分子

Based on the conservation of miRNAs sequence, we compared the known miRNAs among five mam-mals, i.e., human, mouse, cattle, pig and dog with the sequence of sheep genome that is highly homologous to goat genome, published on the NCBI, and 11 candidate miRNAs were eventually obtained. RT-PCR analysis showed the expression of the 11 miRNAs in brain and 5 in liver, indicating that they might be novel miRNAs. The methodology provides an alternative approach to the exploration of new miRNAs in goat.

根据miRNA分子具有一定的保守性，文章将人、小鼠、牛、猪和狗5种哺乳动物已知的miRNA分子与NCBI公布的与山羊具有极高同源性的绵羊基因组序列对比，获得11条miRNA候选分子，然后通过逆转录聚合酶链反应验证，发现在山羊脑组织中这11条分子均有表达，肝脏组织中有5条分子表达，初步确定为山羊新的miRNA分子，为寻找山羊miRNA提供了新的思路。

The influence of position of the substitution, strength and number of donors and acceptors, and their coplanarity and asymmetry is discussed. The results indicate that the molecules may have larger first hyperpolarizabilities when the molecules have stronger and more donors and acceptors, large asymmetry of HOMO and LUMO, better coplanarity and higher accentricity. This work attemps at finding out the relationship between the structure and the property, thus providing theoretical basis for designing nonlinear optical molecules.

进一步研究体系中取代基的位置，给体与受体的数量和得失电子的能力，分子的共面性和对称性对分子第一超极化率的影响，结果表明，有机分子拥有更多数量与更强得失电子能力的给体和受体，最高占据分子轨道和最低未占据分子轨道空间分布的不对称，具有较高的原子共面性和较低的分子中心对称性，都能显著增加

At the normal state, porphyrin molecules do not have EPR signal. However, light excitation may cause a transition of porphyrin molecules from singlet to triplet. At the same time, the change from diamagnetism to paramagnetism occurred to porphyrin molecules. In this case, the two un-paired electrons are nearby each other and cause a strong interaction, giving EPH signal with sharp peak at g = 2.000. The g value increased with an increase in electron cloud density.

常态下卟啉分子没有EPR信号，在光的激发下，卟啉分子由原来的逆磁性分子变成顺磁性的激发三重态分子，这种激发三重态分子在分子轨道上具有两个未成对电子，这两个电子相距很近，彼此之间发生很强的相互作用而产生电子，它的g值随卟啉共轭体系平均电子云密度增大而变大。

At the normal state, porphyrin molecules do not have EPR signal. However, light excitation may cause a transition of porphyrin molecules from singlet to triplet. At the same time, the change from diamagnetism to paramagnetism occurred to porphyrin molecules. In this case, the two un-paired electrons are nearby each other and cause a strong interaction, giving EPR signal with sharp peak at g =2.000. The g value increased with an increase in electron cloud density.

常态下卟啉分子没有EPR信号，在光的激发下，卟啉分子由原来的逆磁性分子变成顺磁性的激发三重态分子，这种激发三重态分子在分子轨道上具有两个未成对电子，这两个电子相距很近，彼此之间发生很强的相互作用而产生电子，它的 g 值随卟啉共轭体系平均电子云密度增大而变大。

The conclusions were as follows: theνO-H andνC=O IR absorption maxima shifted towards higher wave numbers after imprinting 17β-estradiol on TFMAA-co-TRIM copolymer with the red shift of theνO-H groups being apparent after precipitation polymerization for 16h while that forνC=O groups being observed after polymerization for 24h. A strong interaction between TFMAA and 17β-estradiol was confirmed by the high selectivity for 17β-estradiol, as indicted by the values of the separation factor of isomers of 17β-estradiol/17α-estradiol (2.28) and the imprinted factor (3.01). Particle diameter of TFMAA-co-TRIM polymer was between 300 nm and 1.5μm, which suited well for solid phase sorbent throughout at low column pressure. The recognition of imprinting TFMAA-co-TRIM polymer for sterol molecules was driven by enthalpy eluted with acetronitile, and low temperature was in favor of the separation of sterol structure analogues on imprinting column. TFMAA-co-TRIM polymer possessed of determinate anti-heat stability, with melting point beginning at 255.84℃, Tp=257.40℃, control TFMAA-co-TRIM polymer and imprinting TFMAA-co-TRIM polymer were respectively decompounded at 267.79℃and 343.11℃, and solid micro-extraction noddle prepared by the special polymerization also showed definite recognition for 17β-estradiol by GC/MS detecting at 270℃. By selection of various washing and elution solvents, elution reagents of close polymerization system were of more advantage in template molecules retention and recognition on molecularly imprinted solid phase extraction column. At a certain extent, progesterone, 17α-estradiol, 17β-estradiol and 4-androstene-3, 17-dione could be intercepted on the MISPE column. Especially, MISPE had high selectivity for progesterone, and imprinting TFMAA-co-TRIM polymer could achieve adsorption balance within 50 min by absorption kinetics test for 17β-estradiol. However, MISPE column showed better selectivity and enrichment property for 17β-estradiol than C18 and CSPE columns according to the data from HPLC and GC/MS analyses. Recovery of 17β-estradiol on MISPE column was up to 85.5% while when prime extracting solution of milk powder was sampled, the recovery of CSPE and C18 columns were 43.7% and 30.7%, respectively.

通过研究阐明：紫外聚合产物TFMAA-co-TRIM中的νO-H振动吸收峰在聚合16h后红移，νC=O振动吸收峰在聚合24h后红移；TFMAA-co-TRIM对雌二醇异构体的印迹因子达到了3.01，α为2.28，优于其它功能单体参与得到的聚合物识别特性；TFMAA-co-TRIM聚合物粒径介于300 nm至1.5μm之间，作为色谱固定相具有良好的通量和低的柱压；在乙腈流动相中，TFMAA-co-TRIM分子印迹固定相的分离过程主要被焓驱动，低温有利于分子印迹固定相分离甾醇结构类似物；TFMAA-co-TRIM分子印迹聚合物在255.84℃时开始熔融，Tp=257.40℃，聚合物CP的降解温度在267.79℃，MIP降解温度在343.11℃，制备的固相微萃取头初步经GC/MS 270℃的耐热性测定；不同的洗提溶剂筛选证明了选择接近聚合溶剂的洗脱体系更有利于MISPE发挥识别效应；分子印迹固相萃取柱对孕酮、17α-雌二醇、17β-雌二醇和雄烯二酮都具有不同程度的保留特性，可作为此类化合物的吸附材料，特别对孕酮强保留的富集特性，可作为孕酮的选择性识别吸附剂，其分子印迹聚合物对17β-雌二醇的吸附动力学测定显示在50 min内基本达到吸附平衡，具有作为传感器核心敏感材料的潜力；对比萃取奶粉中17β-雌二醇性能，MISPE柱比非分子印迹固相萃取柱和C18柱具有更高的保留，回收率依次为85.5%，43.7%和30.7%。

There are two independent molecules of ZnL or Co(IIL and two water molecules in one asymmetric unit of complex 1(or 2), the crystal structure of CuClL1·2H2O consists of one molecule of CuClL1 and two water solvate molecules in the asymmetric unit, while the ZnL·CH3OH (4) comprises of one molecule of ZnL and a methanol molecule in per unit.

在这四个金属配合物中，配合物(1)和配合物(2)的每个不对称单元中有两个独立的ML 分子和两个水分子，配合物(3)的每个不对称单元中有一个CuClL1分子和两个水分子，而配合物(4)的每个不对称单元中只有一个ZnL 分子和一个甲醇分子。

There are two independent molecules of ZnL or Co(IIL and two water moleculesin one asymmetric unit of complex 1(or 2), the crystal structure of CuClL_1·2H_2O consistsof one molecule of CuClL_1 and two water solvate molecules in the asymmetric unit,while the ZnL·CH3OH (4) comprises of one molecule of ZnL and a methanolmolecule in per unit.

在这四个金属配合物中，配合物(1)和配合物(2)的每个不对称单元中有两个独立的MLZn(IIL、CoL分子和两个水分子，配合物(3)的每个不对称单元中有一个CuClL_1分子和两个水分子，而配合物(4)的每个不对称单元中只有一个ZnL分子和一个甲醇分子。

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。

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。

Based on the changes in the spectrum characters of guest molecules producedthrough inclusion complex formation with cyclodextrins, we have carried out two aspects of investigation:First, the mechanisms for the host-guest recognition reactions have been studied, such as the interactions between 3-CD and curcumin, the main constituent of the rhizomes of the plant Curcuma longa, the recognition of p-CD towards rubidate, the effective component of the Chinese traditional medicine madder, and the reactions of p-CD towards the antileprotic drug dapsone and the antiinflammatory drug nabumetone: The formation of supramolecular complex between P-CD and guest molecule has been discussed and verified in virtue of multitudinous means such asultraviolet-visible absorption, fluorescence emission, infrared spectrogram and so on. The influence of addition of linear alcohols on the supramolecular system has been studied and the reason why the noncovalent interactions in the three-component system could result in a decrease in the apparent association constant of the inclusion complex has been revealed.

本论文基于环糊精对被包结客体光谱性质的改变，开展了两大方面的研究：β-环糊精对姜黄属植物根茎主要成分—姜黄素、中药茜草有效成分—茜草双酯、抗麻风药物氨苯砜及抗炎药物萘丁美酮的主-客体识别反应机制研究：借助超分子包合物的紫外吸收光谱、荧光光谱或红外吸收光谱等手段，通过多种方法探讨并验证了超分子包合物的形成；研究了直链醇的加入对超分子体系的影响，揭示了三元体系中非共价相互作用导致超分子包合物表观结合常数降低的原因：对超分子包结反应进行了热动力学研究，探讨了各热动力学参数的变化趋势并从熵焓互补的角度考察了超分子包结过程；通过荧光猝灭实验进一步揭示了水相中β-环糊精增敏客体荧光的本质原因，从而为超分子化学提供新的理论和研究方法。

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。