The theoretical calculation and spectroscopic experiments indicate a kind of triangular three bonding supramolecular complexes CBr4…X^-…-H-C, which consist of carbon tetrabromide, halide, and protic solvent molecule...The theoretical calculation and spectroscopic experiments indicate a kind of triangular three bonding supramolecular complexes CBr4…X^-…-H-C, which consist of carbon tetrabromide, halide, and protic solvent molecule (referring to dichloromethane, chloroform and acetonitrile), can be formed in solution. The strength of halogen and hydrogen bonds in the triangular complexes using halide as common acceptor obeys the order of iodide〉bromide〉chloride. The halogen and hydrogen bonds work weak-cooperatively. Charge transfer bands of halogen bonding complexes between CBra and halide are observed in UV-Vis absorption spectroscopy in three solvents, and then the stoichiometry of 1:1, formation constants K and molar extinction coefficients ε of the halogen bonding complexes are obtained by Benesi-Hildebrand method. The K and ε show a dependence on the solvent dielectric constant and, on the whole, obey an order of iodide〉bromide〉chloride in the same solvents. Furthermore, the C-H vibrational frequencies of solvent molecules vary obviously with the addition of halide, which indicates the C-H…X- interaction. The experimental data indicate that the halogen bond and hydrogen bond coexist by sharing a common halide acceptor as predicted by calculation.展开更多
Supramolecular polymer complexes with small molecules are self-assembled through non-covalent interactions and have been proposed for a wide variety of applications in materials science and nanoscience.Our research gr...Supramolecular polymer complexes with small molecules are self-assembled through non-covalent interactions and have been proposed for a wide variety of applications in materials science and nanoscience.Our research group has recently shown the possibility of forming highly ordered nanofibers of supramolecular complexes in their thermodynamically stable state using the electrospinning technique.The ultrafast solvent evaporation rate of electrospinning made possible the in-depth characterization of complexes that had never been prepared in their pure state before because of kinetic issues associated with their formation by conventional approaches.The improved understanding of the formation mechanism allowed us to extend the concept to other techniques featuring a fast solvent evaporation rate,such as electrospray and spin-coating.In this article,we review our most significant contributions in this research field.展开更多
The logistics routes allocation discusses optimal routing from origin to destination through distribution center (DC) on condition that both transport and distribution cost should be taken into account. The problem ...The logistics routes allocation discusses optimal routing from origin to destination through distribution center (DC) on condition that both transport and distribution cost should be taken into account. The problem can be solved by the iterative non-linear programming (INLP), in which the transport cost and distribution cost are assumed to be linear and non-linear, respectively. The method works well in most situations. However, when the distribution cost predominates in the total cost, the method falls, and the solution given by the method is not a global minimum but a local minimum. Further study reveals that the INLP method is still a kind of transport routing method like vehicle routing problem (VRP), and the failure of the method must happen when the distribution cost is a major one. On such a condition, further computation on other extreme points, which physically means forcing all routes to pass through one DC one by one, should be carried out. By comparing values on these extreme points, the global optimal solution can be got. The method has both theoretical and practical meaning. In theoretical field, it might force us to seek new method; in practice, it reminds us to do such kind of check when the transport distance is short and warehousing work is major that often happens in local consolidation center or de-vanning center.展开更多
NMR spectroscopy and X-ray crystallography are two premium methods for determining the atomic structures of macro-biomolecular complexes.Each method has unique strengths and weaknesses.While the two techniques are hig...NMR spectroscopy and X-ray crystallography are two premium methods for determining the atomic structures of macro-biomolecular complexes.Each method has unique strengths and weaknesses.While the two techniques are highly complementary,they have generally been used separately to address the structure and functions of biomolecular complexes.In this review,we emphasize that the combination of NMR spectroscopy and X-ray crystallography offers unique power for elucidating the structures of complicated protein assemblies.We demonstrate,using several recent examples from our own laboratory,that the exquisite sensitivity of NMR spectroscopy in detecting the conformational properties of individual atoms in proteins and their complexes,without any prior knowledge of conformation,is highly valuable for obtaining the high quality crystals necessary for structure determination by X-ray crystallography.Thus NMR spectroscopy,in addition to answering many unique structural biology questions that can be addressed specifically by that technique,can be exceedingly powerful in modern structural biology when combined with other techniques including X-ray crystallography and cryo-electron microscopy.展开更多
Charge transport through single molecular neutral mono- and di-cobalt(Ⅱ) complexes with re-conjugated macromolecular wire was investigated. Scanning tunnelling spectroscopy (STS) studies revealed that the mono-co...Charge transport through single molecular neutral mono- and di-cobalt(Ⅱ) complexes with re-conjugated macromolecular wire was investigated. Scanning tunnelling spectroscopy (STS) studies revealed that the mono-cobalt(Ⅱ) complex showed a pronounced rectifying effect with a large rectification ratio and finely featured NDR peaks, while the di-cobalt(Ⅱ) complex showed a relatively symmetric electron transport without clear NDR peaks. The results are explained based on the dipolar and electronic effects.展开更多
基金ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China (No.20675009 and No. 90922023). The basis set aug-cc-pVDZ-PP for iodine atom is downloaded at the website http://bse.pnl.gov/ bse/portal.
文摘The theoretical calculation and spectroscopic experiments indicate a kind of triangular three bonding supramolecular complexes CBr4…X^-…-H-C, which consist of carbon tetrabromide, halide, and protic solvent molecule (referring to dichloromethane, chloroform and acetonitrile), can be formed in solution. The strength of halogen and hydrogen bonds in the triangular complexes using halide as common acceptor obeys the order of iodide〉bromide〉chloride. The halogen and hydrogen bonds work weak-cooperatively. Charge transfer bands of halogen bonding complexes between CBra and halide are observed in UV-Vis absorption spectroscopy in three solvents, and then the stoichiometry of 1:1, formation constants K and molar extinction coefficients ε of the halogen bonding complexes are obtained by Benesi-Hildebrand method. The K and ε show a dependence on the solvent dielectric constant and, on the whole, obey an order of iodide〉bromide〉chloride in the same solvents. Furthermore, the C-H vibrational frequencies of solvent molecules vary obviously with the addition of halide, which indicates the C-H…X- interaction. The experimental data indicate that the halogen bond and hydrogen bond coexist by sharing a common halide acceptor as predicted by calculation.
基金supported by a grant and a graduate scholarship (MRL)from the Natural Sciences and Engineering Research Council of Canada(NSERC)
文摘Supramolecular polymer complexes with small molecules are self-assembled through non-covalent interactions and have been proposed for a wide variety of applications in materials science and nanoscience.Our research group has recently shown the possibility of forming highly ordered nanofibers of supramolecular complexes in their thermodynamically stable state using the electrospinning technique.The ultrafast solvent evaporation rate of electrospinning made possible the in-depth characterization of complexes that had never been prepared in their pure state before because of kinetic issues associated with their formation by conventional approaches.The improved understanding of the formation mechanism allowed us to extend the concept to other techniques featuring a fast solvent evaporation rate,such as electrospray and spin-coating.In this article,we review our most significant contributions in this research field.
基金the National Science Foundation,Ministry of Education and Science, Japan (No. 17330089)
文摘The logistics routes allocation discusses optimal routing from origin to destination through distribution center (DC) on condition that both transport and distribution cost should be taken into account. The problem can be solved by the iterative non-linear programming (INLP), in which the transport cost and distribution cost are assumed to be linear and non-linear, respectively. The method works well in most situations. However, when the distribution cost predominates in the total cost, the method falls, and the solution given by the method is not a global minimum but a local minimum. Further study reveals that the INLP method is still a kind of transport routing method like vehicle routing problem (VRP), and the failure of the method must happen when the distribution cost is a major one. On such a condition, further computation on other extreme points, which physically means forcing all routes to pass through one DC one by one, should be carried out. By comparing values on these extreme points, the global optimal solution can be got. The method has both theoretical and practical meaning. In theoretical field, it might force us to seek new method; in practice, it reminds us to do such kind of check when the transport distance is short and warehousing work is major that often happens in local consolidation center or de-vanning center.
基金supported by grants from the Research Grants Council of Hong Kong to M.Z.supported by the National Major Basic Research Program of China (Grant No. 2011CB910500)+3 种基金the National Natural Science Foundation of China (Grant No. 31070657)the Knowledge Innovation Program of the Chinese Academy of Sciences (Grant No. KSCX2-YW-R-154)The NMR spectrometers used in our studies were funded by donations from the Hong Kong Jockey Club Charity Foundationthe Special Equipment Grant from RGC of Hong Kong (Grant No. SEG_HKUST06)
文摘NMR spectroscopy and X-ray crystallography are two premium methods for determining the atomic structures of macro-biomolecular complexes.Each method has unique strengths and weaknesses.While the two techniques are highly complementary,they have generally been used separately to address the structure and functions of biomolecular complexes.In this review,we emphasize that the combination of NMR spectroscopy and X-ray crystallography offers unique power for elucidating the structures of complicated protein assemblies.We demonstrate,using several recent examples from our own laboratory,that the exquisite sensitivity of NMR spectroscopy in detecting the conformational properties of individual atoms in proteins and their complexes,without any prior knowledge of conformation,is highly valuable for obtaining the high quality crystals necessary for structure determination by X-ray crystallography.Thus NMR spectroscopy,in addition to answering many unique structural biology questions that can be addressed specifically by that technique,can be exceedingly powerful in modern structural biology when combined with other techniques including X-ray crystallography and cryo-electron microscopy.
基金the financial supports of the National Science Foundationthe NSF MRSEC program at the University of Chicago
文摘Charge transport through single molecular neutral mono- and di-cobalt(Ⅱ) complexes with re-conjugated macromolecular wire was investigated. Scanning tunnelling spectroscopy (STS) studies revealed that the mono-cobalt(Ⅱ) complex showed a pronounced rectifying effect with a large rectification ratio and finely featured NDR peaks, while the di-cobalt(Ⅱ) complex showed a relatively symmetric electron transport without clear NDR peaks. The results are explained based on the dipolar and electronic effects.