亮绿褪色分光光度法测定阴离子表面活性剂

在硫酸介质中,微量阴离子表面活性剂、十二烷基苯磺酸钠、十二烷基磺酸钠、十二烷基硫酸钠能使亮绿产生灵敏的褪色反应,最大褪色波长位于640nm。十二烷基苯磺酸钠、十二烷基磺酸钠、十二烷基硫酸钠的浓度分别在0—6、0—10、0—8mg/L范围符合比耳定律,表观摩尔吸收系数分别为8.89×10~3、4.03×10~3、5.28×10~3L·mol~(-1)·cm~(-1)。该法用于生活废水中微量阴离子表面活性剂的测定,结果满意。     

激光诱导金纳米棒图案化光纤SERS探针

研究了激光诱导沉积制备光纤表面增强拉曼散射(SERS)探针,并对探针的SERS性能进行检测。探讨光纤探针制备过程中金纳米棒溶液的浓度对探针灵敏度的影响。结果表明,将不同浓度的金纳米棒溶液进行激光诱导,在光纤端面会形成金纳米棒团簇和分散两种纳米结构。金纳米棒溶液的浓度、激光功率、诱导时间等因素都会对诱导沉积图案产生影响。实验利用功率为5 mW的激光进行诱导,在1.5×10^-9, 1.0×10^-9和7.5×10^-10 mol·L^-1的金纳米棒溶液中,经5 min沉积,制备出不同图案的光纤SERS探针。采用晶种法合成金纳米棒,用透射电子显微镜(TEM)观察金纳米棒形貌,并根据TEM图像分析计算了合成金纳米棒的长径比约为3.8。用扫描电子显微镜(SEM)观察金纳米棒的形貌以及激光诱导沉积后的纤维修饰端形貌,7.5×10^-10 mol·L^-1的金纳米棒溶液进行激光诱导,金纳米棒在光纤端面分布较为分散,而1.5×10^-9和1.0×10^-...     

纳米金比色法测定6-巯基嘌呤

在pH 7.0的HAc-NaAc缓冲液溶中,6-巯基嘌呤可以通过Au-S键自组装于金纳米粒子的表面.以Cu2+作为交联剂,Cu2+与6-巯基嘌呤间的配位作用导致金纳米粒子快速发生团聚,金纳米粒子溶液的颜色由红色变为蓝色,最大吸收波长从520nm红移至660nm.660nm和520nm处吸光度的比值(A660/A520)与6-巯基嘌呤的浓度在5.0×10-8-1.0×10-6moL/L范围内存在线性关系.该方法测定6-巯基嘌呤的检出限为1.4×10-8moL/L,相对标准偏差为2.9％(2.0×10-7mol/L 6-巯基嘌呤溶液,n=11).该方法已用于人血清中的6-巯基嘌呤含量的测定.     

流动注射化学发光法测定L-乳酸铝

发现L-乳酸铝对纳米金-酸性高锰酸钾体系化学发光的增强作用,其增强化学发光强度的能力与高锰酸钾及溶液的介质硫酸浓度、金浓度以及蠕动泵的转速、流动注射化学反应体系的流路设计等因素有关,在此基础上首次建立了测定L-乳酸铝的增强化学发光分析法。测定L-乳酸铝的线性范围为7.0×10-5～1.0×10-2g.mL-1,检出限为1.04×10-6g.mL-1(S/N=3),对8.0×10-4g.mL-1的L-乳酸铝标准溶液进行11次平行测定,相对标准偏差(RSD)为1.48%。该法直接用于L-乳酸铝制备合成反应液以及分离纯化废液中L-乳酸铝的测定,其回收率为95.8%～100.4%,本法与GB/T6987.8-2001法进行了对照,结果令人满意。探讨了该化学发光增强作用是由于L-乳酸铝注入体系后,加速了纳米金与酸性高锰酸钾的反应所致。     

基于石墨烯量子点的荧光探针应用于抗坏血酸检测的研究

基于石墨烯量子点(GQDs)的荧光性能建立了一种非标记荧光方法,用于灵敏和选择性测定抗坏血酸(AA)。GQDs溶液在紫外光激发下发出很强的蓝色荧光,当向溶液中加入AA后,GQDs溶液的荧光被猝灭。猝灭机理可能为在弱酸性介质中,AA与GQDs发生氧化还原反应,AA转移电子给GQDs。荧光猝灭强度与AA浓度在5.0×10~(-6)~7.5×10~(-5)mol/L范围内呈良好的线性关系,检出限低至1.0×10~(-6)mol/L。该体系成本低、操作简单,并且在多种可能干扰的物质存在下对AA表现出很高的选择性。本方法应用于生物样品中AA的检测,回收率在95.2%~115.3%之间。     

苯并噻唑类探针取代基结构对金属离子识别性能的影响

荧光探针对识别金属离子具有检测快、选择性好等特点,设计合成了两个苯并噻唑类探针分子6-(3,5-二甲基苯氧基)-5-胺基-2-苯基苯并噻唑(L4)和6-(3,5-二甲基苯氧基)-5-苯甲酰胺基-2-苯基苯并噻唑(L5),并通过探针分子的紫外可见光谱和荧光光谱的变化特征,详细研究了探针L4和L5对溶液中三价金属离子Al~(3+), Fe~(3+), Cr~(3+)和二价金属离子Cu~(2+)的识别性能。研究结果表明,当L4分子中的识别基团胺基与苯甲酰基键合形成L5分子结构时,会发生荧光猝灭,同时获得了开启式荧光探针L4和关闭式荧光探针L5。紫外可见光谱检测结果表明,在有机溶液中,探针L4选择性地识别出Al~(3+), Fe~(3+), Cu~(2+);在含水乙腈溶液中,探针L4高选择性地识别出Cu~(2+);通过紫外光照射下的裸眼检测,含探针L4的试纸有效地识别出纯水中的Cu~(2+);在有机溶液中,探针L5选择性地识别出Al~(3+)和Fe~(3+)。荧光光谱检测结果表明,当探针L4与Fe~(3+), Al~(3+), Cu~(2+)存在于有机溶液中时, L4将发生荧光猝灭;在含水乙腈溶液中,探针L4对Cu~(2+)具有高选择性识别作用;当探针L5与Cr~(3+), Fe~(3+), Al~(3+), Cu~(2+)存在于有机溶液中时, L5的荧光强度依次增强。利用溶液浓度对吸收强度作图,计算出了探针L4对Cu~(2+)的检出限为4.51×10~(-6) mol·L~(-1),络合常数Kα为1.12×10~3 M~(-1);探针L5对Al~(3+), Cr~(3+), Fe~(3+), Cu~(2+)的检测限分别为2.85×10~(-6), 4.79×10~(-6), 5.95×10~(-6)和3.23×10~(-6) mol·L~(-1),络合常数分别为:Kα(Al~(3+))=2.17×10~3 M~(-1),Kα(Cr~(3+))=2.06×10~3 M~(-1),Kα(Fe~(3+))=3.92×10~3 M~(-1),Kα(Cu~(2+))=4.43×10~3 M~(-1)。根据探针与识别金属离子的荧光滴定实验结果,推测出探针分子与金属离子之间形成了1∶1络合物。抗金属离子干扰实验结果表明,探针分子对特定金属离子的识别基本不受其他干扰金属离子的影响。~1H NMR滴定结果表明,探针L4分子结构中胺基和二甲基苯氧基,探针L5分子结构中的苯甲酰胺基和二甲基苯氧基取代基在识别金属离子过程中发挥了重要作用。探针L4在识别Cu~(2+)方面具有更广阔的应用前景。     

流动注射电化学发光分析法测定注射液中的硫酸庆大霉素

基于硫酸庆大霉素对鲁米诺在铂电极上弱的电氧化发光信号的强增敏作用与流动注射技术的结合,建立了一种测定硫酸庆大霉素的电化学发光分析新方法。该法测定硫酸庆大霉素的检出限为8.0×10-10 g·mL-1,线性范围为1.2×10-9～4.0×10-6 g·mL-1,相对标准偏差为2.0%(n =11)。该法简单、快速、灵敏,已成功地用于注射液中硫酸庆大霉素的测定。     

盐水溶液跨混合纤维素膜扩散机制的定量可视化实验研究

介绍了一种改进的高时空分辨率相移干涉仪,测量了不同浓度的NaCl溶液跨过5 μm孔径醋酸-硝酸混合纤维素膜进入去离子水的跨膜扩散过程。实验观察到NaCl溶液在膜-液界面附近的质量输运行为受膜结构的影响而表现出的特征:相对分散的浓度高值分布、均流传质现象、对流的快速纵向进行和横向扩散的缓慢发展等。实验计算得10.0 mg/mL、7.5 mg/mL、5.0mg/mL、2.5 mg/mL 和 1.0 mg/mL 的 NaCl 溶液跨膜传质系数分别为 3.0×10~(-6) m~2/s、8.5×10-7 m~2/s、7.8×10~(-7)m~2/s、2.9× 10~(-7)m~2/s和6.0×10~(-8)m~2/s。本实验结果可为跨膜扩散机理的研究提供参考。     

用于中红外甲烷检测的压强测量与补偿（英文）

利用一个波长为3.291μm的室温连续、带间级联激光器和一个有效光程长为54.6 m的多通池,研究了用于中红外甲烷检测的压强测量及补偿技术。通过对测得的甲烷直接吸收光谱信号进行洛伦兹吸收线型拟合,测量了吸收池内气体压强并补偿了压强变化对甲烷浓度的影响。利用浓度为2.1×10~(-6)的甲烷气体样品,在1.33×10~4~10.64×10~4 Pa的范围内进行了压强标定;对压强为9.31×10~4 Pa、浓度为2.1×10~(-6)甲烷气体样品的压强测量结果进行阿仑方差分析,结果表明,当积分时间为2.2s时,压强的测量精度约为219.5Pa。在1.33×104、3.99×10~4和6.65×10~4 Pa三种不同压强条件下,对浓度分别为1.0×10~(-6)、1.2×10~(-6)、1.4×10~(-6)、1.6×10~(-6)、2.1×10~(-6)甲烷气体样品的浓度和压强做了15组测量,验证了所给出的压强测量和补偿技术的可行性。     

铈(Ⅳ)和罗丹明B体系中化学发光测定硫酸沙丁胺醇

探索了硫酸沙丁胺醇在酸性介质中与铈()和罗丹明B的化学发光行为,对影响该体系的化学发光强度的诸因素进行实验和探讨,建立了流动注射化学发光法检测硫酸沙丁胺醇的新方法,检测的线性范围为4.0×10-8—2.0×10-6g/mL,检出限为1×10-8g/mL,对5.0×10-7g/mL硫酸沙丁胺醇连续11次测定的相对标准偏差为2.4%。该方法应用于硫酸沙丁胺醇片剂含量的测定并与标准方法(中国药典法)比较,结果满意。     

EXAFS研究硫酸硫脲反萃季铵氰化金的机理

季铵盐可以直接从氰化浸出液中萃取金 ,但反萃困难。酸性硫脲通空气反萃体系是目前从季铵盐中反萃氰化金最有效的体系 ,但对其机理的研究很少。文章采用扩展X射线吸收精细结构 (EXAFS)等方法研究了硫酸硫脲从负载氰化金季铵盐中反萃金的机理。研究结果表明 ,在反萃过程中 ,硫酸、硫脲和硫脲金都能以中性分子进入有机相 ,中性缔合在季铵盐反萃过程中不可忽视。反萃机理如下 :(1)硫酸和硫脲首先进入有机相被萃取 ;(2 )在有机相中 ,硫脲争夺金的氰根配位 ,使氰化金变成硫脲金 ,同时游离出来的氰根与硫酸中的氢离子作用变成氢氰酸 ,在鼓空气搅拌条件下氢氰酸被空气迅速带走排除 ;(3)硫脲金配合物在有机相和水相中分配 ,大部分硫脲金进入水相 ,从而达到反萃的目的。     

Spectrophotometric Study of Basicity of Some Substituted α-(Benzamtoomethyl)phenylhydrazines

The protonation behavior at 25°C in water and in aqueous sulfuric acid solutions of some substituted α-(p-R-benzamidomethyl)phenyl hydrazines (R=H, CH₃, Cl, Br) was investigated by UV spectrophotometry. The absorption spectra in sulfuric acid solutions were analyzed by the method of multivariate analysis. The premonition constants of hydrazine (pK₁) and amide (pK₂) moieties were determined; pK₂ values were calculated from the reconstituted absorption spectra by Cox - Yates method. Dependence of pK₂ on Hammett's a constants was discussed.     

A rapid ICP-OES strategy for determination of gold and silver in blister copper by nitric acid digestion

A rapid strategy for the analysis of gold and silver in blister copper by inductively coupled plasma optical emission spectrometry (ICP-OES) was firstly proposed. Nitric acid was used to digest blister copper instead of commonly used sulfuric acid. This prevented forming the salt of copper sulfate in the filtration process when the volume of the mixture is very small. Thus, the time of filtration was saved. After filtrating, aqua regia was used to digest the residue and acidize the filter liquor. Two parts of gotten solution were directly determined by ICP-OES. The cycle of analysis was shortened compared with sulfuric acid-fire assay. The proposed method was successfully applied to determine gold and silver in blister copper, and the results were in good agreement with those obtained by lead fire assay.     

Electron absorption spectra of univalent copper-, silver-, and gold-thiourea complexes in aqueous solutions

Using data on the stability of complex forms, electron absorption spectra of copper (I)-, silver (I)-, and gold (I)—thiourea complexes in an aqueous solution M_itu_j (Ag: i=1, 2, j=1–3; Cu: j=1, 2; Au: j=2) are calculated from the spectra of solutions of a known analytical composition. Parameters of particular bands of the absorption spectra of these complexes are given. It is found that the integral intensity of the spectra of the solutions is proportional to the concentration of thiourea in the solution with high accuracy. The same is also valid for the spectra in solutions that contain mercury (II) and thiourea. The total intensity of longwave bands in the spectra of the complexes is proportional to the number of ligands in a molecule of the complex. Institute of Ionorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, 3, Lavrent’ev Ave., 630090, Novosibirsk-90, Russia, Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 4, pp. 458–462, July–August, 1997.     

Comparison between the single-bubble sonoluminescences in sulfuric acid and in water

Single-bubble sonoluminescence (SBSL) is achieved with strong stability in sulfuric acid solutions. Bubble dynamics and the SBSL spectroscopy in the sulfuric acid solutions with different concentrations are studied with phase-locked integral stroboscopic photography method and a spectrograph, respectively. The experimental results are compared with those in water. The SBSL in sulfuric acid is brighter than that in water. One of the most important reasons for that is the larger viscosity of sulfuric acid, which results in the larger ambient radius and thus the more contents of luminous material inside the bubble. However, sonoluminescence bubble’s collapse in sulfuric acid is less violent than that in water, and the corresponding blackbody radiation temperature of the SBSL in sulfuric acid is lower than that in water. Supported by the National Natural Science Foundation of China (Grant Nos. 10434070 and 10704037) and the Ministry of Education Priorities Project of China (Grant No. 103078)     

A thermodynamic and photophysical study of the effects of thiourea on the micellar properties of aqueous sodium dodecyl sulphate solution

The micellar properties of sodium dodecyl sulphate (SDS) in aqueous thiourea solutions were investigated with the aim of studying the effect of thiourea on these properties. The critical micelle concentrations (cmc) and the degree of dissociation of the micelle were determined by the conductometric method over the temperature range 298–323 K for different concentrations of thiourea. The cmc values of the surfactant in the presence of thiourea were obtained by following the change in the relative intensities of vibrational fine structure of the pyrene fluorescence spectra. The aggregation numbers were determined by employing the static quenching fluorescence method. The cmc values in the presence of varying electrolyte concentrations (NaCl) were obtained with 8-anilinonaphthalene 1-sulphonate (ANS) as a fluorescence probe, and from these values the degree of dissociation was calculated. The mass action model was applied in the present study to obtain various thermodynamic parameters of micellization. All these properties were compared with the micellar properties of an aqueous urea/SDS system, and it was found that thiourea is a better demicellization agent.     

Intercalation and exfoliation behavior of carbon fibers during electrolysis in H2SO4

Electrochemical preparation of intercalation compounds of carbon fibers in sulfuric acid solutions and their exfoliation were studied. Effect of the concentration of sulfuric acid on the intercalation was examined. In low concentration of sulfuric acid solutions, the formation of intercalation compound and subsequent exfoliation were accelerated. By rapid heating at 1000 °C, the residue compounds of carbon fibers formed by electrolysis in 2.3–9.0 mol dm⁻³ were found to exfoliate and showed marked morphological changes. In high concentration electrolytes, however, the formation of intercalation compounds of carbon fibers and their exfoliation were depressed. The successful intercalation in low concentration electrolytes might be due to oxygen generated by anodic polarization, which resulted in marked exfoliation.     

Modeling the physico‐chemistry of acid sulfate waters through Raman spectroscopy of the system FeSO4?H2SO4?H2O

Mine waters containing extremely high concentrations of sulfuric acid and dissolved iron are found in the Rio Tinto (Spain) area. In this study, Raman spectroscopy has been used to investigate the speciation of the system iron(II)–sulfuric acid–water as an approach to study Rio Tinto's stream water. Several solutions of aqueous sulfuric acid containing iron(II) sulfate in the range 0–1.65 mol/kg were prepared, and qualitative and quantitative analyses of the ions present in the solutions were carried out using Raman spectroscopy. The intrinsic features of Raman spectroscopy allowed the identification of the species present in solution and calculation of the species concentration through band‐fitting of the Raman spectra. The activity coefficient product of the system iron(II) sulfate–sulfuric acid–water as a function of salt concentration is reported. Previous findings on the formation of iron(II) hexahydrate complexes in the mentioned system have been corroborated by means of Raman spectroscopy. Copyright © 2007 John Wiley & Sons, Ltd.     

火焰原子吸收光谱法测定砂金中金,银

本文研究了用王水溶解砂金样品，在１％王水介质中，使银生成氯化银沉淀与金定量分离。滤液控制１％王水介质用以测定金。沉淀用５％热硫有脲溶解，控制为１％硫脲介质用以测定银。利用本方法测定了砂金样品中金和银得到了满意结果。金的回收率为９９．６％－１００．８％，银的回收率为９７．２－９９．２％。     

低氧低分压环境下泡塑吸附原子吸收光谱法测定矿石中的金

在青海低氧低分压环境下,试样用王水分解,在王水介质中用多孔聚氨酯泡沫振荡吸附富集,然后用硫脲加热解脱,再直接用火焰原子吸收分光光度计测定。通过对泡塑的吸附振荡,解脱时间,硫脲浓度等条件的探讨,确定了最佳分析条件,解决了低氧低分压环境下常量A u的测定。