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571.
The BLUF (blue light sensor using flavin adenine dinucleotide) domain is widely studied as a prototype for proton coupled electron transfer (PCET) reactions in biological systems. In this work, the photo-induced concerted PCET reaction from the light state of the AppA BLUF domain is investigated. To model the simultaneous transfer of two protons in the reaction, two-dimensional potential energy surfaces for the double proton transfer are first calculated for the locally excited and charge transfer states, which are then used to obtain the vibrational wave function overlaps and the vibrational energy levels. Contributions to the PCET rate constant from each pair of vibronic states are then analyzed using the theory based on the Fermi's golden rule. We show that, the recently proposed light state structure of the BLUF domain with a tautomerized Gln63 residue is consistent with the concerted transfer of one electron and two protons. It is also found that, thermal fluctuations of the protein structure, especially the proton donor-acceptor distances, play an important role in determining the PCET reaction rate. © 2018 Wiley Periodicals, Inc. 相似文献
572.
Awatef Hattab Zoubeida Dhaouadi Alhadji Malloum Jean Jules Fifen Souad Lahmar Nino Russo Emilia Sicilia 《Journal of computational chemistry》2019,40(18):1707-1717
The possible isomers of [Mg(NH3)n = 1 − 10]+ clusters have been investigated using both M06-2X/6-31++G(d,p) and MP2/6-31++G(d,p) levels of theory. The isomeric distribution for each n size has been studied as a function of temperatures ranging from 25 to 400 K. To the best of our knowledge, for clusters size n > 6, this is the first theoretical study available in the literature. From the calculated values in the considered clusters and using a fitting procedure, we have evaluated the binding energies (−14.0 kcal/mol), clustering energies (−10.1 kcal/mol), clustering free energies (−2.8 kcal/mol), and clustering enthalpies (−10.3 kcal/mol). On the basis of our structural and infrared (IR) spectroscopy outcomes, we find that the first solvation shell can hold up to six ammonia molecules. © 2019 Wiley Periodicals, Inc. 相似文献
573.
Tymofii Y. Nikolaienko Leonid A. Bulavin 《International journal of quantum chemistry》2019,119(3):e25798
We present the procedure for transforming delocalized molecular orbitals into the localized property-optimized orbitals (LPOs) designed for building the most accurate, in the Frobenius norm sense, approximation to the first-order reduced density matrix in form of the sum of localized monoatomic and diatomic terms. In this way, a decomposition of molecular properties into contributions associated with individual atoms and the pairs of atoms is obtained with the a priori known upper bound for the decomposition accuracy. Additional algorithm is proposed for obtaining the set of “the Chemist's LPOs” (CLPOs) containing a single localized orbital, with nearly double occupancy, per a pair of electrons. CLPOs form an idealized Lewis structure optimized for the closest possible reproduction of one-electron properties derived from the original many-electron wavefunction. The computational algorithms for constructing LPOs and CLPOs from a general wavefunction are presented and their implementation within the open-source freeware program JANPA ( http://janpa.sourceforge.net /) is discussed. The performance of the proposed procedures is assessed using the test set of density matrices of 33 432 small molecules obtained at both Hartree-Fock and second-order Moller-Plesset theory levels and excellent agreement with the chemist's Lewis-structure picture is found. 相似文献
574.
针对“低慢小”目标探测面临的问题,提出了一种栅格化理念解决问题思路,给出了栅格化感知系统的定义,设计了栅格化感知系统,包括传感器分系统、通信分系统、管理控制中心和综合保障分系统等组成和工作过程。分析了栅格化感知系统的关键技术,包括传感器低成本设计、“低慢小”目标检测、数据融合处理等技术。研究了栅格化感知系统的部署原则,建立部署原则模型,对于解决“低慢小”目标探测具有现实指导意义。 相似文献
575.
Cui Ping YU Li Fang ZHANG Zhi Quan SHEN Institute of Polymer Science Zhejiang University Hangzhou 《中国化学快报》2003,(10)
The ring-opening polymerization of e-caprolactone (CL) initiated by novel single lanthanide tris(4-tert-butylphenolate)s [Ln(OTBP)3] is reported. Single-component La(OTBP)3 can effectively prepare polycaprolactone (PCL) with over 90% yield and viscosity average molecular weight about 60 x 10 under quite mild conditions: molar ratio of CL to initiator is 1000, 60 C, 2 h in toluene. Mechanism study indicates that the monomer inserts into the growing chain via the break of acyl-oxygen bond of CL. 相似文献
576.
Well‐defined poly(ethylene oxide)s (PEOs) bearing reactive sites regularly distributed along the chain have been synthesized by the polycondensation of PEO containing a central tertiary amino group with dichloromethane, followed by quaternization with suitable reagents to obtain polyzwitterionic or cationic PEOs with alkyl, allyl, or fluorocarbon pendant groups. The pendant allyl groups have been converted into primary amino groups by reaction with 2‐aminoethanethiol hydrochloride to obtain polyamino‐functionalized PEO.
577.
578.
H. Lawrence Clever 《Monatshefte für Chemie / Chemical Monthly》2003,134(5):745-750
Summary. There are more than 150 papers that report on the solubility of the four chloromethanes in water. Volume 62 of the Solubility
Data Series compiles and evaluates the papers concerned with the liquid–liquid solubility of the chloromethanes with water.
A similar evaluation has not been carried out for the vapor–liquid solubility at a partial pressure up to the saturation vapor
pressure of the four chloromethanes. This paper uses the liquid–liquid evaluated solubility values to calculate vapor–liquid
Henry’s constants. They are compared with a compilation of Henry’s constants with good agreements between the calculated constants and the median of the compiled constants. It is believed
that the calculated constants are a reliable set of values to use for the vapor–liquid solubility of the chloromethanes in
water.
E-mail: hlclever@worldnet.att.net
Received October 11, 2002; accepted October 22, 2002
Published online April 24, 2003
RID="a"
ID="a" Dedicated to Prof. Dr. Heinz Gamsj?ger on the occasion of his 70th birthday 相似文献
579.
Asymmetric hetero‐Diels‐Alder (AHDA) reactions provide a multitude of opportunities for the highly efficient, regio‐ and stereoselective construction of various heterocycles in enantiomerically pure form. The asymmetric aza‐Diels‐Alder (A‐aza‐DA) reaction using diversely hetero‐dienophiles and hetero‐dienes have been increasingly developed as a valuable method for the synthesis of functionalized nitrogen ring systems. The purpose of this review is to give a detailed discussion of the A‐aza‐DA reaction particularly, the stereoselective reactions of imines as dienophiles with Dainshefsky dienes to obtain optically pure aza‐Diels‐Alder products. The development of stereoselective variants of the reaction make use of imines as the dienophile and Dainshefsky dienes is at the forefront of these studies. This review updates the A‐aza‐DA reactions covering the literature from 1972 till date 相似文献
580.
Harald Hillebrecht Natascha Vojteer Vanessa Sagawe Kathrin Hofmann Barbara Albert 《无机化学与普通化学杂志》2019,645(3):362-369
Transparent and nearly colorless single crystals of r‐LiB13C2 were obtained by reaction of boron with Li2CO3 in a Cu melt at 1250–1300 °C. The structure analysis [R3 m, a = 5.6535(1), c = 12.5320(2) Å, 421 independent reflections, 22 parameters, R1 = 0.034, wR2 = 0.093] revealed a crystal structure that can be described as a filling variant of rhombohedral B13C2. Li+ is located in a void above or below the linear CBC unit. The site occupation is close to 50 % resulting in an electron‐precise composition according to Wade's rules if a positive charge is given to the CBC entity: Li+(B12)2–(CBC)+. The displacement parameters of the CBC unit indicate disorder in the [001] direction, that relates to the short Li–C distance and the partial occupation of the Li+ site. The composition is confirmed by EELS measurements of single crystals. Band gap calculations give a value of 2.94 eV, which is in agreement to the crystals being colorless. The evaluation of the electron density by application of the QTAIM formalism as proposed by Bader modifies the assignment pictured above according to Wade's rules. In agreement to the electronegativities the carbon atoms carry a negative charge (–2.31/–2.42) and the effective charges are: Li+0.81(B12)+2.02(CBC)–2.83. 相似文献