Planning and combining of isochronous stability studies of CRMs

The first part of this paper discusses some critical factors in planning and evaluation of isochronous stability studies. Recommendations on the number of time-points, number of items, and number of replicates to be measured on each unit are given. In general, more than two time-points should be used. The effect of batch heterogeneity can be eliminated by spreading the results over more units. An approach for combining two or more isochronous stability studies is developed in the second part. This approach includes a potential correction of the earlier stability study, pooling of data of the stability studies, and an uncertainty evaluation taking into consideration the uncertainty of the initial correction. The statistical basis for this approach is developed and equations for evaluation of the uncertainty of stability of the combined study are given.     

pH诱导两性离子配体修饰的金溶胶的浓缩与保存

研究了两性离子配体修饰的金纳米颗粒在酸性和碱性溶液中的稳定性和可逆聚集性. 测量了金溶胶在不同条件下的UV-Vis 吸收光谱, 通过光谱的变化揭示其稳定性和可逆聚集性. 结果表明: 经配体修饰的金纳米颗粒在酸性和碱性溶液中的稳定性有了很大的提高; 强酸性条件可诱导金溶胶失稳聚沉, 回调pH值又可使其重新分散. 利用这种pH依赖的可逆聚集特性, 可以将稀溶胶浓缩成浓溶胶或固体保存, 一旦需要又可加水恢复到分散的状态.     

Electrochemical stability of polyaniline

The kinetics of the electrochemical degradation of polyaniline (PANI) films has been investigated in 0.5 M sulfuric acid solution at different electrode potentials ranging from 0.3 to 1.0 V vs. Ag/AgCl. Two kinds of PANI films were used, one doped with poly(styrene sulfonate) (PSS), and the other—with indigotetrasulfonate (ITS). Within a range of relatively low electrode potential (0.3-0.6 V), the degradation was found to proceed at a first-order rate constant of 4×10⁻⁵ to 5×10⁻⁵ s⁻¹, corresponding to degradation half-period of 4-5 h. A sharp increase in the degradation rate proceed by extending the electrode potential to higher values, with a maximum rate constant of ≈2.5×10⁻³ s⁻¹ for PANI-PSS, and ≈1.2×10⁻³ s⁻¹ for PANI-ITS films, obtained at a higher potential of 0.9-1.0 V. The data obtained are interpreted by different degradation rate for two distinct redox forms of PANI—emeraldine (slow degradation), and pernigraniline (fast degradation).     

Preservation of arsenic species in water samples using phosphoric acid--limitations and long-term stability

The preservation of arsenic species in water samples is an indispensable method to avoid their changes during storage, if it is not possible to analyse them immediately. The aim of this investigation was to demonstrate the limitations of the suggested method by using phosphoric acid as a preservation agent. The samples remain stable for 3 months, even if they show evidence of high concentrations of iron or manganese. Critical is an increasing pH > 3. Theoretically, a precipitation of strengite (Fe₃(PO₄)₂) could occur, which should be avoided. Phosphoric acid with a final concentration of 10 mM is recommended as a preservation agent, combined with keeping the samples cool (6 °C) and dark. Filtration of samples before preservation may be carried out with respect to the analytical aim to distinguish between the total and soluble fraction (without colloids). It was shown that filtered and non-filtered samples can be preserved by utilising the above mentioned scheme.     

Conclusions from 13 years of stability testing of CRMs for determination of metal species

We present results of the systematic stability monitoring of certified reference materials (CRMs) for the mass fractions of metal species. Materials are tested regularly for the mass fractions of organotin, organomercury, organolead and organoarsenic species. Evaluation is based on ratios of results on samples stored under normal conditions and under even safer conditions (“reference stock”) to eliminate the effects of laboratory-to-laboratory variation. Of all results in this study, the results of organotin measurements show the highest relative standard deviations (up to 45%). Determination of methylmercury in sediment and fish is possible with much better precision (standard deviations of reproducibility below 5%). The accuracies of determinations of trimethyllead and organoarsenic species are slightly worse but still below 10%. The data confirmed stability since production (i.e. up to 13 years). However, shelf lives cannot be extended into the future based on these data, as uncertainty contributions for stability need to be included in the uncertainty budgets of CRMs to allow positive demonstration of the validity of certificates. Estimation of typical measurement uncertainties based on the data obtained from stability monitoring shows that potential degradation is negligible compared to uncertainties typical for this kind of measurement, demonstrating that the materials are still sufficiently reliable to demonstrate laboratory proficiency.     

Optical monitoring the degradation of PLGA inverse opal film

Implantable materials have broad applications in tissue engineering and in vivo sensors.It is essential to know the detailed information of the implantable materials during their degradation.In this paper,we developed a method to monitor the degradation process of a well-used biomaterial,poly(lactide-coglycolide) (PLGA) by taking advantage of inverse opal structure.We found that mass loss,molecular weight and glass transition temperature of PLGA during the degradation process in Hank’s artificial body fluid can be in situ monitored by measuring the optical properties of PLGA inverse opal.     

Limitations of aqueous model systems in the stability assessment of electrocatalysts for oxygen reactions in fuel cell and electrolyzers

Cost and stability remain the greatest technical barriers to sustainably commercialize low-temperature fuel cells and electrolyzers. For tackling this problem, numerous advanced electrocatalysts have been proposed and tested in aqueous model systems. There are, however, increasing and evident concerns regarding the value of stability data coming from such studies. Hence, we anticipate that finding new approaches to assess degradation will be a major undertaking in electrocatalysis research in the next years. Specifically, existing differences between fundamental and actual systems have to be addressed first: (a) electrode architecture; (b) electrolyte; (c) reactant and product transport; and (d) operating conditions. In this perspective, we discuss their influence on the stability of electrocatalysts using the challenging oxygen reduction and oxygen evolution reactions as illustrative cases.     

Perovskite solar cells: Thermal and chemical stability improvement,and economic analysis

Perovskite solar cells (PSCs) are highly efficient and are comparatively cheaper than the large silicon crystals primarily used in solar cells. Their outstanding photovoltaic performance makes them a potential alternative to silicon solar cells. While efficiency and photovoltaic performance have been investigated in recent decades, a knowledge gap on the degradation, economic feasibility and stability of PSCs exists, and their poor stability remains a barrier to commercialization. Thus, this review aims to fill this knowledge gap by focusing on approaches to improve PSCs’ thermal and chemical stability, and their economic viability under different conditions. The structure and manufacture of PSCs are also discussed along with an economic analysis of different perovskite devices. Improvements in thermal stability can be reached by incorporating inorganic materials into the PSC. A PSC model optimized with ZnO improves chemical stability by 8% and works well under low temperatures. To make PSCs more economically feasible, certain parts like counter electrodes (CE) and hole transport materials (HTMs) can be replaced with alternative elements like carbon and inorganic HTMs, respectively. PSCs with long durability and high conversion efficiency will expand the commercial prospects for this material. To bridge the lack of knowledge, further investigation is required on the sustainability and longevity of PSCs.     

Highly efficient photocatalytic degradation for antibiotics and mechanism insight for Bi2S3/g-C3N4 with fast interfacial charges transfer and excellent stability

Bi₂S₃/g-C₃N₄ (BSCN) samples with different mass ratios of CN to BS were prepared by a facile and practicable hydrothermal method with 2D g-C₃N₄ nanosheets (CN). The microscopic morphology and structure of pure CN, BS and BSCN were measured by multiple testing methods. Analysis results show that the BSCN was prepared successfully, and the Bi₂S₃ nanoparticles closely and uniformly adhered to the surface of CN with sheet-like structure. The introduction of Bi₂S₃ did not change the structure of the CN. The results of the ultraviolet–visible spectroscopic analysis, photoluminescence spectra and electrochemical performance indicated that BSCN showed superior visible-light response compared with CN, and the separation and transfer efficiency of photogenerated carriers was significantly improved. With the decrease of mass ratio of CN/BS, the photocatalytic activity of BSCN initially increased and then decreased for 20 ppm of Rhodamine B solution (RhB), and the Bi₂S₃/g-C₃N₄-B with a mass ratio of 8:1 for CN to BS showed optimal photocatalytic performance (98.98%). Furthermore, the Bi₂S₃/g-C₃N₄-B exhibited apparent degradation effects (1.021 x10^-2, 0.879 x10^-2 and 0.793 x10^-2 min^?1) to three kinds of antibiotics (tetracycline, ciprofloxacin, and oxytetracycline). The BSCN samples still maintained higher degradation efficiency after five cycles of degradation to tetracycline. The capture experiments and the electron spin resonance (ESR) spectra analysis indicated that the h⁺ and ·O₂^? played a major role, and ·OH played secondary role during the photocatalytic reaction.     

羧甲基壳聚糖在果蔬保鲜中的应用研究进展

综述了羧甲基壳聚糖的特性及其在果蔬的涂膜保鲜中的应用研究进展,讨论了羧甲基壳聚糖的浓度、分子量、pH值、取代度对其特性的影响,介绍了羧甲基壳聚糖对果蔬的涂膜保鲜效果。本文对开发羧甲基壳聚糖在果蔬防腐保鲜方面的应用具有理论指导意义。     

Electrochemical stability and transformations of fluorinated poly(2,6-dimethyl-1,4-phenylene oxide)

Fluorination of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) leads to narrowing of its window of electrochemical stability in a cathodic range of potentials. It is found this is connected with appearance of both perfluorinated and incompletely fluorinated units in the polymer. The former units are liable to electrochemical reduction (at potentials <−2.0 V) followed by elimination of fluorine anions and the latter react with basic products (generated at potentials <−1.8 V) of electrochemical reduction of the background solution. In the both cases this results in appearance of conjugated multiple bonds in the fluorinated macromolecules. Quantities of these units in fluorinated PPO were determined with a help of direct and indirect electrochemical reductive degradation techniques.     

An Assessment of Sample Preservation Methods for the Determination of Stable Carbon and Nitrogen Isotope Ratios in Mollusks

The aim of this study was to quantify the effects of preservation methods and preservation times on the stable carbon and nitrogen isotope values in the tissues of six mollusk species (Mytilus edulis, Crassostrea gigas, Ruditapes philippinarum, Acanthochiton seulschnochilon, Littorina brevicula, and Rapana venosa). To identify potential preservation effects on δ¹³C and δ¹⁵N values and to examine temporal changes in the effects of preservation, repeated analyses were carried out after 1 day, 5 days, 15 days, 1 month, 3 months, 6 months, and 12 months of preservation. The results showed that drying preservation was the most suitable method for preserving samples, while freezing and chemical preservation significantly affected the stable isotope values compared with those of the controls. The effects of preservatives on the tissues of different mollusk species were statistically significant for both δ¹³C and δ¹⁵N values. Shifts in the δ¹³C and δ¹⁵N values, due to freezing and chemical preservation, were higher in Acanthochiton seulschnochilon, Littorina brevicula, and Rapana venosa than in the other three species. The effects of preservatives on carbon isotope values were variable. In most cases, the shift of the δ¹³C values from the control samples were less than 1% for those of the treated samples. The δ¹³C and δ¹⁵N data from the preserved samples could thus be used in food web reconstruction studies. Further studies will be necessary, however, in order to elucidate the effects of preservation type and time on other species.     

Geometry,stability and aromaticity of β-diketiminate-coordinated alkaline-earth compounds

The nucleus-independent chemical shifts (NICS), anisotropy of the induced current density (AICD), and molecular orbital (MO) analyses demonstrated the non-aromaticity of the β-diketiminate-coordinated Ae compounds. The DFT calculations revealed relatively high isomerization energies (ISE) for β-diketiminatecoordinated Ae compounds, which contribute to their stability.     

Application of the ANOVA-PCA method to stability studies of reference materials

Near infrared spectroscopy (NIRS) is an analytical technique that can be very useful for stability studies in particular because of its non destructive analytical capability. However, the spectral interpretation and treatment of this kind of multivariate data remains difficult without the use of chemometrics. In this article, a recent chemometrics method, analysis of variance - principal component analysis (ANOVA-PCA), was used for NIRS stability studies of sunflower and bread wheat external reference materials (ERM). It provided a practical tool for the study of the significance of various storage conditions according to an experimental design. Thus, the effect of the temperature, the nature of the atmosphere in the packaging and the storage duration were tested. ANOVA-PCA highlighted the influence of temperature and storage duration on the stability of the sunflower materials. For the bread wheat materials, the storage conditions did not have a significant effect on stability. Consequently, by applying ANOVA-PCA to near infrared spectral data, the sunflower materials were found to be considered stable for the time length of the study, i.e. 18 months stored in a cold room, while the bread wheat materials were found to be considered stable for the time length of the study, i.e. 12 months under the same conditions.     

Preservation and stability of inorganic selenium compounds at ppb levels in water samples

The stability of inorganic selenium(IV) and selenium(VI) species at levels of 1 and 10μg l^-1 has been studied under various conditions of pH, type of water and type of container. Polyethylene containers and adjustment to pH 1.5 provide optimum conditions of preservation for both distilled and natural water samples up to 125 days. Algal growth is detrimental to solution stability at natural pH values of 5.4–7.2, but adjustment to pH 1.5 with sulfuric acid successfully avoids this effect. Container size and temperature are also discussed. Storage of samples at 4°C gives satisfactory stability but is less practicable. The essential nature of preservation techniques applicable to interlaboratory quality control studies is emphasized.     

Stressed Kinetics of Nanoemulsion Formulation Encapsulated Ropinirole with a Validated Ultra High Performance Liquid Chromatography–Synapt Mass Spectrometry (UPLC‐MS/MS ESI‐Q‐TOF)

A highly sensitive ultra high pressure liquid chromatography (UHPLC‐MSMS) method for estimation of ropinirole in rat brain homogenate and plasma has been validated. The method was successfully used for the degradation kinetics in different stress condition and regulated temperature. The chromatographic separation was achieved using isocratic mobile phase, consisting of acetonitrile–2mM ammoniumacetate (28:72 v/v; 0.25 mL min^?1). The mass spectrometer was operated in synapt mass spectrometry mode via positive electrospray ionization using the transitions m/z 260 → m/z 261 for ropinirole, and m/z 324.39 → m/z 262.161 as a parent ion of escitalopram (IS). The assay for ropinirole was linear over the range of 0.5–100 ng mL^?1 (r²; 0.999). The intra‐ and inter day precisions were less than 11.2% in terms of relative standard deviation (R.S.D.), and the accuracy was within ±6.4% in terms of relative error (RE). The mean extraction‐efficiency of QC samples (MQC, 8 ng/mL) was ≥80%. The lower limit of quantification (LLOQ) was 0.049 ng/mL where as lower limit of detection (LLOD) was 0.016 ng/mL. All the peaks of degradation were well resolved. The degradation kinetics of ropinirole, showed highest stability (t_1/2 256.66/h; t_0.9, 39.11/h) in acidic medium, lower stability in alkaline environment (t_1/2, 103.43/h; t_0.9, 15.76/h) and highly susceptible in oxidative environment (t_1/2, 21.58/h; t_0.9, 3.28/h). The applicability of this assay was demonstrated and successfully applied for pharmacokinetic profiling of ropinirole in Wister rat brain homogenate after intranasal administration.     

Development and validation of a reversed phase HPLC method for quantitative analysis of bis-isoxazolylnaphthoquinone

The goal of this study was to determine the kinetic parameters involved in the decomposition of 2-(5-methyl-4-isoxazolylamino)-N-(5-methyl-4-isoxazolyl)-1,4-naphthoquinone-4-imine (1) in aqueous solution and to identify the main degradation products. An isocratic HPLC assay was used to study the degradation rate of 1. The products of hydrolysis were identified by comparison of their retention times with those of authentic samples. The amount of 1 and the two degradation products resulting from storage of 1 in various buffer solutions was followed in function of time by a reversed-phase HPLC stability-indicating method. The observed degradation rates followed pseudo-first-order kinetics at constant pH, temperature and ionic strength. The log k–pH-profile was constructed at 35°C from the first-order rate constants obtained from studies at pH values ranging from 0.88 to 10.80 (μ=0.5 M). Hydrolysis in the acidic and alkaline media resulted in the formation of two degradation products in each case. The pH-rate profile of 1 in buffer solution was adequately described using a four-term rate equation. The obtained pH-rate profile indicated specific acid–base catalysis with a region of maximum stability between pH 6.40 and 7.40 which can be adequate for formulations of 1.     

Bioinspired design of highly sensitive flexible tactile sensors for wearable healthcare monitoring

The design of microscale architectures integrated with low-dimensional nanomaterials for tactile sensors has attracted considerable attention owing to their high performance for various potential applications, especially in the field of healthcare monitoring. However, there still remains a critical challenge to achieve high sensitivity in response to different magnitude external pressure. Herein, we introduce a high performance capacitive tactile sensor based on Silver nanowires coated biomimetic hierarchical array architecture, which consists of mini-domes by the way of vacuum adsorption from through-hole arrays and micro-cones by duplicating Calathea zebrina leaf, respectively. This hybrid graded microstructure as electrode exhibits remarkably improved sensitivity and stimulus responding range when compared with the other monotonous counterparts. Moreover, an optimized ionic gel film with remarkable interfacial capacitance is sandwiched by microstructured electrodes as the dielectric layer, further boosting the performance of the tactile sensor. As a result, the obtained sensor demonstrates a board detection range from 24 Pa to 90 kPa with a maximum sensitivity of 37.8 kPa^?1, and a fast response time (<78 ms). These superior performances of our tactile sensor lay a foundation for various applications in healthcare monitoring. It can not only sense and distinguish subtle arterial pulse signals even under different ages, genders and states of motion but also monitor physiological activity with large pressure as well, such as breathing, plantar pressure, and so on. We envision this bionic tactile sensor holds great potential in wearable electronics.     

Stability indicating high-performance thin-layer chromatographic determination of nelfinavir mesylate as bulk drug and in pharmaceutical dosage form

A sensitive, selective, precise and stability indicating high-performance thin-layer chromatographic method of analysis of nelfinavir mesylate both as a bulk drug and in formulations was developed and validated. The method employed TLC aluminium plates precoated with silica gel 60F-254 as the stationary phase. The solvent system consisted of toluene-methanol-acetone (7:1.5:1.5, v/v/v). This system was found to give compact spots for nelfinavir mesylate (R_f value of 0.45±0.02). Nelfinavir mesylate was subjected to acid and alkali hydrolysis, oxidation, dry heat treatment and photodegradation. Also the peaks of degraded products were well resolved from the pure drug with significantly different R_f values. Densitometric analysis of nelfinavir mesylate was carried out in the absorbance mode at 250 nm. The linear regression analysis data for the calibration plots showed good linear relationship with r²=0.999±0.002 in the concentration range of 1000-6000 ng per spot. The mean value of correlation coefficient, slope and intercept were 0.999±0.002, 0.014±0.001 and 21.73±1.26, respectively. The method was validated for precision, robustness and recovery. The limits of detection and quantitation were 60 and 140 ng per spot, respectively. Statistical analysis proves that the method is repeatable and selective for the estimation of the said drug. As the method could effectively separate the drug from its degradation products, it can be employed as a stability indicating one.     

Controlled PEGylation of periodic mesoporous organosilica nanospheres for improving their stability in physiological solutions

Thioether-bridged PMO nanospheres are synthesized and modified with different molecular weighted polyethylene glycol (PEG) via click reaction for the irst time. This work provides important method and knowledge to guide the modification of PMO for biomedical applications.