查询词典 intramolecular

However, this amino acid substitution could have an effect on intramolecular interactions.

然而，这种氨基酸的替换却对分子内相互作用有影响。

For intramolecular electron transfer reactions in solution,the fluctuations of the intramolecular vibrational modes are much faster than that of solvent mode.Thus,the reaction-diffusion equation is commonly used to describe the motion of solvent,with a sink function to treat the vibrational high-frequency mode.Based on this theory-so -called the Sumi-Marcus theory,we proposed an imaginary-time split operator approach to solve the reaction-diffusion equation.The approach is applied to evaluate the intermolecular ET rate between oxazine 1 and N,N-dimethlaniline.By measuring the two average survival times of the donor state probability and the rate constant in long time limit,the full kinetics of the ET is revealed with a variety of sink functions.

对于扩散控制的溶液中的电子转移反应，分子内振动模的运动比溶剂运动快很多，Sumi-Marcus理论提出用反应扩散方程(reaction-diffusion equation)处理溶剂的扩散运动，而分子内的振动用sink函数来表示，我们基于此理论发展了用虚时间分裂算符的方法(imaginary-time Split operator approach)解反应扩散方程，并将其应用于嗪1(oxazine 1，OX1)和N，N-二甲基苯胺分子之间的电子转移反应，Sink函数采用几种不同的微扰表达式，通过计算得到给体几率衰减的两种平均速率和长时间极限下的速率常数，揭示了该体系电子转移过程中的一些动力学性质。

It was found that the geometries of the studied materials were significantly affected by the ring size and intramolecular charge transfer. The HOMO level, LUMO level, and band gap of the studied model compounds were well controlled by the acceptor strength. However, the electronic properties of the studied polymer showed a significant different trend with the acceptor strength due to the geometrical transformation. The model compound of EDOT-TP and T-TP has the aromatic geometry but is transformed to the quinoid geometry for large intramolecular charge transfer. The small bond length alternation and large acceptor strength in the EDOT-BDP polymer also results in the smallest Eg of 0.7 eV among the studied polymers.

我们发现环的大小以及分子内电荷转移对结构有很大的影响，而小分子的HOMO、LUMO和能隙受到电子受体强度所控制，然而，高分子的电子特性与其构成分子却有明显不同的趋势，这主要是由於分子结构的转变，如小分子EDOT-TP以及T-TP因分子内电荷转移，使其高分子结构由aromatic转变成quinoid；而EDOT-BPP因其键长改变量小和良好的电子受体强度，使其能隙仅0.7个电子伏特。

During the investigation of the reactivity of O_SCl_2(PPh_3)_2CH=C(PPh_3CHCH=CH_2 and O_SCl_2(PPh_3)_2CH=C(PPh_3C(=CH_2)CH=CH2, several stable osmacycles with novel structure, such as osmabenzenes, osmafurans, osmacycles containing intramolecular-coordinated allene, intramolecular-coordination osmacycles containing osmacarbene, an osmacyclopentadiene, were isolated during the investigation of the reactivity of O_SCl_2(PPh_3)_2CH=C(PPh_3CHCH=CH_2 and O_SCl_2(PPh_3)_2-CH=C(PPh_3C(=CH_2)CH=CH_2.In addition, some convenient and efficient methods to prepare these osmacycles were developed.

首先，合成出两种具有反应活性的金属杂五元环IC配合物OsCl_2(PPh_3)_2CH=C(PPh_3CHCH=CH_2和OsCl_2(PPh_3)_2CH=C(PPh_3C(=CH_2)-CH=CH_2，并对它们进行了系统表征；进而，研究了这些活性五元配合物的反应性，合成出多种稳定的锇杂环配合物，其中包括锇苯、锇呋喃、含配位联烯的锇杂IC环化合化物、含锇卡宾的IC环化物、首例锇杂环戊二烯化合物等多元化的产物。

In this thesis,the AM1,MNDO,MINDO/3(mainly AM1)and INDO/S-CI semiempirical MO methods were used toinvestigate the excited-state intramolecular protontransfer reactions of salicylic acid derivatives—salicylic acid,methyl salicylate,salicylaldehyde,o-hydroxyaceto-phenone,salicylamide and 3-hydroxy-picolinamide (6 conformers and 2-3 anion species);2-(2'-hydroxy-5' methylphenyl) benzotriazole(4 conformers),2-(2' hydroxyphenyl) benzimidazole (3 conformers and 3anion species),Bis-2,5-(2-benzoxazolyl)hydroquinone(3 conformers),2-(2'-hydroxyphenyl)benzothiazole(2conformers) and 7-azaindole dimer (2 conformers).Theinvestigations were described as follows.Geometry optimization,relative stability andhydrogen bonding energy First,for sylicylic acid derivative molecules,the AM1,MNDO and MINDO/3 methods were used toinvestigate ground-state geometry optimization,energies,relative stabilities and hydrogen-bondingenergies on the five kinds of the molecules(designing 6 conformers and 2-3 anion species).Comparing with experimental data,the optimizedgeometry,the order of stability,the hydrogen-bonding energies and the distances between O-O in O-H..O hydrogen bonds by AM1 method were in agreementwith the experimental data,however,the C-C bondlengths optimized by MNDO and MINDO/3 were longer,C-O and O-H bond lengths were shorter;for C-N bondlengths,the results opitimized by MNDO method werethe same as those by AM1 method,nevertheless the C-Nbond lengths given by MINDO/3 method were muchshorter.For some sylicylic acid derivatives(e.g.methyl salicylate,salicylamide),the order ofstabilities on the conformers given by MNDO andMINDO/3 methods were not in agreement with theexisting conformers deduced by experimental methods,and the hydrogen bonding energies calculated by MNDO.and MINDO/3 methods were smaller.Second,the studyon the other systems found that the optimizedgeometry of the proton-transfered product with INDOmethod could not be obtained,only could theoptimized geometry of reactant be obtained,and thecalculated hydrogen bonding energies were greater.Many results of calculation indicated that the studyon the excited-state intramolecular proton transferreaction system using AM1 method was suitable andreliable.

本论文用AM1、MNDO、MINDO/3（主要是AM1）和INDO/S-CI半经验分子轨道方法对水杨酸衍生物系列——水杨酸、水杨酸甲酯、水杨醛、O-羟基乙酰苯酮、水杨酰胺和3-羟基吡啶酰胺（6种异构体和2-3种阴离子）；2-（2'-羟基-5'-甲基苯基）苯并三〓唑（4种异构体）；2-（2'-羟基苯基）苯并咪唑（3种异构体和3种阴离子）；2，5-二间氮杂氧茚氢醌（3种异构体）；2-（2'-羟基苯基）间〓杂硫茚（2种异构体）和7-〓吲哚二体（2种异构体）的激发态分子内质子转移反应在以下几个方面进行了较系统的理论研究：几何构型优化和相对稳定性及氢键能首先以水杨酸衍生物系列分子为例，用AM1、MNDO和MINDO/3方法考察了5种分子（每种分子设计6种异构体和2-3种阴离子）的基态几何构型优化，能量、相对稳定性和氢键能计算，通过和实验数据进行比较，AM1方法给出的优化几何构型、稳定性次序、氢键能和O—H。。。O氢键的0—0距离与实验数据吻合最好，MNDO和MINDO/3方法优化的C-C键长偏长，C-O键和O-H键长偏短；对于C-N键长，MNDO和AM1优化结果差别不大，而MINDO/3给出了过短的C-N键长，MNDO和MINDO/3方法给出的有些水杨酸衍生物分子（如水杨酸甲酯和水杨酰胺）异构体的稳定性次序和实验上推测的可存在异构体结果不一致，MNDO和MINDO/3方法给出的氢键能偏低，对其他体系的研究发现INDO方法常常不能得到质子转移产物的优化几何构型，只能得到反应物的优化构型，并且估算的氢键能偏高，大量的计算结果表明AM1方法对本论文研究的激发态分子内质子转移反应体系是适宜和可靠的。

The dissertation is focused on the research of organic supramolecular self-assembly and molecule folding. It consists of four parts. In the first part, three new model molecules for investigating intramolecular coaggregation behavior have been designed and synthesized. Fluorescence studies reveal that intramolecular coaggregation of these molecules take place with the increase of the solvent polarity because of hydrophobic-lipophilic interaction .

本论文主要对有机超分子自组装和分子折叠做了一些研究，共分四个部分：第一部分中，我们设计并合成了一个新的研究分子内自簇集的模型，用荧光光谱法对该模型进行了研究，研究表明，在促簇能力较强的溶剂体系中，这一类模型分子可在疏水亲脂作用的驱动下发生分子内自簇集而形成卷曲的构象。

Results show that intramolecular hydrogen transfer is not favored in view of the energy trend along IHT coordinate in the region such as hypericin's peri region, where two hydrogens of hydroxyl groups bond with a common oxygen of carbonyl group and exists two IHBs in the peri region. However, intramolecular proton transfer often occur in the molecule with hexahydric cycle hydrogen bond, where only one pair of adjacent hydroxyl group and carbonyl group.

此外选择设计了一个具有三个分子内氢键的体系，兼具金丝桃蒽酮和其他苝醌类光敏剂的分子内氢键特点，研究表明两个羟基氢与共同的羰基氧形成的氢键由于存在较高的势垒，很难发生分子内氢传递，即具有金丝桃蒽酮端位结构的分子其分子内氢传递很难发生，而一般的能形成六元环状结构的分子内氢键体系容易发生分子内氢传递。

However, Fermi resonance is an important role in the intramolecular vibrational energy transfer process, so we use the bend triatomic molecule model described by potential energy calculated from U(4) algebra, and the chaos of high excited molecular vibration can be studied by analyses of the intramolecular vibrational energy transfer process.

Fermi共振相互作用作为分子内能量转移的一种机制，在描述分子激发的完全振动方面有着重要的作用，因此，我们在构建弯曲三原子分子模型时引用了U(4)代数方法获得的势能面，从能量传递角度研究体系的混沌性质，是在多原子分子激发态领域研究非线性问题的合理延伸。

The intramolecular hydrogen bonding energies for some special systems were evaluated by means of the substitution method, cis-trans method, and supermolecular approach. The intramolecular hydrogen bonding energies predicted by the substitution method agree well with the values obtained by the cis-trans method and the supermolecular approach.

对一些特殊体系，使用取代法，cis-trans方法和超分子方法计算了氢键键能，取代法计算得到的氢键键能与cis-trans方法、超分子方法的计算结果相符。

An intramolecular α-addition of hydroxy or amine-substituted electron-deficient alkyns catalyzed by phosphines was developed. An intramolecular β-addition of hydroxysubstituted 2-alkynoates trigged by the tributylphosphine was also achieved.

在上面的研究中发现低活性的亚甲基取代的环内酰胺的[3+2]环加成反应也能顺利进行，因此我们研究并实现了β-位取代的贫电子烯烃的环加成反应，进一步拓展了叔膦催化的[3+2]环加成反应。

The split between the two groups can hardly be papered over.

这两个团体间的分歧难以掩饰。

This approach not only encourages a greater number of responses, but minimizes the likelihood of stale groupthink.

这种做法不仅鼓励了更多的反应，而且减少跟风的可能性。