大环硫氮冠醚金属配合物的研究──Ⅱ．1，4，10，13－四硫－7，16－二氮杂环十八烷硝酸铜配合物的合成、结构及立体化学

作为系统研究大环硫氮杂冠醚配合物的第二部分，合成了四硫二氮杂环十八冠的硝酸铜配合物［Ｃｕ（Ｃ＿（１２）Ｈ＿（２６）Ｎ＿２Ｓ＿４）］·（ＮＯ＿３）＿２·Ｈ＿２Ｏ，测定了元素分析和红外光谱。利用Ｘ－射线衍射分析方法，测定其晶体结构。晶体学参数ａ＝１７．５７６（４），ｂ＝１１．７５３（３），ｃ＝１０．４８５（５），Ｖ＝２１６３．９（７），Ｚ＝４，Ｄ＿ｃ＝１．６３２ｇ／ｃｍ￣３，Ｆ（０００）＝１１０８，μ＝１．４２ｃｍ￣（－１）（ＭｏＫα），最终偏离因子Ｒ＝０．０３２和Ｒｗ＝０．０３４。晶体测定结果表明：有杂原子组成的四硫二氮大环冠醚比含氧冠醚有更大的柔变性；四硫二氮大环冠醚与Ｃｕ离子配位前后，大环的构象发生了变化。     

二苯并18冠6及二苯并24冠8与六聚钼钨杂多酸超分子配合物的合成与晶体结构

报道了两种超分子配合物［Ｎａ（ＤＢ１８Ｃ６）（ＣＨ＿３ＯＨ）］＿２Ｗ＿４Ｍｏ＿２Ｏ＿（１９）·（ＤＢ１８Ｃ６）·（ＣＨ＿３ＯＨ）（Ⅰ）和［Ｎａ（ＤＢ２４Ｃ８）］＿２Ｗ＿１Ｍｏ＿５Ｏ＿（１９）（Ⅱ）的合成方式，用元素分析、电子能谱、ＩＲ和１ＨＮＭＲ等手段进行了表征，并用Ｘ射线测定了晶体结构。结构分析表明：配合物（Ⅰ）属单斜晶系，空间群为Ｐ２１／ｃ，晶胞参数：α＝１．８６９９（５）ｎｍ，ｂ＝１．９５４３（５）ｎｍ，ｃ＝２．２８０８（６）ｎｍ，β＝１１２．８７°，Ｚ＝４．冠醚与多酸根之间通过Ｎａ＋在ＤＢ１８Ｃ６空腔中的镶嵌和Ｏ—Ｎａ—Ｏ键的桥联结合在一起。超分子配合物（Ⅱ）则为Ｎａ＋与ＤＢ２４Ｃ８作用形成配位阳离子，然后与多酸阴离子静电吸引相结合。不同空腔孔径的冠醚与钼钨杂多酸配位时呈现出分子识别与选择性。     

Ln(NO_3)_3·C_(26)H_(38)N_2O_4(Ln=La、Ce)配合物的合成和La(NO_3)_3·C_(26)H_(38)N_2O_4·CH_3CN的晶体结构

合成了２个新的希土冠醚配合物Ｌｎ（ＮＯ３）３·Ｃ２６Ｈ３８Ｎ２Ｏ４（Ｌｎ＝Ｌａ、Ｃｅ；Ｃ２６Ｈ３８Ｎ２Ｏ４＝１，７，１０，１６－四氧－４，１３－二氮杂－Ｎ，Ｎ′－二苄基环十八烷）。通过元素分析，红外光谱，拉曼光谱及其１Ｈ核磁共振谱进行表征。用四圆衍射仪测定了Ｌａ（ＮＯ３）３·Ｃ２６Ｈ３８Ｎ２Ｏ４·ＣＨ３ＣＮ的晶体结构。晶体属三斜晶系，Ｐ１空间群，晶胞参数：ａ＝１．２８６９（４）ｎｍ，ｂ＝１．５８６８（６）ｎｍ，ｃ＝０．９１４７（２）ｎｍ；α＝１０１．８９（２）°，β＝１０５．３８（２）°，γ＝７１．９６（３）°；Ｚ＝２。ｄｃａｌｄ．＝１．５８ｇ·ｃｍ－３，μ（ＭｏＫα）＝１３．２５ｃｍ－１。中心镧离子与冠醚配体中的４个氧原子和２个氮原子配位，３个硝酸根中的６个氧原子也与Ｌａ３＋配位，形成配位数为１２的配合物。     

（C_5H_7S_2）_3〔Bi_2Cl_9〕的合成和晶体结构

标题化合物由ＢｉＣｌ３和乙酰丙酮在ＨＣＩ（气）／Ｃ２Ｈ５ＯＨ溶剂中通入Ｈ２Ｓ气体反应而得。晶体属四方晶系，Ｍｒ＝１１３０．７６，空间群Ｐ４１２１２。晶胞参数ａ＝ｂ＝８．８６７（２），ｃ＝４１．５１１（４）Ａ；Ｖ＝３２６４（１）Ａ３，Ｚ＝４，Ｄｃ＝２．３０ｇｃｍ（－３），μ（ＭｏＫα）＝１１８．６０７ｃｍ（－１），Ｆ（０００）＝２１０４．晶体结构由重原子法求得。最终偏离因子Ｒ＝０．０７２。晶体由分立的（Ｃ５Ｈ７Ｓ２）＋阳离子和［Ｂｉ２Ｃｌ９］３－阴离子组成。每个Ｂｉ原子和６个Ｃｌ原子形成畸变的八面体配位。２个［ＢｉＣｌ６］八面体共面构成具有２次轴对称的［Ｂｉ２Ｃｌ９］（３－）配阴离子。还讨论了阳离子种类对Ｂｉ配阴离子结构类型的影响。     

3－乙酰乙酰基－4－羟基香豆素希土配合物的合成和性质

本文报道了希土与３－乙酰乙酰基－４－羟基香豆素（Ｈ２ａａｃ）配合物的合成．其化学组成为Ｌｎ（Ｈａａｃ）３·ｎＨ２Ｏ（Ｌｎ为Ｌａ、Ｐｒ、Ｎｄ、Ｅｕ、Ｇｄ．Ｄｙ、Ｅｒ，ｎ为１或２）．基于Ｈ－ＮＭＲ、ＩＲ的结果，提出了希土离子与配位体４位羟基氧与邻近羰基双齿配位结构．对Ｎｄ（３＋）及Ｅｒ（３＋）配合物的超灵敏吸收带的形状和吸收强度等也作了讨论．     

吡啶－2，6－二甲酸镧钇异核配合物的合成及晶体结构

合成了吡啶－２，６－二甲酸镧钇异核配合物晶体。元素分析结果表明，化学式为ＬａＹ（ＨＤＰＡ）＿２·（ＤＰＡ）＿２．１２Ｈ＿２Ｏ，ＤＰＡ为吡啶－２，６－二甲酸根。用Ｘ射线衍射法测定了配合物的单晶结构，其结构式为［ＬａＹ（ＨＤＰＡ）＿２（ＤＰＡ）＿２（Ｈ＿２Ｏ）＿４」·８Ｈ＿２Ｏ，属单斜晶系，Ｐ２＿１／ａ空间群。晶胞参数：ａ＝１．２９７５（４）ｎｍ，ｂ＝１．１２６６（３）ｎｍ，ｃ＝１．４０７９（３）ｎｍ；β＝１０２；１５（２）°，Ｖ＝２．０１１９０（１）ｎｍ￣３，Ｚ＝４，Ｄｃ＝１．８３ｇ／ｃｍ￣３，稀土离子的配位数为９，其配位多面体为扭曲的三冠三角棱柱体。     

［La（EO_3）_3（H_2O）］（ClO_4）_3·H_2O的晶体结构

稀土高氯酸盐开环冠醚三缩乙二醇（ＥＯ_３）［Ｌａ（Ｃ_６Ｈ_（１４）Ｏ_４）_３（Ｈ_２Ｏ）］（ＣｌＯ_４）_３·Ｈ_２Ｏ，单斜晶系，Ｐ２_１／ｃ空间群。晶胞参数为：ａ＝１５．４７４（２），ｂ＝１１．３８６（１），ｃ＝２０．８４１（４），β＝９９．８２（１）°，Ｖ＝３６１８（１），ＭｏＫα，Ｚ＝４，Ｄ_ｃ＝１．７１８ｇ／ｃｍ３，μ＝１．４９９ｍｍ￣（－１）。全矩阵最小二乘精细修正，结构因子Ｒ＝０．０５６，Ｒ_ｗ＝０．０８３。中心原子Ｌａ与开环冠醚醚链上的Ｏ（１）～Ｏ（９）及一个水分子形成１０配位双帽四方反棱柱结构。弱配体高氯酸根不参加配位。     

[Ln(EO_2)_3](ClO_4)_3·3H_2O的晶体结构研究

合成了希土高氯酸盐开环冠醚二缩乙二醇（ＥＯ２）晶体，（Ｌｎ＝Ｎｄ，Ｈｏ），测定了结构，文内以Ｎｄ－Ｌ的数据为主要研究对象（方括号内是Ｈｏ－Ｌ的数据）。晶体属单斜晶系，Ｐ２１／ｎ空间群，化学式［Ｌｎ（ＥＯ２）３］（ＣｌＯ４）３·３Ｈ２Ｏ，晶胞参数为：ａ＝１４．１２４（１）［１４．０８７］，ｂ＝１３．９９０（１）［１４．０３９］，ｃ＝１５．２６５（１）［１５．０１４］；β＝９５．７８（１）［９５．６４］°；Ｖ＝３００１．１（６）［２９５５］３；Ｍｒ＝８１５．０１［８３５．７０］；Ｚ＝４；Ｄｃ＝１．８０４［１．８６５］ｇ／ｃｍ３；石墨单色器，μ（ＭｏＫα）＝２．０９［３．０７］ｍｍ－１，最终偏离因子Ｒ＝０．０５５［０．０７４］，ＲＷ＝０．０７１［０．１０９］。研究结果表明晶体具有相同的结构，配位多面体为九配位三帽三棱柱。发现ＥＯ２醚链有绕Ｃ－Ｃ键呈ＳＴＴＳ分布的规律。弱配体高氯酸根不参加配位。     

四甲基双硅桥联环戊二烯基稀土金属有机配合物的合成及［Me_4Si_2（C_5H_

四甲基双硅桥联环戊二烯基钠与无水三氯化稀土在ＴＨＦ溶剂中反应合成了标题配合物Ｍｅ１Ｓｉ２（Ｃ５Ｈ４）２ＬｎＣｌ［Ｌｎ：３Ｎｄ，４Ｓｍ，５Ｇｄ，６Ｙ］和配合物Ｍｅ４Ｓｉ２（Ｃ５Ｈ４）：Ｌｎ（Ｃ５Ｈ５）（ＴＨＦ）ｎ［Ｌｎ：１Ｌａ，ｎ＝１；２Ｐｒ，ｎ＝０］。通过元素分析、１ＨＮＭＲ、１３ＣＮＭＲ和ＭＳ确证了配合物的结构，在ＴＨＦ溶液中重结晶获得配合物４的单晶，ｘ射线衍射证明晶体结构为二聚体，４为单斜晶系，空间群为Ｐ２１／ｃ，晶体学数据ａ＝１．２９８２（３）ｎｍ，ｂ＝１．２２６９（３）ｎｍ，ｃ＝１．３６８１（２）ｎｍ，β＝９６．７９（２）°，Ｖ＝２．１６２（１）ｎｍ３，Ｚ＝２，Ｄｘ＝１．５３ｇ／ｃｍ３，偏差因子Ｒ＝０．０６８。     

Mn（Ⅲ）－苯甲酰丙酮缩乙二胺－有机碱配合物的合成及结构

合成了４种锰（Ⅲ）－苯甲酰丙酮缩乙二胺－有机碱配合物：Ｍｎ（ｂｚａｃｅｎ）ＬＣｌＯ＿４．（Ｌ为哌嗪，吡啶，γ－甲基吡啶和乙腈），测定了配合物［Ｍｎ（ｂｚａｃｅｎ）（ＣＨ＿（３）ＣＮ）ＣｌＯ＿４］的结构．晶体属正交晶系．空间群Ｐ＿ｎｍａ．晶胞参数：ａ＝０．９０７７（１）ｎｍ，ｂ＝１．５５６３（１）ｎｍ，ｃ＝１．７２０５（２）ｎｍ，Ｖ＝２．４３０５ｎｍ￣３，Ｚ＝４，Ｄ＿ｃ＝１．４８ｇ／ｃｍ￣３，Ｄ＿ｍ＝１．４９ｇ／ｃｍ￣３．配合物呈拉长八面体结构．对配合物的电子光谱和红外光谱进行了归属．     

SPECTRAL CHARACTERISTICS OF THE EXCITED STATES OF THE PRODUCT OF THE CHEMILUMINESCENCE OF LUMINOL*

Abstract— In dimethylsulfoxide the emission spectrum of luminol chemiluminescence is red-shifted by 300 cm^-1 from the photoexcited fluorescence of the product 3-aminophthalate dianion, while in aqueous solvent the two spectra are identical. The spectral properties of the product dianion have been measured in aqueous solvent and in a number of aprotic solvents, both at room temperature and at 77°K. The ground states and the excited states from which emissions are observed are characterized. Two alternatives are presented to explain the aprotic emission spectra.     

ON THE ACCURACY OF DIFFERENTIAL MEASUREMENTS OF THE MINIMAL ERYTHEMA DOSE: INFLUENCE OF THE DISCRETENESS OF THE SCALE

The minimal erythema dose (MED) is often used as a quantity by which the influence of certain treatments of the skin can be measured. Differential measurements are performed by assessing the difference of the MED on the skin treated in some way and the untreated skin.
As the MED-measuring scale is discrete, the question is sometimes raised whether it is possible to measure differences smaller than one scale unit. In the present paper it is shown that this is indeed possible; in principle the discreteness of the scale does not impose any restriction on the smallest value of the difference that can be measured. The discreteness of the scale introduces an extra random variation into the measurement. This variation is estimated theoretically. It is automatically included in the usual error analysis.
The discreteness variance is small when compared to other variance components, which are computed from an analysis of variance of actual experiments. Reducing the discreteness variance, by reducing the dose decrement of the MED-measuring scale, therefore, does not enhance the overall accuracy considerably. Finally, it is found that the assessments of the MED by the various observers do not differ significantly from each other, and that multiple assessments do increase the accuracy, especially for small effects.     

丙烯聚合络合催化剂形成过程的研究

以倍半物为还原剂还原TiCl_4,经异戊醚络合处理,然后在TiCl_4己烷溶液中35℃条件下热处理,制得对丙烯聚合具有高活性和高定向度的络合催化剂。研究了制备过程中各步反应产物的组成和结构特征,并讨论了TiCl_3低温晶型转变机理。     

光谱透射比标准物质的研究

研制了紫外、可见、近红外光谱区通用光谱透射比较标准物质。以高纯熔融石英为基片材料，镍铬合金的镀膜材料，采用双光楔对称光胶结构以消除同色杂散光的影响，对镀膜进行光胶处理以保证膜层的强度、稳定性及光学中性，采用高精度分光光度测量装置作为定值手段的以保证准确的定值，设计定位保护架以消除多次反射误差。该光度标准适用的光谱范围的200-2600nm，光谱透射比定值不确定度为0.5%。     

分光光度法低浓度区不成线性关系的探讨

本文研究分光光度法低浓度区不成线性的有关因素及其克服方法,以铝-二甲酚橙体系为例,通过对体系不同条件下吸收光谱及其等色点的研究,发现当体系pH渐变时(铝,二甲酚橙浓度固定不变),曲线簇现两个等色点.从对等色点的分析,证明体系形成络合物须按一个反应式进行才能出现等色点,而与反应式是否涉及到两个或三个有色化合物无关.若同时按两个反应式进行,则不能得到等色点,测定时也无线性关系.所以用这个体系进行铝的测定,铝浓度的变化范围只能限于存在等色点的区间才有线性关系. 为了克服常法测定铝时不符线性的现象,本文采用的方法是在二甲酚橙中预先加适量的铝作为显色剂,使反应严格按一个反应式进行,所得结果为一直线.     

对苯二胺衍生物的光催化氧化

以ＴｉＯ２作为催化剂，利用波长＞３３０ｎｍ的光辐照研究了Ｎ－取代的对苯－二胺衍生物的光催化氧化。研究表明，氧分子与光生电子 反应生成羟基自由基，羟基自由基氧化ＰＰＤｓ，生成醌二亚胺，后者在羟基的进攻下脱氨生成苯醌，苯醌继续光解无机化。ＰＰＤｓ光催化氧化近似遵循一级反应动力学，醇类和硫酸根离子可抑制ＰＰＤｓ的光催化氧化。催化剂表面荷影响电子转移速率，从而控制光催化氧化的反应速率。     

六氟丙烯等离子体聚合机理研究

<正> 在以前的工作中,我们曾应用色谱-质谱(GC-MS)及顺磁共振(ESR)等方法研究了四氟乙烯和三氟氯乙烯等离子体聚合过程中气体冷凝物的组成及结构,提出自由基引发聚合反应机理。本文用类似方法研究六氟丙烯(HFP)等离子体气体冷凝物的组成与结构和冷凝物的ESR信号及其从低温到高温的变化规律,证实了自由基的稳定性并提出气相聚合反应机理。     

THE COMPLEXITY OF THE FLUORESCENCE OF CHLORELLA PYRENOIDOSA

Abstract— The complexity of the room-temperature emission spectrum of Chlorella was investigated by a matrix analysis method. This approach revealed the presence of two independently fluorescent components in the short-wave region of the spectrum. These components, maximal at about 687 and 695 nm, appeared to correspond to the fluorescence of the bulk pigments of PS II and PS I respectively. The analysis was insensitive to the individual species within the photosystems. As such, other minor fluorescent species, usually observed at low temperatures, which presumably correspond to fluorescence from the trapping centres, did not appreciably complicate the analysis. The absorption spectra of the two photosystems were calculated from the fluorescence data. The results were similar to those that have been obtained by other workers from oxygen evolution and DCMU poisoning data but differed from those obtained by computer analysis of the absorption spectrum. Addition of reduced DCPIP was observed to reverse the increase in fluorescence yield and changes in the spectral distribution of emission taking place on poisoning the algae. The correlation between this and the catalysis of photophos-phorylation in aged or poisoned chloroplasts was noted. This correlation was tentatively interpreted as evidence for a direct interaction between the donor system and the photochemical apparatus associated with PS II, rather than with a member of the electron transport chain as is normally assumed.     

THE KINETICS OF THE DECOMPOSITION OF CYCLOHEXYL HYDROPEROXIDE IN THE PRESENCE OF VANADYL DIBENZOYLMETHANE

The kinetics of the decomposition of cyclohexyl hydroperoxide(CHHP) in benzene catalyzed by vanadyl dibenzoylmethane[V0(DBM).,] has been studied.It was found that the products of decomposition of CHHP were cyclohexanol and cyclohexanone,which are produced in about equimolar amount,and the product cyclohexanol obviously inhibited the decomposition of CHHP.The kinetics data can be satisfactorily described by the following equation (with [CHHP]0>>[VO(DBM)2]0)R0=kK[CHHP]0[VO(DBM)2]0/(1+k[CHHP]0)This is the kinetic evidence for the formation of a catalyst-hydro-peroxide intermediate.In the equation K is the stability constant of the catalyst-hydroperoxide intermediate complex;k is the rate constant for the decomposition of the complex.The rate constant K at 500℃ may be expressed as follows:k=1.9×108exp(-53.7×103/RT)S-1 with the activation energy Ea=53.7kJ mol-1