催化动力学光度法测定痕量NO2^—的研究

本文研究了在稀硫酸介质中,ＮＯ２＾－对ＫＢｒＯ３氧化甲基橙褪色反应的催化作用及其动力学分析,建立了测定痕量ＮＯ２的新方法,该方法的检出限为１．３×１０＾－１０μｇ／ｍＬ,线性范围为０．－１．４×ｇ／１０ｍＬＮＯ２,方法简便、灵敏、选择性好,于水及蔬菜中痕量ＮＯ２的测定,结果满意。     

溴酸钾氧化溴百里酚蓝催化光度法测定痕量亚硝酸根

基于磷酸介质中ＮＯ２＾－催化溴酸钾氧化溴百里酚蓝的褪色反应,建立了测定痕量ＮＯ２＾－的新方法。方法检出限为２．６×１０＾－６ｇ．ｌ＾－１,线性范围０．４～３μｇ／２５ｍｌ方法简便,已用于雨水塘水中痕量ＮＯ２＾－的测定。     

溴酸钾氧化靛红催化光度法测定痕量亚硝酸根

基于磷酸介质中ＮＯ２＾－催化溴酸钾氧化靛红的褪色反应，建立了测定痕量ＮＯ２＾－的新方法，并讨论了其动力学条件。方法检测限为１．３６×１０＾－６ｇ／Ｌ，线性范围０．３￣２μｇ／２５ｍＬ，方法简便，已用于环境水样中痕量ＮＯ２＾－的测定。     

基于偶联反应新极谱法测定痕量亚硝酸根的研究：II.以苯酚为偶联试剂

本研究了苯酚在氨性缓冲溶液中与ＮＯ２＾－－磺胺重氮盐偶联反应的实验条件，建立了一个灵敏快速测定痕量ＮＯ２＾－的新方法。ＮＯ２＾－离子浓度在１．０×１０＾－１０－－４．８×１０＾－７ｇ／ｍｌ范围内，与峰高呈良好的线性关系。４０００倍量ＮＯ３＾－存在不干扰。     

溴酸钾氧化中性红催化光度法测定NO-2的研究

研究了盐酸介质中,痕量亚硝酸根催化溴酸钾氧化中性红褪色反应及其动力学条件,建立了催化动力学光度法测定痕量亚硝酸根的新方法,ＮＯ＾－２的测定线性范围为１－７μｇ／２５ｍｌ,检出限为１．５＊１０＾－８ｇ．ｍｌ＾－１。用于化学试剂及唾液中痕量ＮＯ＾－２的测定,结果满意。     

3,3′,5,5′—四甲基联苯胺吸光光度法测定水中NO2^——N

提出用３,３′,５－５′－四甲基联苯胺（ＴＭＢ）吸光光度法测定水中ＮＯ２＾－－Ｎ。在ＨＯＡｃ－ＮａＯＡｃ缓冲液（ｐＨ３．６）中,ＴＭＢ与ＮＯ２＾－反应生成蓝色的ＴＭＢ－ＴＭＢ亚胺传荷络合物,其最大吸收波长为６５０ｎｍ,表观摩尔吸光系数为２．５９×１０＾４,ＮＯ２＾－－Ｎ与０～０．５μｇ·ｍｌ＾－１范围内服从比耳定律。运用此法测定了环境水样并进行了加标回收试验,结果满意。     

藉溴酸钾氧化酸性间胺黄反应催化光度测定痕量亚硝酸根和硝酸根

本文基于ＮＯ２＾－对ＫＢｒＯ３氧化酸性间胺黄而使其褪色的催化作用，以及ＮＯ３＾－经锌粉还原为ＮＯ２＾－，建立了灵敏的催化光度测定痕量ＮＯ２＾－、ＮＯ３＾－的新方法，并讨论了其动力学条件，测定范围１０－９０μｇ／Ｌ，方法简便快速、选择性好，用于水及食品中痕量ＮＯ２＾－、ＮＯ３＾－的测定，结果满意。     

3,5—二溴—PADAP分光光度法测定微量NO2—离子的研究

系统研究了３,５－二溴－ＰＡＤＡＰ在酸性介质中质子化后与ＮＯ２和ＳＣ怙元离子缔合物的最佳条件。提出了测定微量ＮＯ２的光度新方法,表观摩尔吸光系数ε６３０＝１．２×１０＾４Ｌ·ｍｏｌ＾－１·ｃｍ＾－１,缔合物组成比为ｎ（３,５－ｆｇ ｉｔｈｄ－ＰＡＤＡＰ）：ｎ（ＮＯ２）：ｎ（ＳＣＮ）＝１：１：！。ｓｇ ｉｆ ｙｉｅｔｇｇｆｕｉｉ ｗｓｇ ｋ ｔｍｇ ｊｇ ＮＯ２ｒ ｉｍｐｇ,ｇｎ ｘ ｍａｗ ｙｙｉ     

流动注射光度法同时测定血清中NO3^—和NO2^—

采用流动注射分析技术、以分光光度计为检测器,建立了同时测定血清中ＮＯ３和ＮＯ２的方法。以α－萘胺－７－磺酸为显色剂,在５２０ｎｍ比色,测定流路中装有锌－镉还原柱,将ＮＯ３在线还原为ＮＯ２。分析速度达４５样·ｈ＾－１,ＮＯ３和ＮＯ２的检出限分别为０．０１ｍｇ·Ｌ＾－１、０．００３ｍｇ·Ｌ＾－１,相对标准偏差分别为１．０％、０．５％。     

偶合反应化学发光法测定痕量银的研究

本将Ａｇ（Ⅰ）催化Ｓ２Ｏ＾２－８氧化Ｍｎ（Ⅱ）生成ＭｎＯ＾－４的催化反应与ＬｕｍｉｎｏｌＭｎＯ＾－４－ＯＨ＾－的化学发光反应相偶合，建立起一种新的灵敏测定痕量银的化学发光分析法，在所研究的优化条件下，该法测定银的选择性较好，检测限达到３．２×１０＾－１２ｇ／ｍＬＡｇ线性浓度范围为１．０×１０＾－１１－１．０×１０＾－５ｇ／ｍＬＡｇ，用于水样分析，结果较为满意。     

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%。     

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。     

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。     

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.     

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.     

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。     

纳米SiO2锚固光敏基团引发MMA光接枝聚合研究

对纳米SiO2进行了锚固光引发剂的表面修饰,进而引发甲基丙烯酸甲脂(MMA)光接枝聚合制备有机/无机复合粒子.纳米SiO2粒子首先用氯化亚砜进行表面氯化,再与光引发剂2-羟基-4-(2-羟基乙氧基)-2-甲基苯丙酮(Irgacure2959)反应从而锚固上光引发剂.通过紫外光引发MMA在经过修饰过的纳米SiO2表面上进行表面光接枝聚合.采用IR、TGA和TEM等方法表征了接枝前后纳米粒子的变化,证明了表面接枝物的存在,并研究了不同反应条件对单体转化率、接枝率和接枝效率的影响.研究结果表明,搅拌对接枝过程的影响比较显著.TGA结果显示未搅拌聚合时接枝率只能达到比较小的程度,而在搅拌条件下180min内MMA的接枝率可达到110%.