双波长分光光度法测定水中硝酸盐

用紫外法测定水中硝酸盐已被美国列为标准方法,但易受常见化合物干扰,需进行不同的校正。我们根据硝酸盐的紫外吸收特征和双波长分光光度计的优点,对硝酸盐的吸收曲线用数学方法处理,其微分系数dA/dλ与硝酸盐的浓度有线性关系。以A/2.0毫微米为纵座标,波长(λ)为横座标作图,获得一级导数光谱,最高点在271毫微米,是吸收曲线斜率最大的地方,此波长用做λ_2,λ_1选用226毫微米,硝酸盐用氮计算时其线性范围在0—6毫克/升,检测限为0.07毫     

金纳米粒子的非线性共振散射及光强度函数研究

液相金纳米粒子在320nm、470nm、580nm720nm处产生四个共振散射峰。它是一种非线性光学介质,当入射光的频率v不同时可获得金纳米粒子的2v倍频、v/2分频、v/3分频、2v/3 分频、3v／2分频散射峰。探讨了影响液相金纳米粒子散射光信号强度I（λ）的主要因素即散射光能量分布、粒径d、△λ（λem-λex)和散射光辐射度Rλex。给出了共振散射光强度与△λ之间的高斯分布函数。建立了一个合理的金纳米粒子的共振散射光强度函数。     

导数光谱法测定食品中的山梨酸

采伤脑筋导数光谱法测定食品中的山梨酸，在265.8nm波长下测定样品，一阶导数峰峰高与样品溶液的浓度线性相关，线性方程为dA/dλ=9.3109c 4.6143，相关系数r=0.9990，线性范围为0-10mg/L。样品测定结果的相对标准偏差为0.1%-4.3%，加标回收率为98.0%-101.0%，共存的苯甲酸和糖精钠对测定结果无影响。该法快速、简便、可靠。     

卟啉试剂导数光谱PLS法同时测定血清中的铜锌及其比值

本研究了ｍｅｓｏ－四－（４－甲氧苯基）卟啉与Ｃｕ（Ⅱ）、Ｚｎ（Ⅱ）的共显色条件和导数光谱条件，提出了用偏最小二乘法解析导数光谱进行Ｃｕ、Ｚｎ同时测定的计算分析方法。在ｐＨ７．０５的介质中，有表面活性剂Ｔｗｅｅｎ－８０存在时，于沸水浴内加热１６ｍｉｎ，Ｃｕ（Ⅱ）、Ｚｎ（Ⅱ）均能显色完全。采用四阶导数光谱进行测量，其摩尔响应系数（峰－峰法）分别达９．１４×１０＾６和１．５３×１０＾７。该法用于Ｃｕ∶     

导数光谱法测定歧化松香中树脂酸异构体

用紫外（UV）导数光谱法建立了同时测定歧化松香中五种树脂酸异构体的新方法。通过选择合适的求导阶数（n）、微分波长差（△λ）、扫描速度和定量方法,对不同批号的歧化松香中的主成分脱氢枞酸和微量组分枞酸、新枞酸、左旋海松酶及长叶松酸进行了测定（其中左旋海松酸和长叶松酸测定的是合量）,实验结果令人满意。该法可消除树脂酸各异构体及同系物的背景干扰,对迭加的树脂酸的检出和定量很有效。方法的平均回收率为99．0％,相对标准偏差小于0．2％。     

逆最小二乘法—导数谱同时测定锌,镉,汞和铅

本文研究了在碱性介质中，ＣＰＢ存在下，ｍｅｓｏ－四（４－三甲铵基苯）卟啉与Ｚｎ（Ⅱ），Ｃｄ（Ⅱ），Ｈｇ（Ⅱ）和Ｐｂ（Ⅱ）络合物的导数光谱，提出了应用逆最小二乘法（或称ＣＰＡ－矩阵法）原理对导数光谱进行解释，同时测定四组分的方法。应用本法对合成样品和水进行分析，结果满意。     

一种新的FIA导数光谱技术测定食盐中碘含量

提出一种新的流动注射导数光谱检测技术,即双光束同时扫描法。将自行研制的流动池比色装置分别安置在双光束检测器中样品光束和参比光束的光路中,实现同时扫描,获得响应曲线为一阶导数光谱。对该方法的原理和实验技术进行了讨论,基于碘酸根与碘化钾生成碘,并与淀粉生成蓝色络合物(λmax=574 nm)原理,确定了最佳实验条件,建立了一种导数光谱法测定加碘食盐中的碘含量。该法分析速度为130次/h,方法灵敏度比普通FIA法提高了1.8倍,测定结果的相对标准偏差为0.97%(n=9),方法可直接用于实际样品中碘含量的检测。     

比值-导数荧光法测定藤茶中的蛇葡萄素

以10 g/L AlCl3溶液为络合剂,在λex=442 nm,λem=503、505、507 nm下,建立比值-一阶导数荧光分析法测定藤茶中的蛇葡萄素.蛇葡萄素质量浓度在l0.08～151.2μg/mL范围内与比值导数光谱的峰谷差值呈良好的线性关系(r=0.9979),平均回收率为97.35%,(RSD=2.3%,n=9).经配对t检验法分析,与HPLC法的测定结果无显著差异.该法可用于藤茶提取过程中质量控制的检测方法.     

八和九元硼环配位的平面超配位过渡金属钴、铁和镍的理论研究

对一系列潜在的八和九元硼环配位的平面超配位过渡金属，包括单态的1^FeB8^2-，多重态的k^FeB9^n（n=0，k=2；n=-1，k=1），单重态的1^CoB8^n（n=-1，＋1，＋3），多重态的k^CoB9^n（n=＋1，k=2；n=-1，k=1）和单态的1^NiB9^＋，在B3LYP和BP86理论水平下进行了理论计算研究，其几何结构已经被优化为相应势能超曲面局域极小值，电子结构用轨道分析进行了讨论，并用核独立化学位移值对其芳香性进行了预测．计算结果建议所有上述这些具有高对称性的结构是稳定的，并且具有6个π电子，显示有芳香性．     

分子荧光法测定水中的微量铁

基于Fe（Ⅱ）与邻菲口罗啉生成络合物使其荧光猝灭的特性,讨论了在室温下,pH 5.5的乙酸-乙酸铵的缓冲介质中,以λex=270 nm为激发波长,于eλm=365 nm波长处测定该络合物荧光强度。结果表明Fe（Ⅱ）质量浓度在0.8-120.0 ng/mL范围内与络合物的荧光强度具有良好的线性关系,相关系数0.9994,检出限0.50 ng/mL。对60 ng/mL的Fe RSD（n=9）为2.8%。Fe的回收率为98.03%-102.9%。方法已用于水中微量铁的测定。     

Fixation of a cholesteric helical structure by the photopolymerization of a cholesteryl derived monomer

A cholesteryl derived monomer was synthesized according to a conventional synthetic route; it exhibits a cholesteric phase above 129°C, and shows a red colour due to selective reflection in the cholesteric phase. Photopolymerization of the monomer was carried out at 135°C in the cholesteric phase. The helical structure of the cholesteric phase of the monomer was frozen by photopolymerization. A peak based on the selective reflection of the cholesteric phase was detected at 615 nm in the transmittance UV-Vis spectrum. Mixtures of the monomer with a binaphthyl derivative were prepared to control the selective reflection wavelength; they all also exhibited a cholesteric phase. The selective reflection wavelength of the mixture was dependent upon the ratio of the binaphthyl derivative in the mixture. This wavelength became shorter with increasing ratio of the binaphthyl derivative. The polymer films obtained by photopolymerization displayed almost the same selective reflection wavelength as the corresponding mixtures before photopolymerization. The selective reflection wavelength of the polymer films did not change up to about 250°C.     

Fixation of a cholesteric helical structure by the photopolymerization of a cholesteryl derived monomer

A cholesteryl derived monomer was synthesized according to a conventional synthetic route; it exhibits a cholesteric phase above 129°C, and shows a red colour due to selective reflection in the cholesteric phase. Photopolymerization of the monomer was carried out at 135°C in the cholesteric phase. The helical structure of the cholesteric phase of the monomer was frozen by photopolymerization. A peak based on the selective reflection of the cholesteric phase was detected at 615 nm in the transmittance UV-Vis spectrum. Mixtures of the monomer with a binaphthyl derivative were prepared to control the selective reflection wavelength; they all also exhibited a cholesteric phase. The selective reflection wavelength of the mixture was dependent upon the ratio of the binaphthyl derivative in the mixture. This wavelength became shorter with increasing ratio of the binaphthyl derivative. The polymer films obtained by photopolymerization displayed almost the same selective reflection wavelength as the corresponding mixtures before photopolymerization. The selective reflection wavelength of the polymer films did not change up to about 250°C.     

火灾探测器滤光片校准方法

以紫外可见近红外分光光度计为计量标准器建立火灾探测器滤光片校准方法。火焰探测器紫外滤光片校准选择波长范围150~300 nm进行光谱扫描,测量滤光片在紫外区域的透射比;红外滤光片校准选择波长范围800~1 100 nm进行光谱扫描,测量滤光片在红外区域的透射比。线型光束感烟火灾探测器滤光片校准波长扫描范围设置为700~1 100 nm,取850~950 nm透射比平均值计算减光值。火焰探测器紫外滤光片校准结果为220,240,260,280 nm波长下的透射比,红外滤光片校准结果为850,900,950,1 000 nm波长下的透射比,不作合格性判定。线型光束感烟火灾探测器滤光片减光值标称值为0.4,0.9 d B时,误差不超过±0.1 d B;减光值标称值为10.0 d B时,误差不超过±1.0 d B。     

Effect of Nail Thickness on Visible Radiation Transmittance: Implications for New Photodynamic Therapy Technologies in Onychomycosis

Photodynamic therapy is taking importance as a nonintrusive treatment for nail onychomycosis. Knowledge of true transmittance values across nails could lead to qualitative and quantitative improvements in light-based treatments. We have characterized the spectral transmittance of healthy and fungally infected human fingernails and toenails according to nail thickness, and we propose a surface transmittance model for the small-scale optimization of light-based treatments. Transmittance of fingernails and toenails was analyzed by means of spectroradiometric measurements under solar-simulated visible light radiation (400 nm to 750 nm). The nail thickness was measured by means of microscope measurement. Transmittance was highest at longer wavelengths and decreased gradually as the wavelengths became shorter but with a significant nail transmittance of around 20% in the blue region of the spectrum. In the case of nails affected by onychomycosis, transmittance fell to under 10% because of the thickness of the nails, with no changes in spectral characteristics of transmitted light. Nail thickness is the main variable controlling exponentially light transmission in the visible spectrum and not only red radiation is effective for nail onychomycosis PDT. Blue light, the spectral band more effective for PPIX absorption is also effectively transmitted.     

基于多阶导数拉曼光谱组合技术的矿物油模式分类

为了实现对法庭科学领域重质矿物油物证的快速、准确、无损的鉴定,该文基于光谱分析技术提出了一种多阶导数光谱数据组合分析的方法。收集了80种不同型号、不同厂家的重质矿物油样本,利用傅里叶变换拉曼光谱分析法采集样本的原始光谱数据和导数光谱数据,并通过结合化学计量学构建分类模型。在构建的主成分分析(PCA)结合径向基函数神经网络(RBF)分类模型中,对单独的原始光谱、一阶导数谱和二阶导数谱数据的训练集准确率分别为80.0%、86.7%和86.2%,测试集准确率分别为73.3%、80.0%和72.7%;对组合后的原始光谱+一阶导数谱、原始光谱+二阶导数谱和一阶导数谱+二阶导数谱数据的分类中,训练集准确率分别为97.0%、96.7%和100%,测试集准确率分别为85.7%、90.0%和100%。结果表明,对组合后的导数光谱与原始光谱构建分类模型,准确率更高。其中,基于一阶导数谱+二阶导数谱数据构建的PCA结合RBF分类模型的结果最为理想,准确率达100%。而K最近邻算法模型由于受到样本不均匀的影响,整体分类准确率均较低。利用组合的导数光谱与原始光谱数据构建分类模型能够实现对重质矿物油样本的快速、准确、无损鉴别,可为光谱组合技术在法庭科学及其他分析测试领域的应用提供一定的借鉴和参考。     

比值导数波谱法分析混合色素

本文叙述了比值导数波谱法的原理，该法以混合物的波谱除以干扰组分的标准波谱面得到比值波谱，以比值波谱对波长求导得到比值导数波谱，由此得到的波谱可完全消除干扰组分的吸光度贡献。采用此法能方便地对二组分混合体系进行分析，如选择合适的零交点，则可对二组分混合体系进行分析。利用此法对胭脂红、日落黄及柠檬黄三种色素的二组分及三组分混合体系进行了分析，均获较好的结果。     

PHOTOAGING EFFECTS ON SPECTRAL TRANSMITTANCE OF PLASTIC FILTERS

We examined the effects of ultraviolet (UV) radiation in combination with high levels of infrared (IR) radiation on the spectral transmittance of plastic filters. The biological action spectrum for damage to the human eye and skin changes dramatically in the 300-400 nm wavelength range. Cut-off filters used in this region to shape the spectrum of exposure sources are thus critical to the design of experiments which use broadband light sources. The changes in transmittance of three types of plastic filters were observed over an exposure period of 1000 h. One set of three filters was exposed mainly to UV radiation, while the other set was exposed to UV radiation plus IR radiation. Filters exposed to both UV and IR radiation showed spectral changes in their transmittance, while the filters exposed to UV only showed no measurable changes.     

Quantification of paracetamol in intact tablets using near-infrared transmittance spectroscopy.

Production batch samples of paracetamol tablets and specially prepared out-of-specification batches covering the range 90-110% of the stated amount (500 mg) were analysed by the BP official UV assay and by NIR transmittance spectroscopy. NIR measurements were made on 20 intact tablets from each batch, scanned five times each (10 min measurement time per batch) over the spectral range 6000-11,520 cm-1. An average spectrum was calculated for each batch. Partial least squares (PLS) regression models were set up using a calibration set (20 batches) between the NIR response and the reference tablet paracetamol content (UV). Various pre-treatments of the spectra were examined; the smallest relative standard error of prediction (0.73%) was obtained using the first derivative of the absorbance over the full spectrum. Only two principal components were required for the PLS model to give a good relationship between the spectral information and paracetamol content. Applying this model to the validation set (15 batches) gave a mean bias of -0.08% and a mean accuracy of 0.59% with relative standard deviations of 0.75 and 0.44%, respectively. The proposed method is non-destructive and therefore lends itself to on-line/at-line production control purposes. The method is easy to use and does not require a knowledge of the mass of the tablets.     

水溶性C60衍生物的电化学合成及表征

通过电化学方法合成了一种具有良好水溶性并能在水及空气中长期稳定存在的C₆₀衍生物,经电泳实验证实该衍生物带负电荷。红外光谱及近红外光谱显示该水溶物有稳定键合的CO和OH基,所以表现出强亲水性。在可见区(从420nm到700nm)有非常宽的发光谱带,这是由于Jahn-Teller效应以及C₆₀和OH基之间的相互作用引起的。     

Spectrophotometric resolution of ternary mixtures of salicylaldehyde, 3-hydroxybenzaldehyde and 4-hydroxybenzaldehyde by the derivative ratio spectrum-zero crossing method

A new spectrophotometric method for resolving ternary mixtures is proposed. The method is based on the simultaneous use of the first derivative of ratio spectra and measurements of zero-crossing wavelengths. The ratio spectrum is obtained by dividing the amplitudes of the absorption spectrum of the mixture by a standard spectrum of one of the components giving the first derivative of the ratio spectrum. The concentrations of the other components is then determined from their respective calibration graphs established by measuring the ratio derivative analytical signal at the selected zero-crossing points. The method has been applied to resolving ternary mixtures of the isomers salicylaldehyde, 3-hydroxybenzaldehyde and 4-hydroxybenzaldehyde. Previously, we also resolved the binary mixture of salicylaldehyde and 3-hydroxybenzaldehyde. The method compares favourably with other spectrophotometric methods.