Shining a spotlight on our reviewers

Chemical Science is celebrating Peer Review Week 2021 with the launch of Reviewer Spotlights, a new way to highlight the hard work of our reviewers, and encourage further diversity in our reviewer community.

At Chemical Science, we recognize the many and varied contributions our reviewer community make to ensure the quality of the research published in the journal is as high as possible.We also know that a fair and unbiased review system relies on having input from a diverse range of reviewers, whether this is country of origin, gender, ethnicity, career-stage, or affiliated institution, in addition to having the relevant and sufficiently experienced subject expertise.We want our reviewers to reflect the diversity of our community and are actively working to improve this.To enable us to improve the diversity of our reviewers, it is important to start by understanding the current situation. As a first step, we have looked at where our current group of reviewers for Chemical Science are based, and how this compares with our authorship. This is a relatively easy first step, as this geograhical data is collected as part of the peer-review process and, in the case of the authorship, openly available. We have also started asking our reviewers and authors to voluntarily provide us with data on gender so we may analyse this in a similar way in the future. The other characteristics mentioned above are harder to capture, however we are currently exploring whether we should be doing this, and how this might be possible.     

Keeping the spotlight on quality from a distance

 Maintaining the quality of testing in remote locations can be demanding of laboratory resources in terms of daily visits to instruments and providing support outside of normal working hours. Recently technology and software solutions have appeared to reduce this burden for laboratory scientists dramatically. The AVL Auto QC unit, in conjunction with OMNILink software, allow laboratory staff to perform many quality control and maintenance procedures on instruments in wards and medical units from a PC in the central laboratory. Assessment of this technology and software in the Special Baby Care Unit at Bradford Royal Infirmary has demonstrated many benefits including reduction in ward visits, better support out of hours, regular quality control checks, and improved analytical quality. Received: 15 April 2000 · Accepted: 15 April 2000     

Chemometric optimization of a SIA promethazine hydrochloride assay method

A sequential injection analysis (SIA) method for the assay of promethazine hydrochloride, based on its oxidation by acidified cerium(IV), was optimized. Three chemometric approaches were applied: (i) factorial design (3³ applied to surface plot and 2³ applied to effect factor) for screening the potential interacting variables, (ii) univariant for optimizing insignificantly interacting variables and (iii) simplex for optimizing potentially interacting variables. The optimum experimental conditions were 30 μl of 0.38 mol/l sulphuric acid, 30 μl of 3.99 × 10^− 3 mol/l cerium(IV), 20 μl of promethazine hydrochloride and 20 μl/s flow rate. The detection limit was 7.032 × 10^− 5 mol/l and the calibration curve was linear up to 1.563 mol/l with a correlation coefficient 0.9998, accuracy range of 89.0-101.5%, relative standard deviation 1.1% (n = 10) and sample frequency at least 20 samples/h. The method was applied to tablet form and validated with the British Pharmacopoeia method. The developed SIA method is fully automated, reproducible, sensitive, rapid and reagent-saving, and therefore suitable for routine control in tablets form.     

Evaluation of different SIA sample-buffer configurations using a fluoride-selective membrane electrode as detector

The peak profiles of four different buffer-sample SIA configurations, e.g. buffer-sample; sample-buffer; buffer-sample-buffer and sample-buffer-sample with the last two in the sandwich mode were evaluated with a fluoride-selective membrane electrode as detector. The best response characteristics and peak shapes as well as recovery and precision values were obtained for the buffer-sample configuration. For low concentration levels, sandwich SIA configurations are more suitable, when optimum buffer and pH are used. The utilisation of a cheap electrolyte with a minimum consumption of buffer and a cheap, robust instrumentation made the SIA system suitable for on-line determination of fluoride.     

Applying sequential injection analysis (SIA) and response surface methodology for optimization of Fenton-based processes

This work presents the use of sequential injection analysis (SIA) and the response surface methodology as a tool for optimization of Fenton-based processes. Alizarin red S dye (C.I. 58005) was used as a model compound for the anthraquinones family, whose pigments have a large use in coatings industry. The following factors were considered: [H₂O₂]:[Alizarin] and [H₂O₂]:[FeSO₄] ratios and pH. The SIA system was designed to add reagents to the reactor and to perform on-line sampling of the reaction medium, sending the samples to a flow-through spectrophotometer for monitoring the color reduction of the dye. The proposed system fed the statistical program with degradation data for fast construction of response surface plots. After optimization, 99.7% of the dye was degraded and the TOC content was reduced to 35% of the original value. Low reagents consumption and high sampling throughput were the remarkable features of the SIA system.     

EIS multianalyte sensing with an automated SIA system—An electronic tongue employing the impedimetric signal

In this work, the simultaneous quantification of three alkaline ions (potassium, sodium and ammonium) from a single impedance spectrum is presented. For this purpose, a generic ionophore - dibenzo-18-crown-6 - was used as a recognition element, entrapped into a polymeric matrix of polypyrrole generated by electropolymerization. Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data, respectively. In fact, EIS detected the ions exchanged between the medium and the sensing layer whereas ANNs, after an appropriated training process, could turn the impedance spectrum into concentrations values. A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN. Best results were obtained by using a backpropagation neural network made up by two hidden layers: the first one contained three neurons with the radbas transfer function and the second one ten neurons with the tansig transfer function. Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix. The experimental results were compared with reference methods.     

Two analyte calibrations from the transient response of a single potentiometric sensor employed with the SIA technique

Simultaneous quantification of Cd²⁺ and Pb²⁺ in solution has been correctly targeted using the kinetic information from a single non-specific potentiometric sensor. Dual quantification was accomplished from the complex information in the transient response of an electrode used in a Sequential Injection Analysis (SIA) system and recorded after step injection of sample. Data was firstly preprocessed with the Discrete Wavelet Transform (DWT) to extract significant features and then fed into an Artificial Neural Network (ANN) for building the calibration model. DWT stage was optimized regarding the wavelet function and decomposition level, while the ANN stage was optimized on its structure. To simultaneously corroborate the effectiveness of the approach, two different potentiometric sensors were used as study case, one using a glass selective to Cd²⁺ and another a PVC membrane selective to Pb²⁺.     

SIA system employing the transient response from a potentiometric sensor array—Correction of a saline matrix effect

A Sequential Injection Analysis (SIA) system and an 8-potentiometric all-solid-state sensor array were coupled in a simple and automated electronic tongue device. The potentiometric sensors used were planar microfabricated structures with standard PVC membranes deposited onto a gold contact. The SIA system permitted the automated operation and generation of the calibration data, needed to build an Artificial Neural Network model, thanks to the precise dosing and mixing of volumes of stock solutions. The resolution of a four-ion mixture, i.e. ammonium, sodium, nitrate and chloride was the study case used for characterization of the system. Two different variants for signal acquisition, steady-state and transient recording, were arranged and compared. The dynamic treatment is shown to offer improved performance thanks to the benefits of the kinetic resolution. For this, it first extracts meaningful data from a FFT transform of each sensor's transient, which is then fed to an ANN model for estimation of each concentration in the four-ion mixture. While in a standard laboratory situation there was no difference between the two approaches, the dynamic treatment allowed the correction of a matrix effect in the case study, where an uncontrolled saline effect could be counterbalanced.     

The effect of hydrophobic-lipophilic interactions on chemical reactivity. 9. Putting the spotlight on lipophilic forces in solvent-effect studies

The hydrolytic rate constants of thep-nitrophenyl esters of acetic, octanoic, dodecanoic and hexadecanoic acids in six aquiorgano binary mixtures of graded compositions at various initial substrate concentrations were measured and discussed in terms of the hydrophobic-lipophilic interactions between the substrate molecules, and the organic cosolvents which were MeOH, Me₂SO, 1, 4-dioxane, 1,2-dimethoxyethane,n-propanol andt-butanol. The accelerating or retarding effects of the organic cosolvents on the rate constants of hydrolysis were found to be directly related to the lipophilicities of the solvents which were changed either by changing the content (ϕ) or the nature of the organic cosolvent. The classification or ordering of the six solvents on the basis of their solvent effects were found to conform to the lipophilicity order derived from Rekker's Σf values. The results support the proposition that lipophilic interactions can play an important role in solvent effects of aqueous binaries.     

Automated SIA System Using an Array of Potentiometric Sensors for Determining Alkaline‐Earth Ions in Water

This work deals with the simultaneous determination of Mg²⁺, Ca²⁺, and Ba²⁺ in water using a PVC‐membrane potentiometric sensor array and multivariate calibration, in what is known as electronic tongue. The subsequent processing of the data was based on the use of a multilayer artificial neural network (ANN). The information needed for training or generation of the model was obtained with the aid of an automated analytical system based on the Sequential Injection Analysis (SIA) technique. The modeling ability was verified with an external set of standards, and next the determinations were performed in real samples of mineral waters, where close results for Mg²⁺ and Ca²⁺ were obtained to those obtained with reference methods. The determination of Ba²⁺ can be considered as semi‐quantitative for synthetic samples – due to the absence of Ba²⁺ in mineral waters, its concentration in real samples was not measured.     

Quantitative Analysis of Active Pharmaceutical Ingredients (APIs) Using a Potentiometric Electronic Tongue in a SIA Flow System

An advanced potentiometric electronic tongue and Sequential Injection Analysis (SIA) measurement system was applied for the quantitative analysis of mixtures containing three active pharmaceutical ingredients (APIs): acetaminophen, ascorbic acid and acetylsalicylic acid, in the presence of various amounts of caffeine as interferent. The flow‐through sensor array was composed of miniaturized classical ion‐selective electrodes based on plasticized PVC membranes containing only ion exchangers. Partial Least Squares (PLS) analysis of the steady‐state sensor array responses, measured in API mixtures prepared by the SIA system permitted a correct quantitative analysis of acetylsalicylic acid and ascorbic acid. Further optimization using multiway PLS fed by dynamic responses without additional feature extraction did not improve significantly the resolution of acetaminophen. Lastly, the chemometric treatment, involving the extraction of dynamic components of the transient response employing the Wavelet transform, the removal of less‐significant coefficients by means of Causal Index pruning and training of an Artificial Neural Network (ANN) with the selected coefficients, allowed the simultaneous determination of all the three studied APIs, while counterbalancing any interference due to caffeine.     

Discovery of novel regulatory peptides by reverse pharmacology: spotlight on chemerin and the RF-amide peptides metastin and QRFP

Reverse pharmacology is a screening technology that matches G protein-coupled receptors (GPCRs) with unknown cognate ligands in cell-based screening assays by detection of agonist-induced signaling pathways. One decade spent pursuing orphan GPCR screening by this technique assigned over 30 ligand/receptor pairs and revealed previously known or novel undescribed ligands, mostly of a peptidic nature. In this review, we describe the discovery, characterization of the structural composition, biological function, physiological role and therapeutic potential of three recently identified peptidic ligands. These are metastin, QRFP in a context of five RF-amide genes described in humans and the chemoattractant, chemerin. Metastin was initially characterized as a metastasis inhibitor. Investigations using ligand/receptor pairing revealed that metastin was involved in a variety of physiological processes, including endocrine function during pregnancy and gonad development. The novel RF-amide QRFP is implicated in food intake and aldosterone release from the adrenal cortex in the rat. Chemerin, first described as TIG2, is upregulated in tazarotene-treated psoriatic skin. By GPCR screening, bioactive chemerin was isolated from ovarial carcinoma fluid as well as hemofiltrate. Characterization as a chemoattractant for immature dendritic cells and analysis of the expression profile of metastin and its receptor suggested a physiological role of chemerin as a mediator of the immune response, inflammatory processes and bone development.     

Automated SIA e‐Tongue Employing a Voltammetric Biosensor Array for the Simultaneous Determination of Glucose and Ascorbic Acid

An automated voltammetric electronic tongue has been designed employing a biosensor array formed by three different enzymatic Glucose Oxidase (GOD) electrodes and the Sequential Injection Analysis principle. The system is used for its automated training and operation devised for determining glucose and one of its classical interferents, ascorbic acid. The three enzymatic biosensors contain GOD and different metallic catalysts in order to decrease the working potential and to differentiate the response of primary species and interferents. Linear sweep voltammetry has been the chosen technique for data generation and artificial neural networks have been used as the modeling tool. Different learning algorithms have been tried in order to obtaining the best architecture for the neural network. Glucose has been determined in different fruit juice samples by employing this system, correcting the ascorbic acid contents.