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\"This book is a scholarly investigation into the gram sabhas' potential for enhancing the capacity of ordinary citizens to engage with democracy under the enormously wide-ranging conditions and constraints that shape life in rural India. Our data are transcripts from 298 village assemblies from four neighboring South Indian states that were sampled and recorded within the framework of a natural experiment. And we use discourse analysis on this corpus of transcript data to gain insights into how India's rural citizens engage with this form of direct democracy\"-- Provided by publisher.

• Analysis of wood transects in a manner that preserves the spatial distribution of the metabolites present is highly desirable to among other things: (1) facilitate ecophysiology studies that reveal the association between chemical make-up and environmental factors or climatic events over time; and (2) investigate the mechanisms of the synthesis and trafficking of small molecules within specialised tissues. While a variety of techniques could be applied to achieve these goals, most remain challenging and impractical. • Laser ablation direct analysis in real time imaging–mass spectrometry (LADI-MS) was successfully used to survey the chemical profile of wood, while also preserving the small-molecule spatial distributions. The tree species Entandrophragma candollei Harms, Millettia laurentii DeWild., Pericopsis elata (Harms) Meeuwen, Dalbergia nigra (Vell.) Benth. and Dalbergia normandii Bosser & R. Rabev were analysed. • Several compounds were associated with anatomical features. A greater diversity was detected in the vessels and parenchyma compared with the fibres. Analysis of single vessels revealed that the chemical fingerprint used for timber identification is mainly determined by vessel content. • Laser ablation direct analysis in real time imaging–mass spectrometry offers unprecedented opportunities to investigate the distribution of metabolites within wood samples, while circumventing the issues associated with previous methods. This technique opens up new vistas for the discovery of small-molecule biomarkers that are linked to environmental events.

A series of poly(ethylene-co-vinylalcohol)(PE-VOL)/poly(D,L-lactic-co-glycolic acid (PD,L-LGA) blends with different compositions was prepared by solution casting, and its miscibility was proved through viscosimetry and differential scanning calorimetry (DSC) methods through a positive value of α (San et al. Eq.) and negative value of χ1,2 (Nishi–Wang Equation). XRD analysis of the PE-VOL/PD,L-LGA system revealed a homogeneous distribution of PE-VOL molecules aggregated in the PD,L- LGA matrix and the crystalline structure of the semi crystalline copolymer was conserved in the blend in aggregated form. It also revealed that the amorphous copolymer dispersed in the blend acted as a weak nucleating agent. The non-isothermal crystallization kinetics of neat semi-crystalline copolymer and the blend was used to describe the crystallization process using the Ozawa approach. The thermal stability of these materials was investigated by the thermal gravimetry analysis. The isothermal decomposition of copolymers and their blend were carried out by high resolution mass spectrometry using direct-analysis-in-real-time method. Relevant results that could highlight the miscible character of this blend are revealed through comparison of the different fragments resulting from the decomposition of the blend with those of the pure components.

Rapid, efficient, versatile, easy-to-use, and non-expensive analytical approaches are globally demanded for food analysis. Many ambient ionization approaches based on electrospray ionization (ESI) have been developed recently for the rapid molecular characterization of food products. However, those approaches mainly suffer from insufficient signal duration for comprehensive chemical characterization by tandem MS analysis. Here, a commercially available disposable gel loading tip is used as a low-cost emitter for the direct ionization of untreated food samples. The most important advantages of our approach include high stability, and durability of the signal (> 10 min), low cost (ca. 0.1 USD per run), low sample and solvent consumption, prevention of tip clogging and discharge, operational simplicity, and potential for automation. Quantitative analysis of sulfapyridine, HMF (hydroxymethylfurfural), and chloramphenicol in real sample shows the limit-of-detection 0.1 μg mL−1, 0.005 μg mL−1, 0.01 μg mL−1; the linearity range 0.1–5 μg mL−1, 0.005–0.25 μg mL−1, 0.01–1 μg mL−1; and the linear fits R2 ≥ 0.980, 0.991, 0.986. Moreover, we show that tip-ESI can also afford sequential molecular ionization of untreated viscous samples, which is difficult to achieve by conventional ESI. We conclude that tip-ESI–MS is a versatile analytical approach for the rapid chemical analysis of untreated food samples.

The presence, magnitude, and significance of sex differences in the human brain are hotly debated topics in the scientific community and popular media. This debate is largely fueled by studies containing strong, opposing conclusions: either little to no evidence exists for sex differences in human neuroanatomy, or there are small-to-moderate differences in the size of certain brain regions that are highly reproducible across cohorts (even after controlling for sex differences in average brain size). Our Commentary uses the specific comparison between two recent large-scale studies that adopt these opposing views—namely the review by Eliot and colleagues (2021) and the direct analysis of ~ 40k brains by Williams and colleagues (2021)—in an effort to clarify this controversy and provide a framework for conducting this research. First, we review observations that motivate research on sex differences in human neuroanatomy, including potential causes (evolutionary, genetic, and environmental) and effects (epidemiological and clinical evidence for sex-biased brain disorders). We also summarize methodological and empirical support for using structural MRI to investigate such patterns. Next, we outline how researchers focused on sex differences can better specify their study design (e.g., how sex was defined, if and how brain size was adjusted for) and results (by e.g., distinguishing sexual dimorphisms from sex differences). We then compare the different approaches available for studying sex differences across a large number of individuals: direct analysis, meta-analysis, and review. We stress that reviews do not account for methodological differences across studies, and that this variation explains many of the apparent inconsistencies reported throughout recent reviews (including the work by Eliot and colleagues). For instance, we show that amygdala volume is consistently reported as male-biased in studies with sufficient sample sizes and appropriate methods for brain size correction. In fact, comparing the results from multiple large direct analyses highlights small, highly reproducible sex differences in the volume of many brain regions (controlling for brain size). Finally, we describe best practices for the presentation and interpretation of these findings. Care in interpretation is important for all domains of science, but especially so for research on sex differences in the human brain, given the existence of broad societal gender-biases and a history of biological data being used justify sexist ideas. As such, we urge researchers to discuss their results from simultaneously scientific and anti-sexist viewpoints. Highlights Recent large-scale studies have reached different conclusions regarding the presence of sex differences in human neuroanatomy. We show that these contradictory findings are explained by different methodological choices. While multiple large direct analyses highlight small, highly reproducible sex differences, reviews do not account for methodological heterogeneity across studies (e.g., statistical power/sample size, brain size-correction methods, segmentation, region selection, participant age). This explains many of the apparent inconsistencies reported in recent reviews. We also summarize observations that motivate research on sex differences in human neuroanatomy (including potential causes and effects), review methodological and empirical support for using structural MRI to investigate such patterns, and outline best practices for analyzing and describing neuroanatomical sex differences. Finally, we argue that broader historical and societal contexts make it important to reinforce the scientific method by adopting an actively \"anti-sexist\" viewpoint when conducting research on sex differences in the human brain.

Mass spectrometry has recently undergone a second contemporary revolution with the introduction of a new group of desorption/ionization (DI) techniques known collectively as ambient mass spectrometry. Performed in an open atmosphere directly on samples in their natural environments or matrices, or by using auxiliary surfaces, ambient mass spectrometry (MS) has greatly simplified and increased the speed of MS analysis. Since its debut in 2004 there has been explosive growth in the applications and variants of ambient MS, and a very comprehensive set of techniques based on different desorption and ionization mechanisms is now available. Most types of molecules with a large range of masses and polarities can be ionized with great ease and simplicity with the outstanding combination of the speed, selectivity, and sensitivity of MS detection. This review describes and compares the basis of ionization and the concepts of the most promising ambient MS techniques known to date and illustrates, via typical analytical and bioanalytical applications, how ambient MS is helping to bring MS analysis deeper than ever into the “real world” open atmosphere environment—to wherever MS is needed. [graphic removed]

Spilled plant-based oils behave very differently in comparison to petroleum oils and require different clean-up measures. They do not evaporate, disperse, dissolve, or emulsify to a significant degree but can polymerize and form an impermeable cap on sediment, smothering benthic media and resulting in an immediate impact on the wildlife community. The current study explored the application of rapid up-to-date direct analysis in real time (DART) with high-resolution mass spectrometry for plant-based oil typing. The study introduced a new concept of using hydrophobic paper to collect and analyze oil samples, thus minimizing sample preparation and expenses. Application of this technique showed its ability to speedily distinguish plant-based from petroleum-based oils. A microcosm experiment exposing plant-based oil samples to weathering processes for comparison with petroleum-based oils demonstrated the ability of the method to classify weathered oil samples and identify their source oil. It was observed that canola and peanut oil were the most resistant to weathering processes. The developed DART-TOFMS method was shown to be accurate for short-term weathered oil spills up to between 12 and 26 days of exposure. The developed method performed identification in less than a day compared to the established multi-day method for oil spill forensics requiring careful sample collection in glass containers, time-consuming laboratory clean-up, lengthy gas chromatography sequences, and careful integration including integration of retention time markers.

The identification of volatile organic compounds (VOC) such as acetone, a relevant biomarker for diabetes mellitus in exhaled human breath has become essential for early disease diagnostics, prognosis, and monitoring of metabolic responses to pharmacological interventions. Gas chromatography coupled with mass spectrometry (GC–MS) is considered as the gold standard for breath analysis. However, its inability to offer point-of-care monitoring limits its applicability in clinical environments. Optical techniques based on absorption in the mid-infrared range (2.5 to 25 μm) appear as promising alternatives due to their inherent selectivity, potential for miniaturization, portability, and direct analysis with rapid response. Relevant biomarkers present in exhaled breath, are usually observed in the ppb to ppm (v/v) concentration regime. For sensitivity enhancement of optical sensing techniques, appropriate preconcentration schemes are required prior to the optical detection. The present study describes a method combining a multi-channel substrate-integrated preconcentration module (a.k.a., muciPRECON) for enhancing and optimizing the detection of acetone via a mid-infrared photonic sensing system. The sensor system comprises a compact Fourier Transform Infrared (FTIR) spectrometer, a technique that enables detailed infrared spectral analysis, coupled to a substrate-integrated hollow waveguide (iHWG) simultaneously acting as a gas cell and as a photon conduit. Preconcentation experiments were from acetone/nitrogen gas mixtures in the concentration range of 5–100 ppm at − 10 °C followed by desorption at a temperature of 100 °C and direct injection into the IR sensing system Thus obtained acetone spectra were quantified evaluating a molecule-specific vibrational absorption peak area in the spectral window 1260–1170 cm −1 . After extensive screening, Tenax was identified as superior sorbent material providing an enrichment factor of up to 153-times, a limit of detection (LOD) of 0.118 ppm, and a limit of quantification (LOQ) of 0.393 ppm. These results are indeed promising for practical applications, especially since acetone concentrations usually vary between 0.3 and 0.9 ppmv within the exhaled breath of healthy individuals, and in individuals with diabetes, acetone concentrations are typically around 1.7 to 3.0 ppmv. Consequently, the developed systems have the necessary sensitivity and accuracy to detect acetone levels that are in the relevant physiological range indicating their potential use in future real-world scenarios.

The environment of Saudi Arabia is particularly rich in plants utilized in folk medicine to cure various diseases. Therefore, the quality assessment of these plants and the study of their primary constituents are crucial for human health. Chromatographic techniques and mass spectrometry are effective methods for separating, profiling, and analyzing natural products. The primary objective of this work is to extract and profile the natural constituents present in the Moltkiopsis ciliata plant and identify their major bioactive compounds. More than 30 compounds were rapidly identified from the fresh parts of the plant—flowers, leaves, roots, and stems—without any prior sample preparation by direct analysis in real-time of flight-mass spectrometry (DART-ToF-MS), highlighting the novelty of this method in profiling the phytochemical composition of the plant. The total extracts of the plant were fractionated according to their polarity by liquid-liquid extraction and analyzed by gas chromatography-mass spectrometry (GC-MS). In addition, the hexane extracts of flowers, leaves, stems, and roots were analyzed using GC-MS and showed the presence of many volatile constituents, in which more than 60 compounds were successfully identified. Many of the detected compounds highlight the potential biological significance of the plant, such as indolizine, echinatine, heliotrine, vitamin E, campesterol, stigmasterol, γ-sitosterol, and phytol, which are known to have anti-inflammatory, antimicrobial, and antioxidant properties. Whereas the abrine compound was identified in this species for the first time. In a comparison between the two MS techniques used in this work, the results indicate that the proposed methods are complementary and can be used together for the comprehensive screening and regular analysis of bioactive compounds in plants.

•Large dataset that presents the characteristics and the scenario of cocaine in Brazil.•Representative dataset without precedents, 1085 real samples from 375 seizures obtained in different Brazilian States.•Wide characterization of real cocaine samples by an ATR–FTIR/PLS method.•Simultaneous determination of the presentation form, oxidation degree and cocaine content.•Simultaneous determination of the adulterants phenacetin, benzocaine, caffeine, lidocaine and aminopyrine. Middle infrared spectroscopy and multivariate analysis have been applied for the development of methods to perform both quantitative and qualitative analysis of real drug samples seized by the Brazilian Police Federal (BPF). Currently, quantification of cocaine and determination of adulterants in seizures is performed using gas chromatography with flame ionization detection. However, this technique requires a relatively complex sample preparation, higher time of analysis, the destruction of sample and a high cost. In this context, this paper presents a simpler method to quantify cocaine and its major adulterants in seized materials. Out of 375 seizures, taken within a time frame of 2009–2013. A total of 1085 samples were analyzed of which 500 were selected for the calibration set and 585 for the validation set. Cocaine concentration in seized samples was determined by using middle infrared spectroscopy and partial least squares regression (PLSR), obtaining an average prediction error of 3.0% (w/w), precision of 2.0 and 11.8% (w/w) of minimum detectable cocaine concentration in a range varying from 24.2 to 99.9% (w/w). Results indicate that the developed method is able to discriminate between cocaine hydrochloride and free base samples, to quantify cocaine content as well as to estimate the concentration of main adulterants phenacetin, benzocaine, caffeine, lidocaine and aminopyrine.