Analytica Chimica Acta: X

Titanate nanosheets (single layer, typically 200 nm lateral size) deposited from aqueous colloidal solution onto electrode surfaces form lamellar hosts that bind redox active molecular redox probes. Here, hydrophobic redox systems such as anthraquinone, 1-amino-anthraquinone, deca-methylferrocene, 5,10,15,20-tetraphenyl-21H,23H-porphine manganese (III) chloride (TPPMnCl), and α-tocopherol are shown to bind directly from cyclopentanone solution (and from other types of organic solvents) into the titanate nanosheet film. For anthraquinone derivatives, stable voltammetric responses are observed in aqueous media consistent with 2-electron 2-proton reduction, however, independent of the pH of the outside solution phase environments. For decamethylferrocene a gradual decay of the voltammetric response is observed, but for TPPMnCl a more stable voltammetric signal is seen when immersed in chloride containing (NaCl) electrolyte. α-Tocopherol exhibits chemically irreversible oxidation and is detected with 1 mM-20 mM linear range and approximately 10-3 M concentration limit of detection. All redox processes exhibit an increase in current with increasing titanate film thickness and with increasing external electrolyte concentration. This and other observations suggest that important factors are analyte concentration and mobility within the titanate host, as well as ion exchange between titanate nanosheets and the outside electrolyte phase to maintain electroneutrality during voltammetric experiments. The lamellar titanate (with embedded tetrabutyl-ammonium cations) behaves like a hydrophobic host (for hydrophobic redox systems) similar to hydrophobic organic microphase systems. Potential for analytical applications is discussed.

Wulan Tri Wahyuni

Budi Riza Putra

Christian Harito

Dmitry V. Bavykin

Frank C. Walsh

Philip J. Fletcher

Frank Marken

Analytica Chimica Acta X

Extraction of hydrophobic analytes from organic solution into a titanate 2D-nanosheet host: Electroanalytical perspectives

从有机溶液中提取疏水性分析物到钛酸盐二维纳米片主体：电分析学视角

Botulinum neurotoxins (BoNTs) are classified at a highest degree of threat in biodefense, due largely to their high lethality. With the growing risk of biowarfare, the shortcomings of the gold standard test for these neurotoxins, the mouse bioassay, have underscored the need to develop alternative diagnostic testing strategies. This paper reports on the detection of inactivated Clostridium botulinum neurotoxin serotype A (BoNT-A) and serotype B (BoNT-B), the two most important markers of botulism infection, by using a sandwich immunoassay, gold nanoparticle labels, and surface-enhanced Raman scattering (SERS) within the context of two threat scenarios. The first scenario mimics part of the analysis needed in response to a "white powder" threat by measuring both neurotoxins in phosphate-buffered saline (PBS), a biocompatible solvent often used to recover markers dispersed in a powdered matrix. The second scenario detects the two neurotoxins in spiked human serum to assess the clinical potential of the platform. The overall goal is to develop a test applicable to both scenarios in terms of projections of required levels of detection. We demonstrate the ability to measure BoNT-A and BoNT-B in PBS at a limit of detection (LoD) of 700 pg/mL (5 pM) and 84 pg/mL (0.6 pM), respectively, and in human serum at 1200 pg/mL (8 pM) and 91 pg/mL (0.6 pM), respectively, with a time to result under 24 h. The steps required to transform this platform into an onsite biodefense screening tool that can simultaneously and rapidly detect (<1 h) these and other agents are briefly discussed.

China Y. Lim

Jennifer H. Granger

Marc D. Porter

SERS detection of Clostridium botulinum neurotoxin serotypes A and B in buffer and serum: Towards the development of a biodefense test platform

缓冲液和血清中肉毒杆菌神经毒素A型和B型的SERS检测：面向生物防御测试平台的开发

Perfluorinated C8-(PerfluoroC8) and bidentate anchored C8-(BDC8)-modified silica hydride stationary phases have been employed for the isocratic separation of homologous phenylalkanols and phenylalkylamines differing in their n-alkyl chain length, using aqueous-acetonitrile (ACN) mobile phases of different ACN contents from 10 to 90% (v/v) in 10% increments. These analytes showed reversed-phase (RP) retention behaviour with mobile phases of <40% (v/v) ACN content with both stationary phases but with the BDC8 stationary phase providing longer retention. The PerfluoroC8, but not the BDC8, stationary phase also exhibited significant retention of these analytes under conditions typical of an aqueous normal phase (ANP) mode (i.e. with mobile phases of >80% (v/v) ACN content), with the analytes exhibiting overall U-shape retention dependencies on the ACN content of the mobile phase. Further, these stationary phases showed differences in their selectivity behaviour with regard to the n-alkyl chain lengths of the different analytes. These observations could not be explained in terms of pKa , log P, molecular mass or linear solvation energy concepts. However, density functional theory (DFT) simulations provided a possible explanation for the observed selectivity trends, namely differences in the molecular geometries and structural organisation of the immobilised ligands of these two stationary phases under different solvational conditions. For mobile phase conditions favouring the RP mode, these DFT simulations revealed that interactions between adjacent BDC8 ligands occur, leading to a stationary phase with a more hydrophobic surface. Moreover, under mobile phase conditions favouring retention of the analytes in an ANP mode, these interactions of the bidentate-anchored C8 ligands resulted in hindered analyte access to potential ANP binding sites on the BDC8 stationary phase surface. With the PerfluoroC8 stationary phase, the DFT simulations revealed strong repulsion of individual perfluoroC8 ligand chains, with the perfluoroC8 ligands of this stationary phase existing in a more open brush-like state (and with a less hydrophobic surface) compared to the BDC8 ligands. These DFT simulation results anticipated the chromatographic findings that the phenylalkanols and phenylalkylamines had reduced retention in the RP mode with the PerfluoroC8 stationary phase. Moreover, the more open ligand structure of the PerfluoroC8 stationary phase enabled greater accessibility of the analytes to water solvated binding sites on the stationary phase surface under mobile phase conditions favouring an ANP retention mode, leading to retention of the analytes, particularly the smaller phenylalkylamines, via hydrogen bonding and electrostatic effects.

Chadin Kulsing

Yada Nolvachai

Maria T. Matyska

Joseph J. Pesek

Joshua Topete

Reinhard I. Boysen

Milton T.W. Hearn

Origin of the selectivity differences of aromatic alcohols and amines of different n-alkyl chain length separated with perfluorinated C8 and bidentated C8 modified silica hydride stationary phases

不同n-烷基链长芳香醇和胺在全氟化C8和双齿C8改性硅氢固定相上分离的选择性差异的起源

Small organic molecules are used as solution additives in electrospray ionisation mass spectrometry (ESI-MS) to increase the charge states of protein ions and improve the performance of intact protein analysis by tandem mass spectrometry. The properties of the additives that are responsible for their charge-enhancing effects (e.g. dipole moment, gas-phase basicity, Brønsted basicity, and surface tension) have been debated in the literature. We report a series of solution additives for ESI-MS based on cyclic alkyl carbonates and sulphites that have alkyl chains that are from two to ten methylene units long. The extent of charging of [Val [5]]-angiotensin II, cytochrome c, carbonic anhydrase II, and bovine serum albumin in ESI-MS using the additives was measured. For both the alkyl carbonate and sulphite additives with up to four methylene units, ion charging increased as the side chain lengths of the additives increased. At a critical alkyl chain length of four methylene units, protein ion charge states decreased as the chain length increased. The dipole moments, gas-phase basicity values, and Brønsted basicities (i.e. the pKa of the conjugate acids) of the additives were obtained using electronic structure calculations, and the surface tensions were measured by pendant drop tensiometry. Because the dipole moments, gas-phase basicities, and pKa values of the additives did not depend significantly on the alkyl chain lengths of the additives and the extent of charging depended strongly on the chain lengths, these data indicate that these three additive properties do not correlate with protein charging under these conditions. For the additives with alkyl chains at or above the critical length, the surface tension of the additives decreased as the length of the side chain decreased, which correlated well with the decrease in protein charging. These data are consistent with protein charging being limited by droplet surface tension below a threshold surface tension for these additives. For additives with relatively high surface tensions, protein ion charging increased as the amphiphilicity of the additives increased (and surface tension decreased) which is consistent with protein charging being limited by the emission of charge carriers from highly charged ESI generated droplets.

Eric D.B. Foley

Muhammad A. Zenaidee

Rico F. Tabor

Junming Ho

Jonathon E. Beves

William A. Donald

On the mechanism of protein supercharging in electrospray ionisation mass spectrometry: Effects on charging of additives with short- and long-chain alkyl constituents with carbonate and sulphite terminal groups

关于电喷雾电离质谱中蛋白质超电荷化的机制：短链和长链烷基添加剂对碳酸盐和亚硫酸盐端基电荷化的影响

Non-targeted analysis is nowadays applied in many different domains of analytical chemistry such as metabolomics, environmental and food analysis. Conventional processing strategies for GC-MS data include baseline correction, feature detection, and retention time alignment before multivariate modeling. These techniques can be prone to errors and therefore time-consuming manual corrections are generally necessary. We introduce here a novel fully automated approach to non-targeted GC-MS data processing. This new approach avoids feature extraction and retention time alignment. Supervised machine learning on decomposed tensors of segmented chromatographic raw data signal is used to rank regions in the chromatograms contributing to differentiation between sample classes. The performance of this novel data analysis approach is demonstrated on three published datasets.

Kimmo Sirén

Ulrich Fischer

Jochen Vestner

Automated supervised learning pipeline for non-targeted GC-MS data analysis

非目标气相色谱-质谱数据分析的自动化监督学习管道

Water-ethanol mixtures intended for specific purposes, such as bioethanol fuel, can be subject to national quality standards, including the measurement of pHe - a solvent-specific quantification of acidity. This work discusses the shortcomings of the use of pHe in these quality standards, including the lack of metrological traceability of pHe measurements made using combination pH electrodes calibrated using aqueous pH buffers. The feasibility of measuring the acidity of 50-50 wt% water-ethanol mixtures on a non-solvent-specific, unified pH scale, which is traceable to the conventional aqueous pH scale ( pHabsH2O ) is demonstrated. pHabsH2O measurements of buffered and un-buffered water-ethanol mixtures using two cell configurations, including the use of an ionic liquid salt bridge (ILSB), show good agreement. The cell configuration, consisting of a commercial glass (half-cell) electrode and a reference electrode incorporating an ILSB, can be readily adopted by measurement laboratories.

L. Deleebeeck

A. Snedden

D. Stoica

Reconciling the pHe measurements of bioethanol: pHabs measurements of buffered 50-50 wt% water-ethanol mixtures

调和生物乙醇的pHe测量：缓冲50-50 wt%水-乙醇混合物的pHabs测量

In this study, cobalt nanoparticles (CoNPs) were synthesized and cobalt nanoparticles modified glassy carbon electrode (CoNPs/GCE) was prepared by drop coating the nanoparticles on glassy carbon electrode. After preparing polypyrrole modified glassy carbon electrode (PPy/GCE) using electropolymerization of pyrrole in LiClO4 solution, cobalt nanoparticles-polypyrrole composite modified glassy carbon electrode (CoNPs/PPy/GCE) was fabricated by drop coating the CoNPs on the PPy/GCE. Different characterization techniques such as scanning electron microscopy, transmission electron microscopy, energy dispersive spectroscopy, FTIR spectroscopy, electrochemical impedance spectroscopy and cyclic voltammetry were used to study the morphological structure and electrochemical behavior of the sensors. The results demonstrated that PPy chains interacted with CoNPs through donor-acceptor bonds. Among all the electrodes, CoNPs/PPy/GCE exhibited highest electroactive surface area and lowest electron transfer resistance towards phoxim. Under the optimal conditions, the sensor showed linear relationship between the reduction peak current and the concentration of phoxim in the range of 0.025 μM-12 μM with the detection limit as 4.5 nM. Besides, the composite electrode demonstrated excellent reproducibility, good stability and selectivity towards the possible interfering substances. All of these properties made CoNPs/PPy/GCE a suitable electrochemical sensor for the electrochemical determination of phoxim in water samples using square wave voltammetry.

Molla Tefera

Merid Tessema

Shimelis Admassie

Meryck Ward

Lisebo Phelane

Emmanuel I. Iwuoha

Priscilla G.L. Baker

Electrochemical application of cobalt nanoparticles-polypyrrole composite modified electrode for the determination of phoxim

钴纳米颗粒-聚吡咯复合修饰电极在毒死蜱测定中的电化学应用

Within the past few decades, the application of light scattering techniques to a broad range of scientific disciplines has increased significantly, especially in the field of analytical chemistry. The resulting interest in and use of light scattering methods suggests the need for an easily understood introduction and review of material for those new to the method as well as for current users in need of a refresher. In many respects, the theory and its applications may appear so overwhelming for many studying the field for the first time, that they rarely can spend the time just needed to understand the basic measurements and their interpretations. A variety of applications in analytical chemistry especially have resulted in a greater understanding of many of the macromolecular processes themselves from molar mass distributions, to the macromolecular interactions responsible for aggregation processes, to determinations of structure and function. The use of such analytical processes to obtain a better understanding of nanoparticle structure and function has become almost universal.

Philip J. Wyatt

Differential light scattering and the measurement of molecules and nanoparticles: A review

差分光散射与分子和纳米颗粒的测量：综述

This article has been withdrawn at the request of the author(s) and/or editor. The Publisher apologizes for any inconvenience this may cause. The full Elsevier Policy on Article Withdrawal can be found at https://www.elsevier.com/about/our-business/policies/article-withdrawal

Andrea Šlampová

Pavel Kubáň

WITHDRAWN: Volatile free liquid membranes for electromembrane extraction

撤回：用于电膜萃取的无挥发性液体膜

When analyzing experimental chemical data, it is often necessary to incorporate the structure of the study design into the chemometric/statistical models to effectively address the research questions of interest. ANOVA-Simultaneous Component Analysis (ASCA) is one of the most prominent methods to include such information in the quantitative analysis of multivariate data, especially when the number of variables is large. This tutorial review intends to explain in a simple way how ASCA works, how it is operated and how to correctly interpret ASCA results, with approachable mathematical and visual descriptions. Two examples are given: the first, a simulated chemical reaction, serves to illustrate the ASCA steps and the second, from a real chemical ecology data set, the interpretation of results. An overview of methods closely related to ASCA is also provided, pointing out their differences and scope, to give a wide-ranging picture of the available options to build multivariate models that take experimental design into account.

ISSN	2590-1346
h-index	11

涉及主题	物理化学生物工程类色谱法生物化学有机化学量子力学遗传学地质学计算机科学材料科学海洋学物理化学机械工程数学地理
出版信息	出版商: Elsevier B.V.，出版周期: ，期刊类型: journal，开源期刊: 否
基本数据	创刊年份: 2019，原创研究文献占比: 0.00%，自引率:N.A.， Gold OA占比: 0.00%
平均审稿周期	网友分享经验：16 Weeks

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