Two-peak approximation in kinetic capillary electrophoresis

Kinetic capillary electrophoresis (KCE) constitutes a toolset of homogeneous kinetic affinity methods for measuring rate constants of formation (k(+)) and dissociation (k(-)) of non-covalent biomolecular complexes, C, formed from two binding partners, A and B. A parameter-based approach of extracting k(+) and k(-) from KCE electropherograms relies on a small number of experimental parameters found from the electropherograms and used in explicit expressions for k(+) and k(-) derived from approximate solutions to mass transfer equations. Deriving the explicit expressions for k(+) and k(-) is challenging but it is justified as the parameter-based approach is the simplest way of finding k(+) and k(-) from KCE electropherograms. Here, we introduce a unique approximate analytical solution of mass transfer equations in KCE termed a "two-peak approximation" and a corresponding parameter-based method for finding k(+) and k(-). The two-peak approximation is applicable to any KCE method in which: (i) A* binds B to form C* (the asterisk denotes a detectable label on A), (ii) two peaks can be identified in a KCE electropherogram and (iii) the concentration of B remains constant. The last condition holds if B is present in access to A* and C* throughout the capillary. In the two-peak approximation, the labeling of A serves only for detection of A and C and, therefore, is not required if A (and thus C) can be observed with a label-free detection technique. We studied the proposed two-peak approximation, in particular, its accuracy, by using the simulated propagation patterns built with the earlier-developed exact solution of the mass-transfer equations for A* and C*. Our results prove that the obtained approximate solution of mass transfer equations is correct. They also show that the two-peak approximation facilitates finding k(+) and k(-) with a relative error of less than 10% if two peaks can be identified on a KCE electropherogram. Importantly, the condition of constant concentration of B is always satisfied in macroscopic approach to studying kinetics at equilibrium (MASKE) whether or not B is in excess to A* and C*, and, thus, the two-peak approximation is applicable to MASKE. It completes a toolset of fitting-free methods for processing MASKE data and makes MASKE a simple practical method for finding k(+) and k(-) of "fast", "slow", and "intermediate-rate" non-covalent interactions.     

利用流动注射仪测定稻米直链淀粉含量的研究

利用流动注射分析仪,建立了测定稻米直链淀粉含量标准曲线,并进行分析验证．试验结果表明：在检测波长720nm,参比波长880nm,注射比色时间20s,检测时间40s的实验条件下,测定稻米常量(100mg)和微量(10mg)样本直链淀粉含量时,用消解定容好的稻米淀粉分散液直接进行比色测定,所得到的测试数据准确,重现性好．表明流动注射仪用于检测稻米直链淀粉含量完全可行,且比常规的测试方法操作简便、速度快．     

Development of Multi-Wavelength Spectral-Correction Method

Beta-correction theory has been applied extensively for the analysis of metal complex solution1-3. Recently, we found that the beta-correction principle was very useful to the determination of metal complex's properties, for example the stepwise real absorptivity (() and stability constant (Km). The new equations were established as follows: and where Ac=((A-((A')/(1-((). The term, Ac indicated the real absorbance of complex ML( ((, ( and ( were all constants), Cligand and CM were the mola…     

ICP-SSEA 法测定铸铝合金中8种元素

将固体进样装置与电感耦合等离子体发射光谱仪(ICP-SSEA)联用，采用固体进样，直接测定铸铝合金中的铜、铁、镁、锰、镍、钛、硅、锌等元素含量。研究表明，该法与火花光谱法比较，具有很宽的的动态范围，测量精度和普通化学分析方法相当，同时又有火花光谱分析的速度。能满足工厂冶炼控制的要求。     

Parameter estimation in modulated, unbranched reaction chains within biochemical systems

Modern biology is increasingly developing techniques for measuring time series of global gene expression and of many simultaneous proteins or metabolites. These data contain valuable information on the dynamics of cells, which has to be extracted with computational means. Given a suitable mathematical model, this extraction is in principle a straightforward regression task, but the complexity and nonlinearity of the differential equations that describe biological systems cause severe difficulties when the systems are of realistic size. We propose a method of stepwise regression that can be applied effectively to linear portions of pathways. The method may be combined with other estimation methods and either directly yields reasonable parameter estimates or at least provides appropriate start values for subsequent nonlinear search algorithms. We illustrate the method with the analysis of in vivo NMR data describing the dynamics of glycolytic metabolites in Lactococcus lactis.     

X-射线荧光光谱法快速测定半钢发热剂中Si,P,S

目前,国内没有关于半钢发热剂的国家标准检测方法,只能根据组分范围分别检测各个组分,不仅耗时而且使用的大量化学试剂对环境造成污染。故研究了X-射线荧光光谱法快速测定半钢发热剂中Si,P,S的方法。采用粉末压片制样,研究其制样条件,包括磨样时间、压样时间和压力对测定结果的影响。采用其它方法定值提供的检测样品,作为X-射线荧光光谱法内控标准样品,采用经验系数法进行基体校正,通过解谱拟合建立校准曲线,校准曲线建立后仪器建立漂移校正程序。实验结果精密度好,各元素的相对标准偏差在0.15%~1.3%。准确度满足生产需求,实验方法可用于快速检测半钢发热剂化学组分。     

Spatially resolved microrheology through a liquid/liquid interface

We present a light-scattering technique for the measurement of the microrheological properties of viscoelastic liquids in small volumes over a large frequency range (on the order of eight decades). The accuracy of the method for model viscoelastic liquids (polyethylene oxide solutions in water) is demonstrated by comparing the results with conventional mechanical measurements of the loss and storage moduli. Then we show that the method can be used to measure variations in viscoelastic properties in a heterogeneous system by measuring the variation in the moduli with position (and time) across a liquid/liquid interface between a viscoelastic polymer solution and a Newtonian liquid.     

Calculation of X-ray absorption near edge structure of CeO2 using a model cluster

We report result of a first-principle molecular orbital calculation using discrete-variational (DV)-X method on a model of CeO₂ ([CeO₈]¹²⁻), and compare them with experimental date on X-ray absorption-near-edge structure. Even using a small cluster model, we can reproduce the two-peak structure near edge and explain the origin of the peaks. The two-peak structure is relially interpreted from the viewpoint of interactions between atomic orbitals. The theoretical spectra are obtained with the dipole approximation. In addition, we calculate the wave functions, which indicate that the low-energy peak in the two-peak structure originates from a quasi-bound state composed of localized Ce d and O component. The orgin of the high-energy peak is the phase shift between localized Ce d orbital and that of the delocalized standing wave of O atomic orbitals.     

FCC催化剂中锑含量的测定

用火焰原子吸收法测定催化剂中锑含量,考察了消解温度、消解时间、酸度等对测量结果的影响,优选出了最佳分析测试条件.所建方法简便、灵敏、准确,该方法回收率在95%～99%之间,变异系数小于2.5%,最小检出限为0.092mg/L.     

基质辅助激光解吸电离飞行时间质谱研究（I）：林芳烃化合物

采用基质辅助激光解吸电离飞行时间质谱（ＭＡＬＤＩ－ＴＯＦ－ＭＳ）对杯芳烃化合物进行了分析。探讨了样品的制备条件、仪器操作参数等因素对测定结果的影响。２５种样品的质谱数据表明,利用ＭＡＬＤＩ－ＴＯＦ－ＭＳ可非常方便地得到灵敏度、分辨率、准确度均较高,且易于识别和解析的质谱图,为此类化合物的质谱表征提供和建立了一种新的高效分析方法。     

Two-step melting of Na(41)(+)

The heat capacity of the mass selected Na(41) (+) cluster has been measured using a differential nanocalorimetry method. A two-peak structure appears in the heat capacity curve of Na(41) (+), whereas Schmidt and co-workers [M. Schmidt, J. Donges, Th. Hippler, and H. Haberland, Phys. Rev. Lett. 90, 103401 (2003)] observed, within their experimental accuracy, a smooth caloric curve. They concluded from the absence of any structure that there is a second order melting transition in Na(41) (+) with no particular feature such as premelting. The observed difference with the latter results is attributed to the better accuracy of our method owing to its differential character. The two structures in the heat capacity are ascribed to melting and premelting of Na(41) (+). The peak at lower temperature is likely due to an anti-Mackay to Mackay solid-solid transition.     

Characterization of self-assembled films of NiGa layered double hydroxide nanosheets and their electrochemical properties

In this study, we have demonstrated the synthesis and delamination of a rarely studied NiGa layered double hydroxide (LDH) system. Hydrothermal treatment under agitation conditions at 200 °C for 4 h resulted in the formation of highly crystalline NiGa LDHs in a shorter time than those synthesized without agitation. The LDH was delaminated into the individual nanosheets in formamide. The most significant finding in this study is the electrochemical behavior of interlayer ferricyanide anions intercalated with the layer-by-layer (LBL) assembly method. The morphology of LBL film with one layer is also monitored with atomic force microscopy. The cyclic voltammogram is similar to potassium metal hexacyanoferrate systems with its unique two-peak wave. Raman spectrum of the film revealed that the metal center of the interlayer cyano complex is in interaction with the Ni²⁺ of the host layer. It was concluded that the two-peak cyclic voltammogram of the film is a result of two different forms of the hexacyanoferrate in the interlayer.     

Dual-focus fluorescence correlation spectroscopy of colloidal solutions: influence of particle size

Fluorescence correlation spectroscopy (FCS) is a powerful technique for measuring diffusion coefficients of small fluorescent molecules at pico- to nanomolar concentrations. Recently, a modified version of FCS, dual-focus FCS (2fFCS), was introduced that significantly improves the reliability and accuracy of FCS measurements and allows for obtaining absolute values of diffusion coefficients without the need of referencing again a known standard. It was shown that 2fFCS gives excellent results for measuring the diffusion of small molecules. However, when measuring colloids or macromolecules, the size of these objects can no longer be neglected with respect to the excitation laser focus. Here, we analyze how 2fFCS data evaluation has to be modified for correctly taking into a count these finite size effects. We exemplify the new method of measuring the absolute size of polymeric particles with simple and complex fluorophore distributions.     

UV–化学模式识别不同产地的丹参

建立由UV–化学模式识别法评价丹参质量的方法。分别用正己烷、乙酸乙酯、水、乙醇提取不同产地的丹参,并测绘其紫外光谱。取紫外光谱各波长的吸光度为特征数据,进行主成分分析、聚类分析,对不同产地丹参质量的差异进行了评价。不同溶剂提取液的光谱聚类结果有所差异,可将不同产地丹参聚为3类。UV–化学模式识别技术可以从整体上反应丹参所含成分的差异,可为丹参质量控制与评价提供依据。     

卷烟纸中CaCO3的定量方法比较及形貌表征研究

分别采用煅烧法、电位滴定法及络合滴定法定量测定3种卷烟纸中CaCO3的含量,发现煅烧温度和时间对煅烧法的测定结果影响很大,当煅烧温度为900 ℃,煅烧2 h时卷烟纸中的纤维可完全氧化分解;电位滴定法和络合滴定法的结果具有较高的稳定性,但卷烟纸中的金属氧化物和碳酸盐易给电位滴定法带来误差,络合滴定法通过遮蔽剂可消除杂质离子的影响,具有较高的准确性。对3种卷烟纸灰分的XPS分析结果表明,灰分中除CaO外,还含有C、Na2CO3、Na2SiO3、Na3PO4、CaSiO3、Ca3(PO4)2等物质;SEM分析结果表明CaCO3呈纺锤状微晶和团簇状体分布在纤维中。该研究结果提供了一种比较准确的定量测定纸张中CaCO3含量的方法。     

Measurement of gas-liquid partition coefficient and headspace concentration profiles of perfume materials by solid-phase microextraction and capillary gas chromatography-mass spectrometry

An empirical model describing the relationship between the partition coefficients (K) of perfume materials in the solid-phase microextraction (SPME) fiber stationary phase and the Linearly Temperature Programmed Retention Index (LTPRI) is obtained. This is established using a mixture of eleven selected fragrance materials spiked in mineral oil at different concentration levels to simulate liquid laundry detergent matrices. Headspace concentrations of the materials are measured using both static headspace and SPME-gas chromatography analysis. The empirical model is tested by measuring the K values for fourteen perfume materials experimentally. Three of the calculated K values are within 2-19% of the measured K value, and the other eleven calculated K values are within 22-59%. This range of deviation is understandable because a diverse mixture was used to cover most chemical functionalities in order to make the model generally applicable. Better prediction accuracy is expected when a model is established using a specific category of compounds, such as hydrocarbons or aromatics. The use of this method to estimate distribution constants of fragrance materials in liquid matrices is demonstrated. The headspace SPME using the established relationship between the gas-liquid partition coefficient and the LTPRI is applied to measure the headspace concentration of fragrances. It is demonstrated that this approach can be used to monitor the headspace perfume profiles over consumer laundry and cleaning products. This method can provide high sample throughput, reproducibility, simplicity, and accuracy for many applications for screening major fragrance materials over consumer products. The approach demonstrated here can be used to translate headspace SPME results into true static headspace concentration profiles. This translation is critical for obtaining the gas-phase composition by correcting for the inherent differential partitioning of analytes into the fiber stationary phase.     

Production of multi-hollow polymer particles by the stepwise acid/alkali method

 Recently, we reported that multi-hollow polymer particles can be prepared from carboxylated polymer particles by the stepwise alkali/acid method. In this article, an attempt was made to prepare similar particles from acid-swellable polymer particles by the stepwise treatment with acid and alkali, which was named the stepwise acid/alkali method. The acid-swellable particles were produced by emulsion terpolymerization of styrene, butyl acrylate, and dimethyl 2-amino ethyl methacrylate. The effects of initial pH value, temperature, and time in the acid and alkali treatment processes on the multi-hollow structure were examined. Received: 18 December 1996 Accepted: 11 March 1997     

Gold-silver-graphene hybrid nanosheets-based sensors for sensitive amperometric immunoassay of alpha-fetoprotein using nanogold-enclosed titania nanoparticles as labels

A stepwise method development strategy has been employed to develop a robust HPLC method to resolve several closely eluting structurally related impurities in an active pharmaceutical ingredient (API). This strategy consisted of automated column screening, optimization of the most critical chromatographic parameters, DryLab(?) modeling, and experimental verification of optimized separation conditions. DryLab(?) was used to predict an optimized gradient profile and separation temperature and these predictions were verified experimentally. A discussion of the accuracy of these predictions is presented. The robustness of the method was verified and the ability of DryLab(?) to predict, with reasonable accuracy, the outcome of such robustness studies was also examined. Once the robustness was established by the DryLab(?) predictions the remainder of the subsequent verification by experiment becomes a simple reiterative exercise. This study also demonstrates that factors such as column chemistry and critical chromatographic parameters can have a profound and oftentimes interrelated effect on the chromatographic separation of isomers, bromo analogs and other structurally very similar impurities. Therefore, it is critical to adopt a rational strategy, as demonstrated here, to evaluate the interplay of these factors, thereby greatly enhancing method development efficiency.     

Measurement of Gas Adsorption with Jäntti's Method Using Continuously Increasing Pressure

Jäntti et al. published a method to reduce the time necessary for adsorption measurements. They proposed to extrapolate the equilibrium in the stepwise isobaric measurement of adsorption isotherms by measuring at each step three points of the kinetic curve. For that purpose they approximated the kinetic curve by an exponential function which they derived empirically from there measurements. In the present paper we discuss the applicability of the method for adsorption measurements under continuously varying gas pressure.     

超高效液相色谱-三重四极杆质谱联用检测红色糖多孢菌胞内中间代谢物同位素丰度

采用超高效液相色谱-三重四极杆串联质谱联用仪(LC-MS/MS),建立了能精确检测红色糖多孢菌胞内代谢物13C同位素丰度的方法.在优化的超高效液相色谱的条件及三重四极杆串联质谱的离子传输电压和碰撞池电压下,筛选出各胞内代谢物的最佳离子对.根据物质在LC-MS/MS中生成的母离子和子离子碳链长短及子离子是否含有13C等特性,建立了"一对一"法、"一对多"法和单级质谱SIM法等同位素丰度检测方法.利用这些方法,检测了自然标记标准品和13C标记实验样品,根据实验值与理论值的接近程度筛选出最优方法.结果表明,对于以磷酸糖类为代表的子离子不含有13C的代谢物,"一对一"法最有效;对于以有机酸类为代表的母离子和子离子都含有13C的短碳链代谢物,"一对多"法更有优势;对于以辅酶A类为代表的母离子和子离子都含有13C且碳链较长的代谢物,单级质谱SIM法才能发挥作用.建立的同位素丰度检测方法具有较好的准确度,可应用于红色糖多孢菌胞内代谢物同位素丰度的检测,为后续研究菌体的代谢机理,实现红霉素的高效表达奠定了基础.