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951.
Yang Bai Zhong-Jun Zhou Jia-Jun Wang Ying Li Di Wu Wei Chen Zhi-Ru Li Chia-Chung Sun 《Journal of molecular modeling》2013,19(9):3983-3991
How to generate a non-zero first hyperpolarizability for a centrosymmetric molecule is a challenging question. In this paper, an external (pump) electric field is used to make a centrosymmetric benzene molecule generate a non-zero value of the electric field induced first hyperpolarizability (β F ). This comes from the centrosymmetry breaking of electron cloud. Two interesting rules are exhibited. (1) β F is anisotropic for different directional fields (F i, i?=?X, Y, Z). (2) The field dependence of β F is a non-monotonic function, and an optimum external electric field causes the maximum value of β F . The largest first hyperpolarizability β F reaches the considerable level of 3.9?×?105 a.u. under F Y?=?330?×?10?4 a.u. for benzene. The external electric field effects on non-centrosymmetric edge-modified graphene ribbon H2N-(3,3)ZGNR-NO2 was also studied in this work. The first hyperpolarizability reaches as much as 2.1?×?107 a.u. under F X?=?600?×?10?4 a.u. for H2N-(3,3)ZGNR-NO2. We show that the external electric field can not only create a non-zero first hyperpolarizability for centrosymmetric molecule, but also remarkably enhance the first hyperpolarizability for a non-centrosymmetric molecule. 相似文献
952.
Huidong Li Hao Feng Weiguo Sun Qunchao Fan Yaoming Xie R. Bruce King Henry F. Schaefer III 《Journal of molecular modeling》2013,19(7):2723-2737
The bis(heptalene)dimetal complexes (C12H10)2M2 of the first row transition metals from Ti to Ni are predicted by density functional theory to exhibit “submarine” sandwich structures with a pair of metal atoms sandwiched between the two heptalene rings. For the early transition metal derivatives (C12H10)2M2 (M = V, Cr) there are two types of such structures. In one structural type the metals are sandwiched between two heptahapto heptalene rings with metal-metal distances (3.5–3.8 Å) too long for direct metal-metal bonding. The other type of (C12H10)2M2 (M = V, Cr, Mn) structure has a pair of bonded metal atoms sandwiched between a fully bonded heptalene ligand and a heptalene ligand bonded to the metals only through an eight-carbon heptafulvene subunit, leaving an uncomplexed cis-1,3-diene unit. The formal metal-metal bond orders in these latter structures are 3, 2, and 1 for M = V, Cr, and Mn with predicted bond lengths of 2.5, 2.7, and 2.8 Å, respectively. For (C12H10)2Fe2 a singlet structure with each iron atom sandwiched between a hexahapto and a tetrahapto heptalene ring is energetically preferred over an alternate structure with ferrocene-like iron atoms sandwiched between two pentahapto heptalene rings. Partial bonding of each heptalene ring to the metal atoms occurs in the late transition metal derivatives (C12H10)2M2 (M = Co, Ni). This leads to an unsymmetrical structure for the cobalt derivative and a structure for the nickel derivative with each nickel atom sandwiched between a trihapto ligand and a tetrahapto ligand. Figure
The bis(heptalene) dimetal complexes (C12H10)2M2 (M = Ti to Ni) are predicted by density functional theory to have a “submarine” sandwich structure with a pair of metal atoms sandwiched between the two heptalene rings. In the early transition metal derivatives (C12H10)2M2 (M = V, Cr) the metal atoms are sandwiched between two heptahapto heptalene rings. In contrast, for (C12H10)2M2 (M = Mn, Fe, Co, Ni) the heptalene rings are only partially bonded to the metal atoms. 相似文献
953.
In the present paper, a new type of Lewis acid–base complex BX3???Li@Calix[4]pyrrole (X = H and F) was designed and assembled based on electride molecule Li@calix[4]pyrrole (as a Lewis base) and the electron deficient molecule BX3 (as a Lewis acid) by employing quantum mechanical calculation. The new Lewis acid–base complex offers an interesting push-excess electron-pull (P-e-P) framework to enhance the stability and nonlinear optical (NLO) response. To measure the nonlinear optical response, static first hyperpolarizabilities (β 0) are exhibited. Significantly, point-face assembled Lewis acid–base complex BF3???Li@Calix[4]pyrrole (II) has considerable first hyperpolarizabilities (β 0) value (1.4?×?106 a.u.), which is about 117 times larger than reported 11,721 a.u. of electride Li@Calix[4]pyrrole. Further investigations show that, in BX3???Li@Calix[4]pyrrole with P-e-P framework, a strong charge-transfer transition from the ground state to the excited state contributes to the enhancement of first hyperpolarizability. Theory calculation of enthalpies of reaction (ΔrH0) at 298 K demonstrates that it is feasible to synthetize the complexes BX3???Li@Calix[4]pyrrole. In addition, compared with Li@Calix[4]pyrrole, the vertical ionization potential (VIP) and HOMO–LUMO gap of BX3???Li@Calix[4]pyrrole have obviously increased, due to the introduction of the Lewis acid molecule BX3. The novel Lewis acid–base NLO complex possesses not only a large nonlinear optical response but also higher stability. Figure
A novel Lewis acid–base complex is first proposed by the combination of usual Lewis acid and an electride. It offers an interesting push-excess electron-pull framework to enhance the stability and nonlinear optical response. 相似文献
954.
955.
Xiaojing Yan David C. Essaka Liangliang Sun Guijie Zhu Norman J. Dovichi 《Proteomics》2013,13(17):2546-2551
The Escherichia coli proteome was digested with trypsin and fractionated using SPE on a C18 SPE column. Seven fractions were collected and analyzed by CZE‐ESI‐MS/MS. The separation was performed in a 60‐cm‐long linear polyacrylamide‐coated capillary with a 0.1% v/v formic acid separation buffer. An electrokinetic sheath‐flow electrospray interface was used to couple the separation capillary with an Orbitrap‐Velos operating in higher‐energy collisional dissociation mode. Each CZE‐ESI‐MS/MS run lasted 50 min and total MS time was 350 min. A total of 23 706 peptide spectra matches, 4902 peptide IDs, and 871 protein group IDs were generated using MASCOT with false discovery rate less than 1% on the peptide level. The total mass spectrometer analysis time was less than 6 h, the sample identification rate (145 proteins/h) was more than two times higher than previous studies of the E. coli proteome, and the amount of sample consumed (<1 μg) was roughly fourfold less than previous studies. These results demonstrate that CZE is a useful tool for the bottom‐up analysis of prokaryote proteomes. 相似文献
956.
Ganesh Kumar Agrawal Dominique Job Thomas Kieselbach Bronwyn J. Barkla Sixue Chen Renu Deswal Sabine Lüthje Ramesh Sundar Amalraj Georgia Tanou Bongani Kaiser Ndimba Rainer Cramer Wolfram Weckwerth Stefanie Wienkoop Michael J. Dunn Sun Tae Kim Yochiro Fukao Masami Yonekura Lello Zolla Jai Singh Rohila Rungaroon Waditee‐Sirisattha Antonio Masi Tai Wang Abhijit Sarkar Raj Agrawal Jenny Renaut Randeep Rakwal 《Proteomics》2013,13(21):3093-3100
The International Plant Proteomics Organization (INPPO) is a non‐profit organization whose members are scientists involved or interested in plant proteomics. Since the publication of the first INPPO highlights in 2012, continued progress on many of the organization's mandates/goals has been achieved. Two major events are emphasized in this second INPPO highlights. First, the change of guard at the top, passing of the baton from Dominique Job, INPPO founding President to Ganesh Kumar Agrawal as the incoming President. Ganesh K. Agrawal, along with Dominique Job and Randeep Rakwal initiated the INPPO. Second, the most recent INPPO achievements and future targets, mainly the organization of first the INPPO World Congress in 2014, tentatively planned for Hamburg (Germany), are mentioned. 相似文献
957.
Eggshell strength is a crucial economic trait for table egg production. During the process of eggshell formation, uncalcified eggs are bathed in uterine fluid that plays regulatory roles in eggshell calcification. In this study, a label‐free MS‐based protein quantification technology was used to detect differences in protein abundance between eggshell matrix from strong and weak eggs (shell matrix protein from strong eggshells and shell matrix protein from weak eggshells) and between the corresponding uterine fluids bathing strong and weak eggs (uterine fluid bathing strong eggs and uterine fluid bathing weak eggs) in a chicken population. Here, we reported the first global proteomic analysis of uterine fluid. A total of 577 and 466 proteins were identified in uterine fluid and eggshell matrix, respectively. Of 447 identified proteins in uterine fluid bathing strong eggs, up to 357 (80%) proteins were in common with proteins in uterine fluid bathing weak eggs. Similarly, up to 83% (328/396) of the proteins in shell matrix protein from strong eggshells were in common with the proteins in shell matrix protein from weak eggshells. The large amount of common proteins indicated that the difference in protein abundance should play essential roles in influencing eggshell strength. Ultimately, 15 proteins mainly relating to eggshell matrix specific proteins, calcium binding and transportation, protein folding and sorting, bone development or diseases, and thyroid hormone activity were considered to have closer association with the formation of strong eggshell. 相似文献
958.
959.
960.
Jun Qian Chen-xu Liu Wu-deng Wang Jing Chen Yu-dong Li Jing-jun Xu Qian Sun 《Plasmonics (Norwell, Mass.)》2013,8(2):955-962
The optical responses of metal nanoparticles induced by subtle variations in geometry, especially by the rounding of the edges and corners, have generated great interest at present due to the requirement of fabricating refined structures of metal nanoparticles and theoretical simulations of the real particles. We study the effect of both inner and outer edge rounding on the optical properties of gold nanobox and gold nanobox dimer with small interparticle distances by using the discrete dipole approximation method. The shift of extinction peaks, the electric field distribution, and the variation of refractive index sensitivities by changing the curvature of the inner and outer edges of gold nanobox are investigated. We demonstrate that the optical properties of nanobox are more sensitive to the outer edge rounding than the inner edge rounding. By edge rounding of two very close gold nanoboxes, the blue shift of the dipolar and the quadrupolar plasmonic resonances of nanobox dimer are shown. Comparing with the inner edge rounding of nanobox dimer, we find that rounding of the outer edges causes the larger shift of the quadrupolar mode and approximate shift of the dipole mode. 相似文献