Characterization of surfactant complex mixtures using Raman spectroscopy and signal extraction methods: Application to laundry detergent deformulation

This paper presents the analysis of surfactants in complex mixtures using Raman spectroscopy combined with signal extraction (SE) methods. Surfactants are the most important component in laundry detergents. Both their identification and quantification are required for quality control and regulation purposes. Several synthetic mixtures of four surfactants contained in an Ecolabel laundry detergent were prepared and analyzed by Raman spectroscopy. SE methods, Independent Component Analysis and Multivariate Curve Resolution, were then applied to spectral data for surfactant identification and quantification. The influence of several pre-processing treatments (normalization, baseline correction, scatter correction and smoothing) on SE performances were evaluated by experimental design. By using optimal pre-processing strategy, SE methods allowed satisfactorily both identifying and quantifying the four surfactants. When applied to the pre-processed Raman spectrum of the Ecolabel laundry detergent sample, SE models remained robust enough to predict the surfactant concentrations with sufficient precision for deformulation purpose. Comparatively, a supervised modeling technique (PLS regression) was very efficient to quantify the four surfactants in synthetic mixtures but appeared less effective than SE methods when applied to the Raman spectrum of the detergent sample. PLS seemed too sensitive to the other components contained in the laundry detergent while SE methods were more robust. The results obtained demonstrated the interest of SE methods in the context of deformulation.     

Experimental NMR and MS study of benzoylguanidines. Investigation of E/Z isomerism

Molecules containing the guanidinic nuclei possess several pharmacological applications, and knowing the preferred isomers of a potential drug is important to understand the way it operates pharmacologically. Benzoylguanidines were synthesized in satisfactory to good yields and characterized by NMR, Electrospray Ionization Mass Spectrometry (ESI‐MS) and Fourrier Transform InfraRed Spectroscopy techniques (FTIR). E/Z isomerism of the guanidines was studied and confirmed by NMR analysis in solution (¹H‐¹³C Heteronuclear Single Quantum Coherence (HSQC) and Heteronuclear Multiple‐Bond Correlation (HMBC), ¹H‐¹⁵N HMBC, ¹H‐¹H Correlation Spectroscopy (COSY) and Nuclear Overhauser Effect Spectroscopy (NOESY) experiments) at low temperatures. Compounds with p‐Cl and p‐Br aniline moiety exist mainly as Z isomer with a small proportion of E isomer, whereas compounds with p‐NO2 moiety showed a decrease in proportion of isomer Z. The results are important for the application of these molecules as enzymatic inhibitors. Copyright © 2013 John Wiley & Sons, Ltd.     

Bayesian selection of graphical regulatory models

We define a new class of coloured graphical models, called regulatory graphs. These graphs have their own distinctive formal semantics and can directly represent typical qualitative hypotheses about regulatory processes like those described by various biological mechanisms. They admit an embellishment into classes of probabilistic statistical models and so standard Bayesian methods of model selection can be used to choose promising candidate explanations of regulation. Regulation is modelled by the existence of a deterministic relationship between the longitudinal series of observations labelled by the receiving vertex and the donating one. This class contains longitudinal cluster models as a degenerate graph. Edge colours directly distinguish important features of the mechanism like inhibition and excitation and graphs are often cyclic. With appropriate distributional assumptions, because the regulatory relationships map onto each other through a group structure, it is possible to define a conditional conjugate analysis. This means that even when the model space is huge it is nevertheless feasible, using a Bayesian MAP search, to a discover regulatory network with a high Bayes Factor score. We also show that, like the class of Bayesian Networks, regulatory graphs also admit a formal but distinctive causal algebra. The topology of the graph then represents collections of hypotheses about the predicted effect of controlling the process by tearing out message passers or forcing them to transmit certain signals. We illustrate our methods on a microarray experiment measuring the expression of thousands of genes as a longitudinal series where the scientific interest lies in the circadian regulation of these plants.     

How vector feeding preference through an infectious host relates to the seasonal transmission rates in a mathematical vector‐host model

Vector‐borne diseases, such as leishmaniasis, dengue, malaria, and yellow fever, transmitted by microparasites show periodic fluctuations in their prevalence. The novelty of this research is to assess the relationship between the vector feeding preference for an infectious host and the annual seasonal transmission through a vector‐host mathematical model. For the first time, numerical simulations illustrate that by increasing the vector feeding preference value in the transmission dynamics, periodic fluctuations accentuate and the endemic equilibrium average increases in vector and host populations. Moreover, increasing the vector feeding preference value, the amplitude strengthens for the infectious host and vector populations. This periodic behavior shows a similar pattern with the Peruvian incidence data from 2000 to 2016 for Andean cutaneous leishmaniasis provided by the Ministry of Health of Peru (MINSA). In addition, using the Floquet theory, the time average method and the linear operator method provides for the first time that the basic reproduction number for a nonautonomous system depends explicitly on the vector feeding preference for the infectious host. The nonautonomous model system shows that is a threshold parameter for the local stability of the disease‐free periodic solution. Therefore, the vector feeding preference is an important factor that should be considered and attended to for future research. Public and veterinary health in Peru and other countries should consider the vector feeding preference for specific host to vector control.     

高中化学创新实验课程的设计与实施*

将学生所学的化学理论知识与生活实际和学科最前沿的研究热点相结合,开发并实施了 “氢氧化镁纳米材料的制备及其在处理重金属废水中的应用” 创新实验课程。该课程通过文献调研、方案设计、实验操作、结果与讨论以及论文撰写等环节,激发学生的创新潜能,系统培养学生的创新综合素质和责任意识,这有助于更好地达成化学学科核心素养。     

A design of experiments concept for the minimization of nonspecific peptide adsorption in the mass spectrometric determination of substance P and related hemokinin‐1

Substance P and hemokinin‐1 were predominantly examined by immunoassays with their limitation to differentiate appropriately between both peptides. The use of liquid chromatography coupled with tandem mass spectrometry is a promising, highly selective alternative. Adsorption processes have been identified in preliminary experiments to play a crucial role in the loss of mass spectrometry intensity of both peptides. Therefore, a design of experiments concept was created to minimize nonspecific peptide adsorption. For this purpose, the most critical influencing parameters—(1) the composition of the injection solvent as well as (2) the most suitable container material—were systematically and concordantly investigated. The addition of modifiers, such as formic acid, dimethyl sulfoxide, and organic solvents, to the injection solvent led to a substantial gain of intensity of substance P and hemokinin‐1 compared to the start gradient as an injection solvent. Furthermore, the systematic investigation underlined the high impact of the container material, demonstrating polypropylene as the most favorable material. A conjoint injection solvent optimum was found to determine both peptides simultaneously by the conduction of a sweet‐spot analysis. The experimental design substantially reduced nonspecific peptide adsorption and enabled the simultaneous and selective determination of endogenous substance P and hemokinin‐1 plasma levels.     

数学建模思想渗入大学数学课堂教学的试验研究

以高等数学课堂教学为例,通过科学试验的方法分析数学建模思想渗入大学数学课堂教学对学生学习的影响力。通过精心设计教学试验,采集大量试验数据进行建模分析,结果表明,数学建模思想渗入高等数学课堂教学会对学生的学习产生积极影响,值得推广并长期坚持。     

A combined crossed molecular beam and quasiclassical trajectory study of the Titan-relevant N(2D) + D2O reaction

Following a recent investigation on the N(²D) + H₂O reaction [Homayoon et al., J. Phys. Chem. Lett. 5, 3508 (2014)], we report on an experimental and theoretical study of the isotopologue N(²D) + D₂O reaction. Crossed molecular beam (CMB) experiments were conducted at a collision energy of 10.3 kcal mol^–1. Quasiclassical trajectory calculations were performed on a recent potential energy surface to derive the centre-of-mass functions necessary to simulate the CMB laboratory distributions. Excellent agreement was found. The importance of the channel leading to HON/DON was confirmed. The inclusion of this channel, in addition to that leading to the isomer HNO/DNO, can affect the models considering the coupling between nitrogen and oxygen chemistry in the upper atmosphere of Titan.     

Study of the Molecular Mobility in Polymers with the Thermally Stimulated Recovery Technique—A Review

Thermally stimulated recovery (TSR) is a non‐conventional mechanical spectroscopy technique that allows to analyse in detail the relaxation processes of polymeric systems in the low frequency region. This work reviews the main aspects and potentialities of this technique. The different kinds of TSR experiments that can be performed, global and thermal sampling (TS) experiments, are described and illustrated with several examples. Also, the different methods for the determination of the thermokinetic parameters (activation energy and pre‐exponential factor) of the thermal sampling (TS) procedure are explained and compared. In this context, the compensation phenomenon, which always appears in TSR results when the studies are performed in the glass transition region of a given system, is discussed. Examples of the application of this technique to different polymeric systems during the last 20 years are provided. An emphasis will be made on the analysis of the effect of crystallinity degree and crosslink density on the TSR response. A comparison between the results (characteristic times and activation energies) obtained by different techniques, namely TSR, dynamic mechanical analysis (DMA), and differential scanning calorimetry (DSC), is made.     

Contact Angle Determined by Spontaneous Imbibition in Porous Media: Experiment and Theory

In this paper, a theoretical model was established to determine the contact angle by introducing a new defined effective capillary radius into the Lucas–Washburn equation. Based on the theoretical model, capillary rise experiments of water imbibed by different glass beads were carried out to measure the contact angle; the results were similar to the available data published in the literature. In addition, the model was modified to take account of the dynamic contact angle, according to the experimental data. The influence of the dynamic contact angle on the movement of the spontaneous imbibition was studied.