Field assessment of active ingredient quantity in pharmaceutical tablets with limited calibration of near infrared spectra: An application to ciprofloxacin tablets.

Portable near-infrared (NIR) spectrophotometers have emerged as valuable tools for identifying substandard and falsified pharmaceuticals (SFPs). Integration of these devices with chemometric and machine learning models enhances their ability to provide quantitative chemical insights. However, different NIR spectrophotometer models vary in resolution, sensitivity, and responses to environmental factors such as temperature and humidity, necessitating instrument-specific libraries that hinder the wider adoption of NIR technology. This study addresses these challenges and seeks to establish a robust approach to promote the use of NIR technology in post-market pharmaceutical analysis. We developed support vector machine and partial least squares regression models based on binary mixtures of lab-made ciprofloxacin and microcrystalline cellulose, then applied the models to ciprofloxacin dosage forms that were assayed with high performance liquid chromatography (HPLC). A receiver operating characteristic (ROC) analysis was performed to set spectrophotometer independent NIR metrics to evaluate ciprofloxacin dosage forms as "meets standard," "needs HPLC assay," or "fails standard." Over 200 ciprofloxacin tablets representing 50 different brands were evaluated using spectra acquired from three types of NIR spectrophotometer with 85% of the prediction agreeing with HPLC testing. This study shows that non-brand-specific predictive models can be applied across multiple spectrophotometers for rapid screening of the conformity of pharmaceutical active ingredients to regulatory standard.

Agave: a natural renewable resource with multiple applications.

Agaves are a group of succulent plants that thrive in arid or semiarid environments. Indeed, genes associated with their resilience are a potential resource for genetic engineering of other agronomically important crops grown in adverse climates. Agave is mainly used for the production of distilled (spirits) and non-distilled alcoholic beverages, including tequila, mezcal, bacanora, raicilla, and pulque, all of which have special connections to Mexican history and culture, and contribute to the Mexican economy. In recent years, there has been growing interest to maximize the use of agave plant materials for other purposes, as the bulk of their biomass pre- and post-production is wasted. In traditional practice, during the passage from fields to factories, only agave cores are used, and the leaves and bagasse are not always harnessed. To place this in perspective, during the period from 2010 to 2019, 2674.7 × 106 L of tequila was produced in Mexico, which required 9 607 400 tons of agave cores. This generated approximately the same amount of leaves and 3 842 960 tons of bagasse. The economic base of agave plants can be expanded if expended biomass could be transformed into products that are useful for applications in food, forage, ensilage, agriculture, medicine, energy, environment, textiles, cosmetics, and esthetics. This review focuses on the current utility of agave plants, as well as our perspective for future studies and uses of this formidable plant. © 2020 Society of Chemical Industry.

Applicability of Low-Cost Binders for the Quantitative Elemental Analysis of Urinary Stones Using EDXRF Based on Fundamental Parameter Approach.

The pressed powder sample is a common method for elemental analysis using X-ray fluorescence analysis whereas suitable light hydrocarbon materials should be added to the sample as a binder. The present study demonstrates the applicability of using different commercial binders for elemental analysis of urinary stone samples. In order to confirm the obtained results, a comparison with pure chemical grade binders was presented. Different commercial and pure binders were tested for quantitative elemental analysis of urinary stones, namely, cellulose, starch, wax, and urea. Energy dispersive X-ray fluorescence (EDXRF) was used for elemental analysis. Differential thermal analysis was used to estimate the loss on ignition (LOI) in the urinary stone samples. The signal to background ratios (I/IB) of the different detected elements in the commercial and pure binders were calculated, compared, and studied at eight different photon energies starting from 2.5 up to 37 keV. Standard-less quantitative analysis method based on the fundamental parameter approach was applied for elemental analysis of selected urinary stones. The commercial and low-cost binders could be an excellent alternative binder for urinary stone analysis using energy dispersive X-ray fluorescence. The commercial binders could provide an advantage as pure chemical grade binders or even better especially at photon energy higher than 10 keV. The best commercial binder candidate was found to be the wax. The quantitative analysis results using commercial and pure chemical grade binders give good agreement results, which indicate the applicability of commercial binders for quantitative elemental analysis of urinary stones in the form of pressed powder samples.

Assessment of microplastic pollution: occurrence and characterisation in Vesijärvi lake and Pikku Vesijärvi pond, Finland.

In the last few years, several studies have investigated microplastics (MPs) in marine ecosystems, but data monitoring and assessing the occurrence in freshwater environments are still scarce. The present study aims to investigate the occurrence, distribution, and chemical composition of MP pollution in Vesijärvi lake and Pikku Vesijärvi pond close to the city of Lahti (Finland) in winter. Sediment, snow, and ice core samples were collected near the shore of these two aquatic systems. MPs were analysed and identified by a non-destructive method using Fourier transform infrared spectroscopy (FTIR) 2D imaging. The mean concentrations of MPs detected in sediment, snow, and ice samples were 395.5 ± 90.7 MPs/kg, 117.1 ± 18.4 MPs/L, and 7.8 ± 1.2 MPs/L, respectively. FTIR results showed the predominant abundance of microplastics, such as polyamides (up to 53.3%), polyethylene and polypropylene (up to 17.1%), and natural fragments such as cellulose (up to 45.8%) and wool (up 18.8%) in the same size range. The potential release of MPs arising from stormwaters and sport and recreational activities was evidenced.

Experimental assessment and validation of quantification methods for cellulose content in municipal wastewater and sludge.

Cellulose, mostly in the form of toilet paper, forms a major component of the particulates in raw municipal wastewater, which could lead to significant consequences due to the potential accumulation of cellulosic fibers and slow biodegradability. Despite the sparse reports on cellulose content and degradation in wastewater and sludge, an accurate and validated method for its quantification in such matrices does not exist. In this paper, four different methods were compared including dilute acid hydrolysis, concentrated acid hydrolysis, enzymatic hydrolysis, and the Schweitzer reagent method. The Schweitzer reagent method, applied to municipal wastewater and sludge, was found to be a very robust and reliable quantification method in light of its reproducibility, accuracy, and ideal (100%) recovery. The determination of cellulose content is critical to understand its fate in wastewater treatment plants as well as improve sludge management and enhance resource recovery.

Assessment tools for microplastics and natural fibres ingested by fish in an urbanised estuary.

Microplastics and fibres occur in high concentrations along urban coastlines, but the occurrence of microplastic ingestion by fishes in these areas requires further investigation. Herein, the ingestion of debris (i.e., synthetic and natural fibres and synthetic fragments of various polymer types) by three benthic-foraging fish species Acanthopagrus australis (yellowfin bream), Mugil cephalus (sea mullet) and Gerres subfasciatus (silverbiddy) in Sydney Harbour, Australia has been quantified and chemically speciated by vibrational spectroscopy to identify the polymer type. Ingested debris were quantified using gut content analysis, and identified using attenuated total reflectance Fourier transform infrared (ATR-FTIR) and Raman microspectroscopies in combination with principal component analysis (PCA). The occurrence of debris ingestion at the time of sampling ranged from 21 to 64% for the three species, and the debris number ranged from 0.2 to 4.6 items per fish for the different species, with ∼53% of debris being microplastic. There was a significant difference in the amount of debris ingested among species; however, there was no difference among species when debris counts were standardised to fish weight or gut content weight, indicating that these species ingest a similar concentration of debris relative to their ingestion rate of other material. ATR-FTIR microspectroscopy successfully identified 72% of debris. Raman spectroscopy contributed an additional 1% of successful identification. In addition, PCA was used to non-subjectively classify the ATR-FTIR spectra resulting in the identification of an additional 9% of the debris. The most common microplastics found were polyester (PET), acrylic-polyester blend, and rayon (semi-synthetic) fibres. The potential of using Raman microspectroscopy for debris identification was investigated and provided additional information about the nature of the debris as well as the presence of specific dyes (and hence potential toxicity).

Comparative techno-economic analysis of steam explosion, dilute sulfuric acid, ammonia fiber explosion and biological pretreatments of corn stover.

Pretreatment is required to destroy recalcitrant structure of lignocelluloses and then transform into fermentable sugars. This study assessed techno-economics of steam explosion, dilute sulfuric acid, ammonia fiber explosion and biological pretreatments, and identified bottlenecks and operational targets for process improvement. Techno-economic models of these pretreatment processes for a cellulosic biorefinery of 113.5 million liters butanol per year excluding fermentation and wastewater treatment sections were developed using a modelling software-SuperPro Designer. Experimental data of the selected pretreatment processes based on corn stover were gathered from recent publications, and used for this analysis. Estimated sugar production costs ($/kg) via steam explosion, dilute sulfuric acid, ammonia fiber explosion and biological methods were 0.43, 0.42, 0.65 and 1.41, respectively. The results suggest steam explosion and sulfuric acid pretreatment methods might be good alternatives at present state of technology and other pretreatment methods require research and development efforts to be competitive with these pretreatment methods.

Flow cytometry community fingerprinting and amplicon sequencing for the assessment of landfill leachate cellulolytic bioaugmentation.

Flow cytometry (FCM) is a high throughput single cell technology that is actually becoming widely used for studying phenotypic and genotypic diversity among microbial communities. This technology is considered in this work for the assessment of a bioaugmentation treatment in order to enhance cellulolytic potential of landfill leachate. The experimental results reveal the relevant increase of leachate cellulolytic potential due to bioaugmentation. Cytometric monitoring of microbial dynamics along these assays is then realized. The flow FP package is used to establish microbial samples fingerprint from initial 2D cytometry histograms. This procedure allows highlighting microbial communities' variation along the assays. Cytometric and 16S rRNA gene sequencing fingerprinting methods are then compared. The two approaches give same evidence about microbial dynamics throughout digestion assay. There are however a lack of significant correlation between cytometric and amplicon sequencing fingerprint at genus or species level. Same phenotypical profiles of microbiota during assays matched to several 16S rRNA gene sequencing ones. Flow cytometry fingerprinting can thus be considered as a promising routine on-site method suitable for the detection of stability/variation/disturbance of complex microbial communities involved in bioprocesses.

Non-pollen particulates in honey and sugar.

A total of 19 honey samples, mostly from Germany but also from France, Italy, Spain and Mexico, were analysed for non-pollen particulates. Only coloured fibres and fragments were quantified. Transparent fibres, considered to be cellulosic because they could be stained with fuchsin, were not quantified. Coloured material was found in all the samples investigated. Fibre counts ranged from 40/kg to 660/kg of honey, with a mean value of 166 ± 147/kg of honey, whereas fragments were considerably less abundant (0-38/kg of honey; mean 9 ± 9/kg of honey). Sources are tentatively identified as environmental, that is particles having been transported by the bees into the hive, or having been introduced during honey processing or both. In addition, five commercial sugars were analysed. In all the refined samples, transparent and coloured fibres (mean 217 ± 123/kg of sugar) and fragments (32 ± 7/kg of sugar) were found. Unrefined cane sugar had 560 fibres and 540 fragments per kilogram of honey. In addition, in both honey and sugar samples, granular non-pollen material was observed.

Assessment of tree response to drought: validation of a methodology to identify and test proxies for monitoring past environmental changes in trees.

A thinning experiment stand at Avoca, Ballinvalley, on the east coast of the Republic of Ireland was used to test a developed methodology aimed at monitoring drought stress, based on the analysis of growth rings obtained by coring. The stand incorporated six plots representing three thinning regimes (light, moderate and heavy) and was planted in the spring of 1943 on a brown earth soil. Radial growth (early- and latewood) was measured for the purpose of this study. A multidisciplinary approach was used to assess historic tree response to climate: specifically, the application of statistical tools such as principal component and canonical correlation analysis to dendrochronology, stable isotopes, ring density proxy, blue reflectance and forest biometrics. Results showed that radial growth was a good proxy for monitoring changes to moisture deficit, while maximum density and blue reflectance were appropriate for assessing changes in accumulated temperature for the growing season. Rainfall also influenced radial growth changes but not significantly, and was a major factor in stable carbon and oxygen discrimination, mostly in the latewood formation phase. Stable oxygen isotope analysis was more accurate than radial growth analysis in drought detection, as it helped detect drought signals in both early- and latewood while radial growth analysis only detected the drought signal in earlywood. Many studies have shown that tree rings provide vital information for marking past climatic events. This work provides a methodology to better identify and understand how commonly measured tree proxies relate to environmental parameters, and can best be used to characterize and pinpoint drought events (variously described using parameters such as like moisture deficit, accumulated temperature, rainfall and potential evaporation).

Fast assessment of the surface distribution of API and excipients in tablets using NIR-hyperspectral imaging.

The inclusion of hyperspectral imaging systems in the manufacturing and development of pharmaceutical products is allowing a successful improvement in the quality control of solid dosage forms. The correct distribution not only of active pharmaceutical ingredient (API) but also of the rest of excipients is essential to assure the correct behavior of the tablet when ingested. This is especially relevant in tablets with low content of potent APIs, in which the prescribed intake dosage frequently corresponds to half-a-tablet. Therefore, the aim of this work is to study the surface distribution of the compounds in tablets with low API content. The proposed procedure includes the scanning of the tablet surface using near infrared hyperspectral spectroscopy in association with multivariate curve resolution (MCR) techniques to obtain selective pictures for each individual compound and to allow the fast assessment of their distribution in the measured surface. As an example, a set of commercial Lorazepam tablets (approximately 1% mass fraction of API, and four excipients) were analyzed. The results obtained show the capacity of the proposed methodology as an expedite approach to evaluate the uniformity of the contents between and within tablets. A method to estimate the homogeneity distribution of API in the two halves of the tablet is also proposed.

Assessment of the influence factors on nasal spray droplet velocity using phase-Doppler anemometry (PDA).

Droplet velocity is an important parameter that can be used to characterize nasal spray products. In this study, a phase-Doppler anemometry (PDA) system was used to measure the droplet velocities of nasal sprays. A survey of seven commercial nasal spray products showed a range of droplet velocities from 6.7 to 19.2 m/s, all significantly different from each other. A three-level, four-factor Box-Behnken design of experiments (DOE) methodology were applied to investigate the influences of actuation parameters and formulation properties on nasal spray droplet velocity using a set of placebo formulations. The DOE study shows that all four input factors (stroke length, actuation velocity, concentration of the gelling agent, and concentration of the surfactant) have significant influence on droplet velocity. An optimized quadratic model generated from the DOE results describes the inherent relationships between the input factors and droplet velocity thus providing a better understanding of the input factor influences. Overall, PDA provides a new in vitro characterization method for the evaluation of inhalation drugs through assessment of spray velocity and may assist in product development to meet drug delivery equivalency requirements.

Engineering of a high-throughput screening system to identify cellulosic biomass, pretreatments, and enzyme formulations that enhance sugar release.

The recalcitrance of cellulosic biomass, the only abundant, sustainable feedstock for making liquid fuels, is a primary obstacle to low cost biological processing, and development of more easily converted plants and more effective enzymes would be of great benefit. Because no single parameter describes recalcitrance, superior variants can only be identified by measuring sugar release from plants subjected to pretreatment and enzymatic hydrolysis. However, genetic modifications of plants coupled with molecular engineering of deconstruction proteins and definition of pretreatment conditions create a very large sample set, and previous methods for biomass pretreatment at elevated temperatures and pressures prevented use of a fully integrated high-throughput (HTP) screening pipeline. Herein, we report on the engineering of a novel HTP pretreatment system employing a 96 well-plate format that withstands extreme pretreatment conditions for rapid screening of biomass-enzyme-pretreatment combinations. This includes the development of new approaches to steam heating and water quenching the system that result in much faster heat up and cool down than previously possible and show consistent temperature histories across the multiwell plate. Coupled pretreatment and enzymatic hydrolysis performance of the well plate pretreatment system is shown to be consistent among the many wells in the device and also with performance of conventional tubular reactors.

White biotechnology for cellulose manufacturing--the HoLiR concept.

A variety of approaches are available for generation of bacteria-produced nanocellulose (BNC) in different forms. BNC production under static cultivation conditions usually results in fleeces or foils, characterized by a homogeneous, three-dimensional network of nanofibers and a uniform surface. However, under static cultivation conditions in batch vessels, the widths and the lengths of the BNC sheets cultured are determined by the dimensions of the culture vessel. In this contribution, a novel, efficient process for a (semi-)continuous cultivation of planar BNC fleeces and foils with a freely selectable length and an adjustable height is presented. By means of comprehensive investigations, the comparability of the BNC harvested to that gained from static cultivation under batch conditions is demonstrated. A first estimation of the production costs further shows that this type of processing allows for significant cost reductions compared to static cultivation of BNC in Erlenmeyer flasks.

Development of a gel permeation chromatographic assay to achieve mass balance in cellulose acetate phthalate stability studies.

Cellulose acetate phthalate (CAP, cellulose acetate 1,2-benzenedicarboxylate) is a common polymeric oral tablet coating. CAP is also a vaginal microbicide candidate that potently inhibits HIV-1 proliferation. This paper describes the development of a precise, stability-indicating gel permeation chromatography (GPC) assay for CAP. During accelerated stability studies monitored by separate reversed-phase high performance liquid chromatography (RP-HPLC) and GPC analyses, an apparent loss of mass balance was observed. This deficit was corrected by recalculating the response factor (RF) for each degraded sample, proportional to the fraction of phthalate remaining bound to the polymeric CAP. The correction factor enabled CAP and the degradation product phthalic acid (PA) to be quantitated by a single GPC analysis. The chromatographic approach taken here could potentially apply to any polymer containing degradable chromophores.

Life cycle assessment of greenhouse gas emissions from plug-in hybrid vehicles: implications for policy.

Plug-in hybrid electric vehicles (PHEVs), which use electricity from the grid to power a portion of travel, could play a role in reducing greenhouse gas (GHG) emissions from the transport sector. However, meaningful GHG emissions reductions with PHEVs are conditional on low-carbon electricity sources. We assess life cycle GHG emissions from PHEVs and find that they reduce GHG emissions by 32% compared to conventional vehicles, but have small reductions compared to traditional hybrids. Batteries are an important component of PHEVs, and GHGs associated with lithium-ion battery materials and production account for 2-5% of life cycle emissions from PHEVs. We consider cellulosic ethanol use and various carbon intensities of electricity. The reduced liquid fuel requirements of PHEVs could leverage limited cellulosic ethanol resources. Electricity generation infrastructure is long-lived, and technology decisions within the next decade about electricity supplies in the power sector will affectthe potential for large GHG emissions reductions with PHEVs for several decades.