The chemical memory of smoking tobacco.

The concentration in urine of N-acetyl-hydroxy-propyl-cisteine (3HPMA), an acrolein metabolite, has been employed as a marker of the risk of illness of smokers and the relative concentration of creatinine has been evaluated to verify the effect of moving from the practice of burning tobacco to nicotine vaping. From the results concerning the urine samples of 38 subjects, collected from 2021 to 2023 and analyzed by LC-MS/MS, corresponding to 5 active smokers, 13 previously heavy smokers who replaced traditional tobacco by vaping, and 20 non-smokers, a dramatic reduction was found in 3HPMA/creatinine in urine. 3HPMA varied from values of 2150-3100 µg gcreatinine-1 to levels of 225-625 µg gcreatinine-1 found for non-smokers, with the time decay described by the equation y = 0.3661x2 - 94.359x + 6246.4 (R2: 0.757), providing a time of approximately 10 years for tobacco memory after the cessation of the consumption of burned tobacco.

Role of germinal center and CD39highCD73+ B cells in the age-related tonsillar involution.

BACKGROUND: The tonsils operate as a protection ring of mucosa at the gates of the upper aero-digestive tract. They show similarities with lymph nodes and participate as inductive organs of systemic and mucosal immunity. Based on the reduction of their size since puberty, they are thought to experience involution in adulthood. In this context, we have used tonsillar mononuclear cells (TMC) isolated from patients at different stages of life, to study the effect of ageing and the concomitant persistent inflammation on these immune cells. RESULTS: We found an age-dependent reduction in the proportion of germinal center B cell population (BGC) and its T cell counterpart (T follicular helper germinal center cells, TfhGC). Also, we demonstrated an increment in the percentage of local memory B cells and mantle zone T follicular helper cells (mTfh). Furthermore, younger tonsils rendered higher proportion of proliferative immune cells within the freshly isolated TMC fraction than those from older ones. We demonstrated the accumulation of a B cell subset (CD20+CD39highCD73+ cells) metabolically adapted to catabolize adenosine triphosphate (ATP) as patients get older. To finish, tonsillar B cells from patients at different ages did not show differences in their proliferative response to stimulation ex vivo, in bulk TMC cultures. CONCLUSIONS: This paper sheds light on the changing aspects of the immune cellular landscape, over the course of time and constant exposure, at the entrance of the respiratory and digestive systems. Our findings support the notion that there is a re-modelling of the immune functionality of the excised tonsils over time. They are indicative of a transition from an effector type of immune response, typically oriented to reduce pathogen burden early in life, to the development of an immunosuppressive microenvironment at later stages, when tissue damage control gets critical provided the time passed under immune attack. Noteworthy, when isolated from such histologic microenvironment, older tonsillar B cells seem to level their proliferation capacity with the younger ones. Understanding these features will not only contribute to comprehend the differences in susceptibility to pathogens among children and adults but would also impact on vaccine developments intended to target these relevant mucosal sites.

Biomarkers of exposure in urine of active smokers, non-smokers, and vapers.

The exposure to smoking related products has been evaluated through urine illness risk marker determination through the analysis of urine samples of smokers and vapers. Biomarkers and their metabolites such as N-acetyl-S-(2-cyanoethyl)-L-cysteine (CEMA), N-acetyl-S-(3,4-dihydroxybutyl)-L-cysteine (DHBMA), N-acetyl-S-[1-(hydroxymethyl)-2-propen-1-yl)-L-cysteine (MHBMA), N-acetyl-S-(3-hydroxypropyl)-L-cysteine (3HPMA), 2R-N-acetyl-S-(4-hydroxybutan-2-yl)-L-cysteine (HMPMA), and N-acetyl-S-(3-carboxy-2-propyl)-L-cysteine (CMEMA) together with nicotine and cotinine were identified and quantified by LC-HRMS and LC-MS/MS, and data found normalized to the creatinine level. One hundred two urine samples were collected from smokers, non-smokers, and vapers, spanning an age range from 16 to 79 years. Results obtained showed that CEMA was only detected in urine samples from smokers and MHBMA was in the same order of magnitude in all the urine samples analyzed. HMPMA was found in the urine of vapers at the same order of concentration as in non-smokers. 3HPMA in vapers was lower than in the urine of smokers, presenting an intermediate situation between smokers and non-smokers. On the other hand, DHBMA in vapers can reach similar values to those found for smokers, while CMEMA shows concentrations in the urine of vapers higher than in the case of non-smokers and traditional smokers, requiring new research to link this metabolite to the use of electronic cigarettes and possible alternative metabolomic routes. In general, this study seems to verify that traditional smoking practice constitutes a major source of carcinogenic chemicals compared with substitutive practices, although those practices are not free of potential harm.

A green methodology for the determination of cocaine in camouflaged samples.

A methodology based on the ultrasound-assisted extraction with ethanol and the dry film attenuated total reflectance infrared spectroscopy (DF-ATR-FTIR) measurement of extracts has been developed for a fast evaluation of non-conventional ("exotic") solid-sized cocaine samples. The method provides quantitative results in less than three minutes with a limit of detection in the solid sample of 1.6 µg g-1 of cocaine with a variation coefficient lower than 7%. Results found for seized samples of different natures were compared with those obtained by a reference gas chromatography method and the greenness of the whole proposed procedure was evaluated and compared using the analytical eco-scale, green analytical procedure index (GAPI), and analytical greenness metric (AGREE). The green evaluation of the proposed methodology provided green scores by considering different evaluation criteria.

Date-rape evidence through fast determination of γ-butyrolactone in adulterated beverages.

An infrared spectroscopy (IR) based methodology has been developed to determine γ-butyrolactone (GBL) in adulterated beverages. The proposed method permits the direct screening of GBL in beverages and involves a minimum sample treatment requiring less than 2 min for quantitative determination of GBL. Sensitivity of IR method was improved by using liquid-liquid extraction (LLE) providing detection limits of 0.023 mg g-1. Accuracy of the proposed methodology was evaluated through the analysis of soft beverages and alcoholic cocktails spiked with GBL at concentration levels ranging from 0.075 to 10 mg g-1 providing recovery values from 91 to 100%. GBL was determined in twelve blind-spiked beverages, including from mineral water to wine and cocktails. Results obtained were statistically comparable to those provided by a liquid chromatography (LC) reference methodology and consistent with the spiked values. Therefore, the use of LLE-FTIR allowed a simple, sensitive and quantitative determination of GBL in soft beverages and alcoholic cocktails, thus evidencing its use for sex submission intention.

Partial least squares modelization of energy dispersive X-ray fluorescence.

As a proof of concept, a green methodology has been developed for the energy dispersive X-ray fluorescence (ED-XRF) determination of calcium, potassium, iron, magnesium, aluminum, chromium, strontium, phosphorus and nickel in the peel of untreated kaki fruit (Diospyros kaki. L) samples. ED-XRF spectra of fifty-six kakis purchased in the local area of LLombay (Valencia) were obtained directly from samples without any previous treatment and without sample damage just after cleaning the fruit with distilled water. Inductively Couple Plasma Optical Emission Spectrometry (ICP-OES) was used as a reference method to determine the mineral elements after microwave assisted acid digestion. XRF spectra and concentration values obtained by ICP-OES were processed using partial least squares (PLS) data treatment to build the corresponding chemometric models for prediction of mineral profile of samples. PLS-ED-XRF permits a direct and accurate determination of Ca and K in kaki peel. For Al, Fe, Mg, Ni and Sr screening semiquantitative results were obtained. Concentrations obtained directly by the internal calibration of instrument, using GeoChem Trace model, were also compared with data predicted by chemometric models being found that PLS models must replace the calibration of the instrument for thus kind of analysis.

Ion mobility spectrometry and high resolution mass-spectrometry as methodologies for rapid identification of the last generation of new psychoactive substances.

A new drug trafficking trend has been observed in the last years by the introduction in the black market of new psychoactive substances (NPS) in order to difficult competent authority controls. In this study, ion mobility spectrometry (IMS) and high-resolution mass-spectrometry (HRMS) were proposed as vanguard and rearguard methodologies for the rapid identification of the last generation of NPS in seizures. The combined use of IMS and HRMS has been evaluated through the analysis of 24 NPS seized from 2016 to 2018 in Valencia (Spain) to demonstrate the utility of this approach. The characteristic reduced mobility (K0) values for seized NPS were determined and mass-mobility relationships were proposed and evaluated for the main NPS families: amphetamine and cathinone derivatives, and synthetic cannabinoids. IMS did not allow a unequivocal identification by itself; so, HRMS analysis was employed as rearguard confirmation methodology for the right identification of NPS. Thus, the combined use of IMS and HRMS can be considered as promising alternative for the rapid screening and identification of NPS in seizures.

Fast authentication of tea tree oil through spectroscopy.

Two new procedures, based on infrared spectroscopy in the near infrared (NIR) and mid infrared (MIR), have been developed for the authentication of tea tree oil (TTO) commercial samples. Infrared measurements were made on untreated samples by transmission NIR and attenuated total reflectance (ATR) followed by partial least square discriminant analysis (PLS-DA). These methods offer a fast and low cost alternative to enantiomeric two-dimensional gas chromatography coupled to mass detection usually employed to discriminate between authentic and non-authentic samples. In these studies, a set of 267 samples, including authentic and non-authentic labelled tea tree oil samples, were used to build the models based on the wavenumber range, data pre-processing and latent variables number selection. Infrared methods can be discriminant for authentic and non-authentic TTO samples with a 98% certainty for both ATR and NIR methodologies, employing 92 and 142 external samples respectively. Developed PLS-DA infrared based methodologies and the reference methodology have been evaluated and compared from a Green Analytical point of view.

Trace analysis by ion mobility spectrometry: From conventional to smart sample preconcentration methods. A review.

Ion mobility spectrometry (IMS) is a rapid and high sensitive technique widely used in security and forensic areas. However, a lack of selectivity is usually observed in the analysis of complex samples due to the scarce resolution of the technique. The literature concerning the use of conventional and novel smart materials in the pretreatment and preconcentration of samples previous to IMS determinations has been critically reviewed. The most relevant strategies to enhance selectivity and sensitivity of IMS determinations have been widely discussed, based in the use of smart materials, as immunosorbents, aptamers, molecularly imprinted polymers (MIPs), ionic liquids (ILs) and nanomaterial. The observed trend is focused on the development of IMS analytical methods in combination of selective sample treatments in order to achieve quick, reliable, sensitive, and selective methods for the analysis of complex samples such as biological fluids, food, or environmental samples.

Radiation Safety Aspects of Iodine-131 metaiodobenzylguanidine (131I mIBG) Therapy Program Startup.

As a medical center without a pre-existing radiopharmaceutical therapy program, it was a daunting endeavor to implement a I metaiodobenzylguanidine (mIBG) high-dose treatment regimen. It took several years of planning with hospital administration, vendors, and Texas Department of Health Radiological Control regulators to establish a viable program. Effective communication between physicians, nursing, nuclear medicine, environmental services, maintenance, and other support staff is essential and paramount for the successful execution and continued sustainability of the mIBG therapy program. Besides providing an effective treatment for patients, an additional goal for the program is to keep radiation exposure As Low As Reasonably Achievable (ALARA) for staff and patient caregivers. As such, start-up presented many training, logistical, and radiation safety challenges. The location of the isolation room and shielding specifications were designed to keep radiation exposure to public access areas to less than 2 microsieverts per hour. Before the first patient was treated the policies and procedures for training, radiation safety, product quality control, and infusion process needed to be developed, tested, and approved by various committees. Furthermore, a similar process was required for developing room set-up, post therapy cleanup, and waste storage procedures. Throughout the maturation process of the program, the departments involved have found that our safety culture has continually improved by the re-enforcement of knowledge and lessons learned, as both the ancillary and treatment staff grew more confident in each other's ability during more patient treatments are performed. This article describes the process and lessons learned during the time leading up to the startup and early years of the mIBG therapy program.

Evaluation of the Content of Antimony, Arsenic, Bismuth, Selenium, Tellurium and Their Inorganic Forms in Commercially Baby Foods.

Baby foods, from the Spanish market and prepared from meat, fish, vegetables, cereals, legumes, and fruits, were analyzed to obtain the concentration of antimony (Sb), arsenic (As), bismuth (Bi), and tellurium (Te) as toxic elements and selenium (Se) as essential element. An analytical procedure was employed based on atomic fluorescence spectroscopy which allowed to obtain accurate data at low levels of concentration. Values of 14 commercial samples, expressed in nanograms per gram fresh weight, ranged for Sb 0.66-6.9, As 4.5-242, Te 1.35-2.94, Bi 2.18-4.79, and Se 5.4-109. Additionally, speciation studies were performed based on data from a non-chromatographic screening method. It was concluded that tellurium and bismuth were mainly present as inorganic forms and selenium as organic form, and antimony and arsenic species depend on the ingredients of each baby food. Risk assessment considerations were made by comparing dietary intake of the aforementioned elements through the consumption of one baby food portion a day and recommended or tolerable guideline values.

Prediction of organic carbon and total nitrogen contents in organic wastes and their composts by Infrared spectroscopy and partial least square regression.

Middle and near infrared (MIR and NIR) were employed to determine organic carbon (OC) and total nitrogen (TN) in different soil organic amendments including wastes, composts and mixtures of composts and organic wastes. Prediction models based on partial least squares (PLS) regression from the spectra of untreated samples were built. Different spectra preprocessing strategies were adopted and the best number of latent variable was evaluated using leave-one-out cross-validation. Attenuated total reflectance (PLS-ATR-MIR) and diffuse reflectance (PLS-DR-NIR) models were built and evaluated from root mean square error of cross validation and prediction (RMSECV and RMSEP), coefficients of determination for prediction (R2 pred) and residual predictive deviation (RPD). ATR-MIR provided a better prediction capability than DR-NIR with RMSEP, R2pred and RPD values of 2.2%, 0.76 and 2.0 for OC and values of 0.2%, 0.82 and 2.4 for TN, respectively.

Ion mobility spectrometry as a fast analytical tool in benzalkonium chloride homologs determination.

A novel procedure is proposed for the determination by ion mobility spectrometry (IMS) of C12, C14 and C16 benzalkonium chloride (BAC) homologs. The proposed method requires minimum sample treatment and the measurement was made in less than one minute. A high sensitivity was obtained for BAC determination by IMS with limit of detection values from 37 to 69µgL-1. Accuracy of the proposed methodology was evaluated through the analysis of aqueous and alcoholic samples spiked with BAC at concentration levels from 0.002% to 20% (w/v), providing recovery values from 91% to 104%. BAC was determined in sanitary alcohols, nasal sprays, postharvest products, algaecides, and treated swimming pool water. Results obtained by the proposed IMS methodology were statistically comparable to those provided by a liquid chromatography-ultraviolet (LC-UV) reference methodology. The Green Certificate evaluation of the proposed IMS methodology provided 91 score points in the Eco-Scale as compared with 77 for LC-UV method.

Cocaine abuse determination by ion mobility spectrometry using molecular imprinting.

A cocaine-based molecular imprinted polymer (MIP) has been produced by bulk polymerization and employed as selective solid-phase extraction support for the determination of cocaine in saliva samples by ion mobility spectrometry (IMS). The most appropriate conditions for washing and elution of cocaine from MIPs were studied and MIPs were characterized in terms of analyte binding capacity, reusability in water and saliva analysis, imprinting factor and selectivity were established and compared with non-imprinted polymers. The proposed MIP-IMS method provided a LOD of 18µgL-1 and quantitative recoveries for blank saliva samples spiked from 75 to 500µgL-1 cocaine. Oral fluid samples were collected from cocaine consumers and analysed by the proposed MIP-IMS methodology. Results, ranging from below the LOD to 51±2mgL-1, were statistically comparable to those obtained by a confirmatory gas chromatography-mass spectrometry method. Moreover, results were compared to a qualitative lateral flow immunoassay procedure providing similar classification of the samples. Thus, MIP-IMS can be considered an useful alternative that provided fast, selective and sensitive results with a cost affordable instrumentation that does not require skilled operators.

Indoor and outdoor determination of pesticides in air by ion mobility spectrometry.

The use of ion mobility spectrometry (IMS) has been evaluated as analytical methodology to detect and evaluate the occupational exposure to pesticides. The developed IMS methodology was used, in positive and negative modes, to determine the presence of pesticides in air and to evaluate possible inhalation exposures of workers and users based on active sampling on Teflon membranes and direct thermal desorption IMS. The negative IMS mode was used to determine bensulfuron, clorpyrifos, diniconazole, diuron, flutolanil and imidacloprid, while the positive mode was employed to evaluate formetanate, metalaxyl, metamitrone, metribuzin, paclobutrazol and pirimicarb. The IMS measurements provided limits of detection from 8pg to 600pg. Indoor air samples, from phytosanitary plants, and outdoor samples, obtained from pesticide treatments in a local farm, were analysed providing pesticide air concentrations in the range of 0.04 to>0.25mgm-3. Occupational exposure of workers and pesticide users were evaluated and compared with values recommended by the authorities, providing useful information to improve the prevention programs in the phytosanitary field.

Determination of total phenolic compounds in compost by infrared spectroscopy.

Middle and near infrared (MIR and NIR) were applied to determine the total phenolic compounds (TPC) content in compost samples based on models built by using partial least squares (PLS) regression. The multiplicative scatter correction, standard normal variate and first derivative were employed as spectra pretreatment, and the number of latent variable were optimized by leave-one-out cross-validation. The performance of PLS-ATR-MIR and PLS-DR-NIR models was evaluated according to root mean square error of cross validation and prediction (RMSECV and RMSEP), the coefficient of determination for prediction (Rpred(2)) and residual predictive deviation (RPD) being obtained for this latter values of 5.83 and 8.26 for MIR and NIR, respectively.

Passive exposure to nicotine from e-cigarettes.

A procedure based on the use of ion mobility spectrometry (IMS), after liquid-liquid microextraction (LLME), has been successfully employed for the determination of passive exposure to nicotine from cigarette and e-cigarette smoking. Nicotine has been determined in exhaled breath and oral fluids of both, active and passive smokers. The aforementioned studies, made in closed environments, evidenced that the exhaled breath after conventional blend cigarette smoke provides nicotine levels of the order of 220 ng per puff, in the case of experienced smokers, being exhaled only 32 ng in the case of e-cigarettes. On the other hand, the nicotine amount in oral fluids of passive vapers was between 8 and 14 µg L(-1) lower than the average value of 38±14 µg L(-1) found for passive smokers of rolling tobacco and clearly lower than the 79±36 µg L(-1) obtained from passive smokers of classical yellow blend. This study was also placed in the frame of the verification of the e-cigarettes composition.

Green near-infrared determination of copper and mancozeb in pesticide formulations.

A green analytical procedure has been successfully developed for the simultaneous determination of copper and mancozeb in phytosanitary products. The method is based on different direct measurements of diffuse reflectance near-infrared (DR-NIR) spectra. Accuracy of the method has been evaluated by comparison of the obtained copper and mancozeb concentrations with those provided by reference methodologies based on titrimetric procedures. The average relative prediction error was 0.7 and 1.6 % for copper and mancozeb, respectively. The evaluation of the greenness of the DR-NIR procedure provided 100 points, which is the maximum value in the Green Certificate ranking, because of the absence of consumed reagents and waste generation and energy consumption lower than 0.1 kWh.

Fast determination of fish mineral profile. Application to Vietnamese panga fish.

A methodology, based on inductively coupled plasma optical emission spectrometry after microwave-assisted digestion with HNO3/H2O2, was developed to determine the mineral profile of panga fish samples imported from Vietnam. A total of 42 essential and toxic elements were studied in seven samples taken from the local market. Preliminary studies were focused on selecting the best wavelength and the required dilution of samples in order to provide the highest sensitivity to maximize the number of analytes to be determined without spectral or matrix interferences. Adequate accuracy was assured by the analysis of certified reference material TORT-2. Mercury was also determined by a direct method based on atomic absorption spectrometry. Results obtained indicated a low mineral profile, fourteen elements were found at quantitatively levels, Na (6000 µg g(-1)) K (1800 µg g(-1)) Mg (173 µg g(-1)), Ca (80 µg g(-1)), Zn (2.44 µg g(-1)), Fe (1.6 µg g(-1)), Al (1.1 µg g(-1)), Sr (0.4 µg g(-1)) and B, Ba, Hg, Mn, V (under 0.1 µg g(-1)). Additionally data were compared with those previously reported in literature and an estimation of daily intake was calculated and compared with recommended or tolerable guidelines values. Levels of As, Cd, Pb and Hg were far below the established values by the European Community.

Authentication of Alicante's Mountain cherries protected designation of origin by their mineral profile.

Chemometric analysis of inductively coupled plasma optical emission spectroscopy (ICP-OES) data was employed to verify the origin of cherry samples of different areas of Spain: Aragón, Cáceres, Castellón, Huesca and Alicante's Mountain Protected Geographic Indication (PGI). The ability of multivariate analysis methods, such as discriminant analysis (DA), was used to achieve cherry classification from their mineral content. The study was performed using 22 variables (concentrations of Al, As, B, Ba, Be, Bi, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Se, Sr, Ti and Te) and 23 variables (concentrations of Al, As, B, Ba, Be, Bi, Ca, Cd, Cr, Cu, Fe, K, Li, Mg, Mo, Na, Ni, Pb, Se, Sr, Ti, Tl and V), for cherry stone and edible part, respectively, and the best discrimination was found on using edible part mineral composition which permits a correct classification of 100% of the considered samples.