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Structures of Na~+-AD ion-complexes with 1 or 2 H2O molecules were obtained. It was found that H2O can bond with Na~+ in the structure of Na~+-AD to form Na-O van der Waals bond. H2O molecule can also bond with N or O atoms in AD moiety to form H-bonds as N-H…Ow or O…Hw-Ow. The former process takes place more easily. The most stable structures of Na~+-AD ion-complexes with 1 and 2 H2O molecules are W-C7AB and 2W-C7AB, respectively.αB conformer of Na~+-AD can not exist in the presence of 2 H2O molecules.

研究发现水分子可以结合在Na~+-AD络合离子中的Na~+附近形成Na-OW范德华键,也可以与Na~+-AD络合离子骨架结构中电负性较强的N或O原子结合形成N-H…OW或O…HW-OW氢键,相对而言,水分子更容易结合在Na~+-AD络合离子中的Na~+位置,Na~+-AD最稳定的带1个或2个水分子的结构分别为W-C7AB和2W-C7AB,Na~+-AD络合离子的αB构象在2分子水存在的情况下完全消失。

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%。

The advances and existing problems concerning in genetics especially on the sex-inheritance and tolerance to papaya ring spot virus, the genetic improvement (cross breeding, mutation breeding, introduction breeding, culture in vitro, molecular marker assistant selection and bioengineering) on papaya are reviewed; especially on the sex-inheritance, distant hybridization and embryo culture, and breeding for disease resistance to PRSV with gene engineering are discussed in detail.

就番木瓜的株性和抗病性等性状遗传、杂交育种、人工诱变育种、离体培养、分子标记及基因工程育种等现代生物新技术育种方面的研究进展及相关问题进行了评述,重点综述了番木瓜株性遗传、远缘杂交与胚胎学、基因工程在抗环斑型花叶病毒病品种培育及分子标记辅助选择育种应用的研究进展,并分析了今后番木瓜育种的发展趋势。

After the carboxymethylation,the solubility of pachyman in the water was significantly increased,its β-D-glucan characteristic absorption peak at 890 cm-1 became weak obviously,and its methylene vibration absorption peak and CO antisymmetrical stretch vibration absorption peak appeared at 1 333 and 1 606 cm-1 respectively,which indicated that the carboxymethylation succeeded.The analysis of AFM results showed that CMP molecules existed in different morphology under different solution conditions,and that the concentration,ionic strength and solvent physical chemistry characteristics of polysaccharide solution had effects on the CMP chains conformation and the action mode between different molecular chains.The phenomena were considered to be related to hydrogen bond association and intramolecular and intermolecular electrostatic interactions of CMP.

结果表明:经过羧甲基修饰,茯苓多糖在水中的溶解性显著增加,890 cm-1 处的β-D-葡聚糖特征吸收峰明显减弱,1 333 cm-1 处出现次甲基振动吸收峰,1 606 cm-1 处出现〖JG(〗C〖ZJLX,Y〗O〖JG)〗非对称伸缩振动吸收峰,表明羧甲基化成功;原子力显微镜分析表明:在不同溶液条件下,CMP分子以不同形态存在,多糖溶液的浓度、离子强度及溶剂的物化特性均能对CMP的分子链构象及链间相互作用形式产生影响,推测可能与CMP分子内、分子间的氢键缔合及静电作用有关,CMP分子与云母基底间的吸附及静电作用也会对CMP的分子链构象及图像质量产生影响。

The UV and IR spectroscopic studies of the monomer films showed that the photoreaction ratio of monomer (about 50%) was higher than the corresponding photosensitive polymer (about 10%, PVCi). The polarized IR spectra proved that obvious anisotropic absorption was displayed in the irradiated photosensitive film. With polarizing microscopy method, we found that these kinds of photoalignment films exhibited good alignment ability, and the stability of the photoalignment film could reach about 100℃. 2 A photosensitive self-assembled monolayer was fabricated that contained photo-cycloadditable groups, such as, coumarin and cinnamate. The reaction process were detected by contact angle method because the IR absorption of monolayer was very weak. The photosensitive self-assembled monolayer promote uniform alignment of nematic liquid crystals by LPUV, and it thermal stability could reach about 130℃. 3 A cationic bolaform amphiphiles was synthesized that had two photosensitive double bonds, and can be polymerized by ultraviolet. A layer-by-layer self-assembled deposition film was prepared in aqueous solution by using this material and poly (sodium 4-styrenesulfonate). The UV-Vis. spectra proved that the multilayers film was uniform and layer-by-layer. When LPUV irradiated the film, the photopolymerizable double bond underwent [2+2] cycloaddition, and the production of the reaction distributed along the polarized direction of incident LPUV. Polarized UV-Vis. spectra indicated that the irradiated self-assembled multiplayer film was anisotropic, and the dichromic ration is about 0.09, it is higher than the spin-coating method of photosensitive polymer or monomer. We used this anisotropic film as alignment layer of nematic liquid crystals, and obtained a uniform and stability alignment result, the static contrast ratio is about 100, which is very close to application of liquid crystal device. This thesis is an instance that the photochemical material was used in the physics region of liquid crystals, the route that was from photosensitive monomer, self-assembled monolayer film to self-assembled multiplayer film was undergone, by this logical research method photoailgnment of liquid crystal was extended and consummated.

围绕上述思路开展了如下工作:1合成了三种可进行光二聚反应的光敏小分子单体,LPUV 辐照制作了光控取向膜;用紫外-可见光谱法和红外光谱法分析了薄膜中的光化学反应,发现小分子的光反应程度可达到50%以上,至少比光敏高分子高出5倍;薄膜的偏振红外光谱证实,经过LPUV 辐照后薄膜出现了明显的各向异性;将小分子光控取向膜制成液晶器件,在偏光显微镜下观察看到均匀一致的液晶取向;并且热稳定性达到100℃左右,接近实用化要求。2制备了含肉桂酸、香豆素基团的自组装单层膜;采用接触角的方法监测自组装反应的动力学过程;紫外-可见光谱证实了自组装单层膜在石英基板表面形成;自组装单层膜经LPUV 辐照后能诱导液晶均匀取向,而且热稳定性可达130℃,热稳定性进一步提高。3合成了含有光敏双键的双季铵盐,在水溶液状态下将它和聚乙烯基苯磺酸钠沉积生成layer-by-layer 自组装多层膜,紫外-可见光谱证实这是一个逐层均匀的沉积;在LPUV 照射下,自组装膜中的光敏双键按照偏振方向发生[2+2]环加成反应,形成取向膜,用二向色性值评价的分子取向度高于高分子及小分子光控取向膜的水平;实验证明用自组装多层膜制成的液晶器件亮暗态均匀,静态对比度约为100,达到实用化器件的水平。

In addition, molecular orientation behaviors induced by shearing, electric field and magnetic field were investigated. The space group of the monomers A3EO7 and A9EO7 were determined as P2〓2〓2 and P112/m by means of electron diffraction and X-ray diffraction. Liquid crystalline properties of the monomer and the polymer were studied using DSC, variable X-ray diffraction, TEM and polarized optical microscope. Both monomers exhibit monotropic liquid crystalline behavior, and they also give a metastable phase on the cooling process. The polymer PA9EO7 shows enantiotropic liquid crystalline properties. Thus the rigid polymer backbone is not a fatal defect that completely distorts the packing arrangement of the mesogenic moiety in the side chain liquid crystalline polyacetylene.

结合电子衍射倾转方法和粉末X射线衍射技术,确定了两个液晶小分子A3EO7和A9EO7的晶胞参数和空间群,采用Cerius〓模拟软件,运用分子模拟的方法给出了小分子在晶胞中的排列方式;利用DSC、变温X射线衍射技术和透射电子显微镜研究了小分子和聚合物的液晶态,单体A3EO7和A9EO7表现出单向液晶性质,并且在降温过程中都表现出一个亚稳液晶相或亚稳结晶相,聚合物PA9EO7具有双向液晶性;采用偏光显微镜和X射线平板照相技术,研究了剪切和电场对聚合物分子取向的影响,在不同的液晶态,剪切作用对聚合物PA9EO7具有不同的诱导取向结果,直流电场可以诱导聚合物联苯液晶基元沿施加电场方向取向。

In this dissertation, the efforts were focused on design and synthesis of chiral tmsymmetrical urea, cholic acid and heteroaromatic molecular tweezers and their molecular recognition as well as enantioselective recognition. A series of useful and creative results have been obtained.Three new types of chiral molecular tweezers containing unsymmetrically disubstituted urea unit, four new types of chiral molecular tweezers based on steroid cholic acid and one type of heteroaromatic molecular tweezers involving multiple hydrogen-bonding site have been designed and synthesized.

本文致力于新型手性不对称脲、胆甾和芳杂环类分子钳受体的设计合成及其对阴离子、中性分子和手性分子的识别及对映选择性识别性能研究,取得了一系列具有重要学术意义与应用前景的创新性结果。

ABSTRACT It is because that the excellent acceptors for maize transgenic engineering are insufficient in our country, especially in the southwest mountain areas of china and hereditary variation regularity for the two characters such as efficiency of embryonic callus induction and number of regenerating plant (these two characters were abbreviated to the nduction efficiency and number of regenerating in the following of the paper, respectively), which hint the maize culturing capacity, is not very clear. Therefore, aiming at picking out superior acceptors, we had made systematic researches on the two characters with combing traditional quantitative-character genetic analyzing methods such as single-factor genetic mating design, diallel crossing genetic design, genetic effect analyzing method and the modern molecular locating method such as QTLs'. The main results are followed.(1) 50 superior inbred lines and about 30 crosses in our country, especially in the southwest of China were used for identifying and selecting the superior genotypes in the above two investigated characters under the same culturing condition in 2000 and 2001. There was very significant difference among the genotypes in the both characters. But the two characters were not certainly related. Some genotypes such as 18-599 and 18-599 were very good in them. For some ones such as zong 31, induction was higher than 18-599 and 18-599 in the efficiency, but it was only 1/3 to the later in regenerating number. In some genotypes such as S37, R08, R15, P138, A318, induction efficiency was just about 3% and scarcely any regenerating plants were got. On the whole, hybrids acted better than inbreeds in the both characters.(2) Two kind of inbreeds were selected as parents of the Griffing's method 1. 18-599 and 18-599 and the inbred line zong 31 are one kind because they are not only superior in the characters of maize cross breeding, such as CA, resistance to disease and the important agricultural characters, but also excellent in transformation characters as the induction and regeneration.

针对我国、特别是西南山地所需玉米转基因工程育种优良受体极为匮乏和反应玉米幼胚培养能力的2个主要性状,即玉米幼胚胚性愈伤组织诱导率和胚性愈伤组织绿苗发生数的遗传变异规律十分不清楚的实际情况,本研究从筛选玉米转基因工程所需要的优良受体入手,采用单因素遗传交配设计、双列杂交遗传交配设计、世代基因效应等传统数量性状分析方法,以及现代分子标记定位主效QTL分析方法,对玉米幼胚胚性愈伤组织诱导率和胚性愈伤组织绿苗发生数等2个性状进行了较为系统的分析研究,取得以下主要研究结果:(1)于2000年和2001年通过对我国、特别是西南地区近50份优良自交系和近30个杂交组合,在相同培养条件下,对幼胚培养胚性愈伤组织诱导率和胚性愈伤组织绿苗发生数等2个幼胚培养能力性状进行了筛选与鉴定,发现玉米不同基因型具有完全不同的幼胚培养胚性愈伤组织诱导率和胚性愈伤组织绿苗发生数,但幼胚培养胚性愈伤组织诱导率与胚性愈伤组织绿苗发生数并不具有必然的相关关系,有的基因型,如自交系18-599和18-599在胚性愈伤组织诱导率和愈伤组织绿苗发生数等2个性状都表现相当优异;有的基因型,如自交系综31,仅幼胚培养胚性愈伤组织诱导率性状表现高于19-599和18-599,但在胚性愈伤组织绿苗发生数这一性状则与它们有相当大的差距,仅为19-599和18-599的1/3左右;有的基因型,如S37、R08、R15、P138、A318等玉米自交系不仅幼胚培养胚性愈伤组织诱导率很低,平均仅在3%左右,而且胚性愈伤组织绿苗发生数表现也很差,基本上没有分化成苗。

In contrast, deletion of the propeptide yields mature but inactive NK, the inclusion bodies of NK or denatured rNK couldn't be renatured in any condition, but with the aid of exogenously purified propeptide or Ser221Ala proNK, the inactive mature protein could be renatured by an intermolecular pathway in vitro.

此外,我们利用融合基因表达系统在大肠杆菌中高效表达了谷胱甘肽S-转移酶/NK和硫氧还蛋白/NK两种融合蛋白,经体外复性、纯化,均获得活性蛋白。以上结果显示,pro肽在体内体外,通过分子内或分子间的方式均能帮助NK分子的折叠与再折叠,作为一种分子内的分子伴侣,pro肽为NK分子正确折叠所必需。

In this dissertation, the efforts were focused on design and synthesis of new types of chiral and achiral azoamide hosts,bowl-shaped steroid cholic acid methyl esters with one chiral arm under microwave irradiation and heteroaromatic molecular tweezers under microwave irradiation in solid state and their molecular recognition as well as enantioselective recognition.

本文致力于新型手性不对称脲、胆甾和芳杂环类分子钳受体的设计合成及其对阴离子、中性分子和手性分子的识别及对映选择性识别性能研究,取得了一系列具有重要学术意义与应用前景的创新性结果。

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