The interpretation and use of stability data in the certification of reference materials

 Stability tests are carried out on candidate reference materials in order to ascertain that the certification values continue to be valid a reasonable time after completion of the certification analysis. These tests are also used for recommending storage conditions, as well as the duration of storage before certification values need be rechecked. BCR (Community Bureau of Reference) reference materials do not normally have an expiry date, but rely on stability monitoring throughout the lifetime of the certified material. The 1997 version of the BCR Guidelines for the production and certification of reference materials does, however, take into account the necessity of limiting the validity of a certification, when degradation of the material during storage cannot be ignored. This paper discusses an example of significant degradation taking place between the time of completion of the certification analysis and the issue of a formal certificate. Various options are presented together with an account of their influence on the certified values and their uncertainties. Received: 3 October 1997 · Accepted: 3 November 1997     

The Development of a Green Innovative Bioactive Film for Industrial Application as a New Emerging Technology to Protect the Quality of Fruits

Today, the most significant challenge encountered by food manufacturers is degradation in the food quality during storage, which is countered by expensive packing, which causes enormous monetary and environmental costs. Edible packaging is a potential alternative for protecting food quality and improving shelf life by delaying microbial growth and providing moisture and gas barrier properties. For the first time, the current article reports the preparation of the new films from Ditriterpenoids and Secomeliacins isolated from Melia azedarach (Dharek) Azadirachta indica plants to protect the quality of fruits. After evaluating these films, their mechanical, specific respirational, coating crystal elongation, elastic, water vapor transmission rate (WVTR), film thickness, and nanoindentation test properties are applied to apple fruit for several storage periods: 0, 3, 6, 9 days. The fruits were evaluated for postharvest quality by screening several essential phytochemical, physiological responses under film coating and storage conditions. It was observed that prepared films were highly active during storage periods. Coated fruits showed improved quality due to the protection of the film, which lowered the transmission rate and enhanced the diffusion rate, followed by an increase in the shelf life. The coating crystals were higher in Film-5 and lower activity in untreated films. It was observed that the application of films through dipping was a simple technique at a laboratory scale, whereas extrusion and spraying were preferred on a commercial scale. The phytochemicals screening of treated fruits during the storage period showed that a maximum of eight important bioactive compounds were present in fruits after the treatment of films. It was resolved that new active films (1–5) were helpful in the effective maintenance of fruit quality and all essential compounds during storage periods. It was concluded that these films could be helpful for fruits growers and the processing industry to maintain fruit quality during the storage period as a new emerging technology.     

Long-term stability of hydrocarbons in NIST gas standard reference material (SRM) 1800

A gas standard reference material (SRM) containing fifteen hydrocarbons in nitrogen at a nominal 5 nmol mol(-1) was issued in 1993. The certification period for SRM 1800 was assigned as 2 years, because of limited stability data. Over a period of 10 years reanalysis of the lot standard (a sample chosen from the SRM lot to which all other lot samples are compared), SRM samples remaining in stock for sale, and SRMs returned to the National Institute of Standards and Technology (NIST) for recertification, were compared with primary standards to assess the stability of the hydrocarbons. New primary standards were periodically introduced into the original primary standard suite to assess the stability and consistency of the primary standards. Over this ten-year period 11 SRM 1800 samples were reanalyzed, resulting in 210 amount-of-substance fraction (concentration) determinations performed for quality-assurance purposes. Of these measurements 209 (99.5%) agreed within the original 95% confidence interval of the +/-4% expanded uncertainty, demonstrating the stability of the standards. There was also agreement to within +/-2% of the original concentration for 204 (97%) of the measurements. This is well within the original +/-4% expanded uncertainty assigned to the hydrocarbon concentrations at the approximate 95% confidence interval demonstrating stability. These results will enable the expiry date to be increased for future restock issues of SRM 1800.     

Long-term stability study of drug products and out-of-specification test results

A metrological approach for investigating out-of-specification (OOS) test results in long-term stability study of drug products was used. It is shown that OOS test results can indicate an actual change in a measured property of a product or be metrologically related with a certain confidence probability, i.e., be caused by the measurement problems, while the product still meets the quality requirements at the time of testing. As examples, results of testing sodium chloride injections in 500-mL plastic containers and of epinephrine (l-adrenaline) injections in 1-mL ampoules were discussed. Regression analysis of the data was performed, as well as warning and action lines for shelf life of the products calculated for relevant measurement uncertainties and confidence probabilities. Producer’s and consumer’s risks of the established shelf life values were also estimated.     

A technology for manufacturing tapes and pastes of powder solders on organic binders

The results of the development of new domestic semifinished products of nondeformable solders, such as tapes and pastes of solders on an organic binder, are presented. It was shown that the use of a copolymer of BMK-5 acrylic resin as a binder for semifinished products in the form of a tape; and the MBM-5S acrylic dispersion, in the form of pastes, is optimum for meeting such requirements as absence of ash residue during high-temperature heating in vacuum, manufacturability, and shelf life.     

Stabilization Studies on Bacterially Produced Human Paraoxonase 1 for Improving Its Shelf Life

Human paraoxonase 1 (h-PON1) is a ~40 kDa multi-tasking enzyme that plays a major role in determining individual susceptibility towards various disease conditions. It is a strong candidate for the development of therapeutic intervention for various diseases and other conditions in humans. However, purified h-PON1 is unstable and there is a need to find condition(s) that can increase the shelf life of the enzyme. In this report, we present the results of our investigation on the effect of excipients on the stability of bacterially produced human PON1 when stored under different storage conditions. Our results show that (a) glycine and serine are most effective in stabilizing the enzyme when stored in aqueous buffer at 25 °C for 30 days, and (b) trehalose, maltose, and BSA exerted maximum stabilization effect when the enzyme was stored in freeze-dried form at 25 °C for 60 days. Results of this study can be used to increase the shelf life of purified h-PON1 enzyme.     

Stability testing in an integrated scheme

ISO Guide 35 deals with RM stability issues and scrutinizes the evaluation of stability testing results under the assumption that either there is no trend at all (a rather rare situation), or any observed deterministic change is insignificant and thus can be neglected. However, market demands for reliable reference materials are obviously not limited to stable or at least seemingly stable materials. In many analytical applications, analytes and measurands under consideration are known, or at least suspected, to be unstable on time scales that may vary widely from measurand to measurand. The Federal Institute for Materials Research and Testing (BAM) has developed (and successfully uses) an integrated approach in its certification practice. The approach is based on an initial stability study and subsequent post-certification monitoring. Data evaluation is model-based and takes advantage of all information collected in the stability testing scheme(s). It thus allows one to deal with any kind of instability observed, to assess limiting time intervals at any stress condition in the range tested, to estimate a final expiry date for materials with detected instabilities or the maximum admissible re-testing interval for seemingly stable materials, and to assess maximum admissible stress loads during delivery of the material to the customer. The article describes (and exemplifies) typical study layout, the model selection, and the integrated data assessment.     

GHD室温自交联乳液的聚合及贮存稳定性

采用半连续种子乳液聚合技术合成了含甲基丙烯酸缩水甘油酯(GMA)、甲基丙烯酸羟乙酯(HEMA)和甲基丙烯酸二甲氨基乙酯(DMAEMA)的室温自交联乳液(GHD).实验结果表明,在甲基丙烯酸甲酯(MMA)-丙烯酸丁酯(BA)-GMA种子乳液存在下,聚合温度升高,聚合过程稳定性下降,但乳液的贮存稳定性提高;乳化单体滴加速度加快,种子聚合物的玻璃化温度升高,可减少聚合过程的交联凝聚作用,提高聚合过程的稳定性;而HEMA和DMAEMA用量增加对聚合过程的稳定性没有明显影响,但使乳液的贮存稳定性下降.官能团间的交联凝聚作用可能是影响室温自交联乳液聚合及贮存过程稳定性的关键因素.     

Formation of Al2O3–BaTiO3 nanocomposite oxide films on etched aluminum foil by sol–gel coating and anodizing

Barium titanate BaTiO₃ (BT) sol was dip-coated on the etched aluminum foils by a sol–gel process. After annealed at 600 °C in air, the foils were anodized in ammonium adipate solution. The voltage–time variations during anodizing were monitored. The structure, composition, and electric properties of the anodic foils were investigated. The obtained foils were fabricated into aluminum electrolytic capacitors and the load and shelf life test were measured. It was found that the slope of the voltage–time curve of aluminum foil covered with BT films became steeper. A triple layer of Al/Al₂O₃/BT was formed after anodizing Al/BT foil. The specific capacitance and the product of specific capacitance and withstanding voltage of anodic foil with a BT coating were about 46.36% and 38.90% larger than that without a BT coating. After the load life and shelf life of 2500 h at 85 °C, two kinds of capacitors have similar behaviores and meet with Nichicon standard of Japan. From the results, BaTiO₃ is promising to be used as the dielectric of aluminum electrolytic capacitor to increase the specific capacitance.     

Improvements in Polysaccharides for use as Blood Plasma Expanders

Modern blood plasma volume expanders consist of water-soluble polysaccharides that are compatible with the human body. They are more effective for the treatment of intravasal volume deficiency compared to synthetic polymers. These colloidal blood plasma volume expanders, for example pullulan, dextran or hydroxyethyl starch (HES) are used in blood isotonic electrolyte solutions. HES has the lowest tendency to remain in the liver or other organs of the human body in comparison to other expanders. The knowledge of the molar mass and coil dimensions as well as their distribution are essential, since products of low molar masses do not have the desired effect and parts of large molar masses can lead to an anaphylactic shock. Injection of HES enhances the microcirculation and leads to a better oxygen transport into the tissue and the muscle. Because of this, HES was identified as a doping agent in 02/2002. In addition to this it will be shown that starch acetates have an even better physiological compatibility and are an interesting alternative to HES. We will present investigations on the shelf life of a new acetyl starch, which may be an alternative to the blood plasma expanders used to date.     

Food processors requirements met by radiation processing

Processing food using irradiation provides significant advantages to food producers by destroying harmful pathogens and extending shelf life without any detectable physical or chemical changes. It is expected that through increased public education, food irradiation will emerge as a viable commercial industry. Food production in most countries involves state of the art manufacturing, packaging, labeling, and shipping techniques that provides maximum efficiency and profit. In the United States, food sales are extremely competitive and profit margins small. Most food producers have heavily invested in equipment and are hesitant to modify their equipment. Meat and poultry producers in particular utilize sophisticated production machinery that processes enormous volumes of product on a continuous basis. It is incumbent on the food irradiation equipment suppliers to develop equipment that can easily merge with existing processes without requiring major changes to either the final food product or the process utilized to produce that product. Before a food producer can include irradiation as part of their food production process, they must be certain the available equipment meets their needs. This paper will examine several major requirements of food processors that will most likely have to be provided by the supplier of the irradiation equipment.     

Fatigue testing of condoms

Tests currently used for condoms are surrogates for the challenges they face in use. The tests involve looking for holes and slow stretching to break. This article describes a test that adds cyclic strain to a level well below breakage, and examines the differences among brands and types of condom. It is shown that there are very significant differences in resistance to cyclic straining. Such a test could be developed into a standard test for condom acceptability.     

Production and certification of “fresh” reference material for macronutrient analysis

Summary Reference materials for carrying out in-house quality assurance by food laboratories that analyse macronutrients have to date been inadequate. The freeze-dried, very specialized, materials that exist on the market are not always comparable with ordinary food products analysed at those laboratories.A homogeneous, fresh, canned meat material was produced by an ordinary cannery. The total amount of material (pork, nitrite salt and water) was 1700 kg. During production, the fat content was continuously analysed in the different sub-batches and combinations are made accordingly. The material was packed in tin cans containing 200 g, and tested for homogeneity. The shelf life is, by experience, at least five years. A large number of authorized public and industry laboratories participated in the certification procedure. For each constituent different types of standard analytical methods were used. The material is offered for sale together with a certificate, giving mean values for moisture, ash, fat, nitrogen, sodium, sodium chloride and hydroxyproline content. The uncertainty is given as standard deviations including the analytical error and the variations between laboratories, methods and units.     

Thermal stability, texture, liquid holding capacity and colour of smoked salmon on retail level

Retail samples of vacuum-packed sliced cold smoked salmon were investigated for changes in texture, colour and expressible moisture approximately 1 week before expiry date and on the best before date. For comparison, retail samples of gravelax were also investigated. To gather information on alteration in protein caused by processing and refrigerated storage, DSC measurements were performed at the same samples and furthermore on hot smoked salmon and frozen raw material, Salmo salar. Texture parameters varied markedly between the retail samples; however, almost no clear tendencies were observable with increased refrigerated storage time while expressible moisture raised. Colour also differed considerably between the samples. Gravelax behaved almost comparable to cold smoked salmon. DSC curves taken from cold smoked salmon and gravelax were almost comparable and demonstrated that muscle proteins being largely denatured by the influence of salt and cold smoking temperature compared to the raw material.     

Comparative study of biodiesel oxidation stability using Rancimat,PetroOXY, and low P-DSC

Oxidation stability of biodiesel is one of the most important factors used to evaluate its quality, allowing its commercialization and ensuring its shelf life. In this context, several accelerated methods have been used to measure oxidative stability to predict the maximum storage time at which biodiesel can be submitted without compromising its quality. In the present study, the oxidation stability of two commercial biodiesel and of their blends with two antioxidants was evaluated using the standard methods described in the EN 14214 norm (Rancimat Method) and in ASTM D7545 (PetroOXY method), as well as by low pressurized differential scanning calorimetry (low P-DSC). Both biodiesel were obtained from soybean oil, produced by methylic and ethylic route. The antioxidants, which were used in different concentrations, have the following active components: bisphenol and phenol. The three assessed methodologies can be used to determine the effect of the commercial antioxidants on the oxidative stability of the studied biodiesel. As each method is based on the measurement of different parameters to obtain the respective oxidation induction time, their results cannot be compared directly. But when the results are expressed in terms of the percentage change of the respective oxidation induction times, there is a higher correlation between those obtained by Rancimat and PetroOXY methods than when compared with the results obtained by low P-DSC. Because of their characteristics, the bisphenolic antioxidant is more effective than the phenolic one and, at a same antioxidant concentration, the oxidation stability of the ethylic biodiesel is higher than that of the methylic one. Considering analysis time and sensitivity, the low P-DSC method is the one that better attends both parameters among the applied methods.     

Phenolic Compounds in Active Packaging and Edible Films/Coatings: Natural Bioactive Molecules and Novel Packaging Ingredients

In recent years, changing lifestyles and food consumption patterns have driven demands for high-quality, ready-to-eat food products that are fresh, clean, minimally processed, and have extended shelf lives. This demand sparked research into the creation of novel tools and ingredients for modern packaging systems. The use of phenolic-compound-based active-packaging and edible films/coatings with antimicrobial and antioxidant activities is an innovative approach that has gained widespread attention worldwide. As phenolic compounds are natural bioactive molecules that are present in a wide range of foods, such as fruits, vegetables, herbs, oils, spices, tea, chocolate, and wine, as well as agricultural waste and industrial byproducts, their utilization in the development of packaging materials can lead to improvements in the oxidative status and antimicrobial properties of food products. This paper reviews recent trends in the use of phenolic compounds as potential ingredients in food packaging, particularly for the development of phenolic compounds-based active packaging and edible films. Moreover, the applications and modes-of-action of phenolic compounds as well as their advantages, limitations, and challenges are discussed to highlight their novelty and efficacy in enhancing the quality and shelf life of food products.     

Effectiveness of Quaternary Ammonium in Reducing Microbial Load on Eggs

Table eggs are an affordable yet nutritious protein source for humans. Unfortunately, eggs are a vector for bacteria that could cause foodborne illness. This study aimed to investigate the effectiveness of a quaternary ammonium compound (quat) sanitizer against aerobic mesophilic bacteria, yeast, and mold load on the eggshell surface of free-range and commercial farms and the post-treatment effect on microbial load during storage. Total aerobic mesophilic bacteria, yeast, and molds were enumerated using plate count techniques. The efficacy of the quaternary ammonium sanitizer (quat) was tested using two levels: full factorial with two replicates for corner points, factor A (maximum: 200 ppm, minimum: 100 ppm) and factor B (maximum: 15 min, minimum: 5 min). Quat sanitizer significantly (p < 0.05) reduced approximately 4 log10 CFU/cm² of the aerobic mesophilic bacteria, 1.5 to 2.5 log10 CFU/cm² of the mold population, and 1.5 to 2 log10 CFU/cm² of the yeast population. However, there was no significant (p ≥ 0.05) response observed between individual factor levels (maximum and minimum), and two-way interaction terms were also not statistically significant (p ≥ 0.05). A low (<1 log10 CFU/cm²) aerobic mesophilic bacteria trend was observed when shell eggs were stored in a cold environment up to the production expiry date. No internal microbial load was observed; thus, it was postulated that washing with quat sanitizer discreetly (without physically damaging the eggshell) does not facilitate microbial penetration during storage at either room temperature or cold storage. Current study findings demonstrated that the quat sanitizer effectively reduced the microbial population on eggshells without promoting internal microbial growth.     

MSn,LC‐MS‐TOF and LC‐PDA studies for identification of new degradation impurities of bupropion

Three new degradation impurities of bupropion were characterized through high performance liquid chromatography coupled to photodiode array detection and to time‐of‐flight mass spectrometry. Bupropion was subjected to the ICH prescribed stress conditions. It degraded to seven impurities (I–VII) in alkaline hydrolytic conditions which were optimally resolved on an XTerra C₁₈ column (250 × 4.6 mm, 5 µm) with a ternary mobile phase comprising ammonium formate (20 mm , pH 4.0), methanol and acetonitrile (75:10:15, v/v). The degradation impurities (III–V and VII) were characterized on the basis of mass fragmentation pattern of drug, accurate mass spectral and photodiode array data of the drug and degradation impurities. Compound V was found to be a known degradation impurity [1‐hydroxy‐1‐(3‐chlorophenyl)propan‐2‐one], whereas III, IV and VII were characterized as 2‐hydroxy‐2‐(3′‐chlorophenyl)‐3,5,5‐trimethylmorpholine, (2,4,4‐trimethyl‐1,3‐oxazolidin‐2‐yl)(3‐chlorophenyl)‐methanone and 2‐(3′‐chlorophenyl)‐3,5,5‐trimethylmorphol‐2‐ene, respectively. Compound III was a known metabolite of the drug. This additional information on the degradation impurities can help in the development of a new stability‐indicating assay method to monitor the stability of the drug product during its shelf‐life as well as in development of a drug product with increased shelf‐life. Copyright © 2013 John Wiley & Sons, Ltd.     

Synthesis of Highly Stable,Water‐Dispersible Copper Nanoparticles as Catalysts for Nitrobenzene Reduction

We report an aqueous‐phase synthetic route to copper nanoparticles (CuNPs) using a copper–surfactant complex and tests of their catalytic efficiency for a simple nitrophenol reduction reaction under atmospheric conditions. Highly stable, water‐dispersed CuNPs were obtained with the aid of polyacrylic acid (PAA), but not with other dispersants like surfactants or polymethacrylic acid (PMAA). The diameter of the CuNPs could be controlled in the range of approximately 30–85 nm by modifying the ratio of the metal precursor to PAA. The catalytic reduction of p‐nitrophenol to p‐aminophenol takes place at the surface of CuNPs at room temperature and was accurately monitored by UV/Vis spectroscopy. The catalytic efficiency was found to be remarkably high for these PAA‐capped CuNPs, given the fact that at the same time PAA is efficiently preventing their oxidation as well. The activity was found to increase as the size of the CuNPs decreased. It can therefore be concluded that the synthesized CuNPs are catalytically highly efficient in spite of the presence of a protective PAA coating, which provides them with a long shelf life and thereby enhances the application potential of these CuNPs.     

Preparation and certification of a biological reference material (CARP-1) for polychlorinated dibenzo-p-dioxin and dibenzofuran congeners

A biological certified reference material for nine 2,3,7,8-chlorine substituted dibenzo-p-dioxin and dibenzofuran congeners and nine common polychlorinated biphenyl congeners is available for the first time. This material (CARP-1) is in the form of a slurry comprising approximately 9 g of carp homogenate sealed in a glass ampoule. The only foreign materials in the slurry are an antioxidant added to prevent rancidity and water to facilitate homogenization and ampouling. CARP-1 was found to be homogeneous and stable with respect to its organochlorine concentrations under room as well as elevated temperature storage conditions. The minimum projected shelf life for this material is 5 years.