley transport, realized in phononic crystals, has aroused tremendous interest in these years. Many previous researches have further promoted the development of this transport phenomenon. Crucially, the bandwidth of the valley-projected edge mode has been an essential research topic. As is well known, the broadband will improve the adaptability of the acoustic edge-states, which will be more conducive to the transmission of information. Therefore, in this paper, we present a composite structure, composed of the atoms with different shapes forming a hexagonal lattice, which can achieve larger bandwidth than a single structure. Meanwhile, the results demonstrate that the topological protected edge states are also observed in our structure. Furthermore, the backscattering suppressions from associated valley-protected edge states under certain perturbations have also been investigated and demonstrated. Our work can provide a new idea for designing acoustic devices based on valley degree of freedom. 相似文献
86.
C-2位单取代降冰片烯衍生物中降冰片烯环存在各向异性,且多数为外型和内型异构体的混合物,导致其结构解析困难.针对这一问题,本文在制备了单一构型的C-2位羧基和羟甲基取代的降冰片烯衍生物的基础上,利用1H NMR、DEPT135、1H-1H COSY、1H-13C HMQC、1H-1H NOESY谱和相应的耦合裂分信息,对外型-5-降冰片烯-2-羧酸、内型-5-降冰片烯-2-羧酸、外型-5-降冰片烯-2-甲醇和内型-5-降冰片烯-2-甲醇的1H和13C NMR信号进行归属,并探讨了降冰片烯衍生物的取代基种类及空间构型对1H NMR化学位移的影响. 相似文献
87.
88.
以1-(2-噻唑偶氮)-2-萘酚(TAN)为络合试剂,非离子表面活性剂Triton X-114为萃取剂,浊点萃取同时富集Cr(Ⅲ)和Cr(Ⅵ),并于RP-C18柱上,用含4.5 mmol/L十六烷基三甲基溴化铵(CTMAB)和0.03mol/L HAc-NaAc缓冲溶液(pH5.5)的甲醇-水(体积比69∶31)溶液为流动相,对富集的Cr(Ⅲ)和Cr(Ⅵ)进行高效液相色谱快速分离、测定。对浊点萃取时溶液的pH值、TAN和Triton X-114的用量等影响因素进行了考察。在优化实验条件下,对100μg/L的Cr(Ⅲ)和Cr(Ⅵ)进行7次平行测定,保留时间的相对标准偏差分别为1.2%和0.9%,峰面积的相对标准偏差分别为4.7%和2.7%。Cr(Ⅲ)和Cr(Ⅵ)的线性范围均为50~5 000μg/L,检出限分别为7.5、3.5μg/L。大部分离子不干扰测定,该方法具有较高的灵敏度,可用于湖泊表层沉积物中铬形态的分析。 相似文献
89.
Luo Mei Sun Jie Zhou Shi-Ming Yin Hao Hu Ke-Liang 《Research on Chemical Intermediates》2010,36(9):1049-1054
Two opposite configuration (R/S) of chiral complexes (C8H11N)2·CuCl2 were obtained from the reaction of chiral d(+)/l(−)-α-ethylphenyl amine with copper chloride (II) in dry ethanol. The crystal structures of 1a and 1b were characterized by
IR, elemental analysis and X-ray crystallography. 相似文献
90.
Mei Luo 《Tetrahedron letters》2010,51(42):5577-5580
A series of novel N-metal complexes containing chiral α-ethylphenyl amines was synthesized and they catalyzed asymmetric Henry reactions affording products with high enantioselectivity. 相似文献