Cigarette butt decomposition and associated chemical changes assessed by 13C CPMAS NMR.
Ontology highlight
ABSTRACT:
SUBMITTER: Bonanomi G
PROVIDER: S-EPMC4307979 | biostudies-literature |
REPOSITORIES: biostudies-literature
Similar Datasets
Project description:Tautomerization of 2-phenylimidazolecarbaldehydes has not been studied in detail so far, although this process is a well-known phenomenon for imidazole derivatives. That is why we focus our study on a series of 2-phenylimidazolecarbaldehydes and their parent alcohols that were synthesized and studied by detailed 1H and 13C NMR in solution and in the solid state. The apparent problem is that the fast tautomerization impedes the full structural description of the compounds by conventional 13C NMR measurements. Indeed, the 13C NMR spectra in solution exhibit poor resolution, and in most cases, signals from the imidazole ring are not detectable. To avoid this problem, we used 13C CP-MAS NMR as an alternative spectroscopic method for unambiguous spectroscopic characterization of the studied series of 2-phenylimidazoles. The data were analyzed in combination with quantum chemical DFT-GIAO methods by considering the tautomerization process and the intermolecular interactions. The DFT (B3LYP/6-31G(d,p)) calculations allowed to identify and suggest the preferred tautomer in the gas phase and in DMSO solvent, which for alcohols are (2-phenyl-1H-imidazol-4-yl)methanol and its analogs, and for the aldehydes are the 2-phenyl-1H-imidazole-5-carbaldehydes. The gas-phase calculated energy differences between the two possible tautomeric forms are in the range 0.645-1.415 kcal/mol for the alcohols and 2.510-3.059 kcal/mol for the aldehydes. In the DMSO solvent, however, for all compounds, the calculated energy differences go below 1.20 kcal/mol. These data suggest that both tautomeric forms of the studied 2-phenylimidazoles can be present in solution at room temperature. Our data from detailed 2D NMR measurements in the solid state (1H-13C HETCOR and 1H-1H double-quantum coherence MAS NMR) suggested that also in the solid state both tautomers coexist in different crystalline domains. This fact does not obscure the 13C CP-MAS NMR spectra of the studied 2-phenyl substituted imidazoles and suggests this spectroscopic method as a powerful tool for a complete structural description of tautomeric systems with aromatic conjugation.
| S-EPMC7504167 | biostudies-literature
Project description:Solar radiation has been regarded as a driver of litter decomposition in arid and semiarid ecosystems. Photodegradation of litter organic carbon (C) depends on chemical composition and water availability. However, the chemical changes in organic C that respond to solar radiation interacting with water pulses remain unknown. To explain changes in the chemical components of litter organic C exposed to UV-B, UV-A, and photosynthetically active radiation (PAR) mediated by water pulses, we measured the chemistry of marcescent Lindera glauca leaf litter by solid-state 13C cross-polarization magic angle spinning (CPMAS) nuclear magnetic resonance (NMR) over 494 days of litter decomposition with a microcosm experiment. Abiotic and biotic factors regulated litter decomposition via three pathways: first, photochemical mineralization of lignin methoxyl C rather than aromatic C exposed to UV radiation; second, the biological oxidation and leaching of cellulose O-alkyl C exposed to PAR and UV radiation interacts with water pulses; and third, the photopriming effect of UV radiation on lignin aromatic C rather than cellulose O-alkyl C under the interaction between radiation and water pulses. The robust decomposition index that explained the changes in the mass loss was the ratio of aromatic C to O-alkyl C (AR/OA) under radiation, but the ratio of hydrophobic to hydrophilic C (hydrophobicity), the carbohydrate C to methoxyl C ratio (CC/MC), and the alkyl C to O-alkyl C ratio (A/OA) under radiation were mediated by water pulses. Moreover, the photopriming effect and water availability promoted the potential activities of peroxidase and phenol oxidase associated with lignin degradation secreted by fungi. Our results suggest that direct photodegradation of lignin methoxyl C increases microbial accessibility to lignin aromatic C. Photo-oxidized compounds might be an additional C pool to regulate the stability of the soil C pool derived from plant litter by degrading lignin methoxyl and aromatic C.
| S-EPMC9504352 | biostudies-literature
Project description:A recently determined set of 20 NMR-derived conformations of a 48-residue all-alpha-helical protein, (PDB ID code 2JVD), is validated here by comparing the observed (13)C(alpha) chemical shifts with those computed at the density functional level of theory. In addition, a recently introduced physics-based method, aimed at determining protein structures by using NOE-derived distance constraints together with observed and computed (13)C(alpha) chemical shifts, was applied to determine a new set of 10 conformations, (Set-bt), as a blind test for the same protein. A cross-validation of these two sets of conformations in terms of the agreement between computed and observed (13)C(alpha) chemical shifts, several stereochemical quality factors, and some NMR quality assessment scores reveals the good quality of both sets of structures. We also carried out an analysis of the agreement between the observed and computed (13)C(alpha) chemical shifts for a slightly longer construct of the protein solved by x-ray crystallography at 2.0-A resolution (PDB ID code 3BHP) with an identical amino acid residue sequence to the 2JVD structure for the first 46 residues. Our results reveal that both of the NMR-derived sets, namely 2JVD and Set-bt, are somewhat better representations of the observed (13)C(alpha) chemical shifts in solution than the 3BHP crystal structure. In addition, the (13)C(alpha)-based validation analysis appears to be more sensitive to subtle structural differences across the three sets of structures than any other NMR quality-assessment scores used here, and, although it is computationally intensive, this analysis has potential value as a standard procedure to determine, refine, and validate protein structures.
| S-EPMC2567219 | biostudies-literature
Project description:PurposeThe diseased myocardium lacks metabolic flexibility and responds to stimuli differently compared with healthy hearts. Here, we report the use of hyperpolarized 13C NMR spectroscopy to detect sudden changes in cardiac metabolism in isolated, perfused rat hearts in response to adrenergic stimulation.MethodsMetabolism of hyperpolarized [1-(13)C]pyruvate was investigated in perfused rat hearts. The hearts were stimulated in situ by isoproterenol shortly after the administration of hyperpolarized [1-(13)C]pyruvate. The hyperpolarized 13C NMR results were corroborated with 1H NMR spectroscopy of tissue extracts.ResultsAddition of isoproterenol to hearts after equilibration of hyperpolarized [1-(13)C]pyruvate into the existing lactate pool resulted in a sudden, rapid increase in hyperpolarized [1-(13)C]lactate signal within seconds after exposure to drug. The hyperpolarized H(13)CO3 (-) and hyperpolarized [1-(13)C]alanine signals were not affected by the isoproterenol-induced elevated cardiac workload. Separate experiments confirmed that the new hyperpolarized [1-(13)C]lactate signal that arises after stimulation by isoproterenol reflects a sudden increase in total tissue lactate derived from glycogen.ConclusionThese results suggest that hyperpolarized pyruvate and 13C MRS may be useful for detecting abnormal glycogen metabolism in intact tissues.
| S-EPMC4344937 | biostudies-literature
Project description:A fast, economic, and eco-friendly methodology for the wine variety and geographical origin differentiation using 13C nuclear magnetic resonance (NMR) data in combination with machine learning was developed. Wine samples of different grape varieties cultivated in different regions in Greece were subjected to 13C NMR analysis. The relative integrals of the 13C spectral window were processed and extracted to build a chemical fingerprint for the characterization of each specific wine variety, and then subjected to factor analysis, multivariate analysis of variance, and k-nearest neighbors analysis. The statistical analysis results showed that the 13C NMR fingerprint could be used as a rapid and accurate indicator of the wine variety differentiation. An almost perfect classification rate based on training (99.8%) and holdout methods (99.9%) was obtained. Results were further tested on the basis of Cronbach's alpha reliability analysis, where a very low random error (0.30) was estimated, indicating the accuracy and strength of the aforementioned methodology for the discrimination of the wine variety. The obtained data were grouped according to the geographical origin of wine samples and further subjected to principal component analysis (PCA) and partial least squares-discriminant analysis (PLS-DA). The PLS-DA and variable importance in projection (VIP) allowed the determination of a chemical fingerprint characteristic of each geographical group. The statistical analysis revealed the possibility of acquiring useful information on wines, by simply processing the 13C NMR raw data, without the need to determine any specific metabolomic profile. In total, the obtained fingerprint can be used for the development of rapid quality-control methodologies concerning wine.
| S-EPMC7466255 | biostudies-literature
Project description:Chemically modified graphenes and other graphite-based materials have attracted growing interest for their unique potential as lightweight electronic and structural nanomaterials. It is an important challenge to construct structural models of noncrystalline graphite-based materials on the basis of NMR or other spectroscopic data. To address this challenge, a solid-state NMR (SSNMR)-based structural modeling approach is presented on graphite oxide (GO), which is a prominent precursor and interesting benchmark system of modified graphene. An experimental 2D (13)C double-quantum/single-quantum correlation SSNMR spectrum of (13)C-labeled GO was compared with spectra simulated for different structural models using ab initio geometry optimization and chemical shift calculations. The results show that the spectral features of the GO sample are best reproduced by a geometry-optimized structural model that is based on the Lerf-Klinowski model (Lerf, A. et al. Phys. Chem. B 1998, 102, 4477); this model is composed of interconnected sp(2), 1,2-epoxide, and COH carbons. This study also convincingly excludes the possibility of other previously proposed models, including the highly oxidized structures involving 1,3-epoxide carbons (Szabo, I. et al. Chem. Mater. 2006, 18, 2740). (13)C chemical shift anisotropy (CSA) patterns measured by a 2D (13)C CSA/isotropic shift correlation SSNMR were well reproduced by the chemical shift tensor obtained by the ab initio calculation for the former model. The approach presented here is likely to be applicable to other chemically modified graphenes and graphite-based systems.
| S-EPMC2857913 | biostudies-literature
Project description:BACKGROUND:Cigarette butts are some of the most common form of litter in the World, causing severe environmental damage. Analysing spatial distribution of cigarette butts in the urban environment may lead to useful insights for further interventions to reduce this form of litter. In this study, we present a GIS-based methodology to estimate the density of cigarette butts across a large urban area. METHODS:We collected information about discarded cigarette butts in outdoor public spaces by systematic social observation in a diverse sample of areas in Madrid, Spain. We used these data to estimate the density of cigarette butts in public spaces around the entire city by performing GIS analyses based on Kernel Density Estimations. Last, we validated these measures using on-field observations in a set of locations across the city. RESULTS:Hospitality venues and public transportation stops were the places with the highest concentrations of cigarette butts, followed by the entrances to educational venues and playgrounds. Central districts showed the highest amount of cigarette butts in contrast to peripheral ones. We found that our measure had good validity, with a correlation coefficient of 0.784. DISCUSSION:This is the first study estimating and mapping cigarette butt litter in a large urban area. We identified a set of outdoor public places with high concentrations of cigarette butts and found geographical unevenness in the distribution of this pervasive form of litter across the study area. Our findings demonstrate the ubiquitous nature of cigarette butts in the urban environment and the need for interventions to reduce its impact on both people's health and the environment.
| S-EPMC7167348 | biostudies-literature
Project description:ObjectivesToxic pollutants leaching from littered cigarette butts (CB) raise environmental impact concerns. The US Food and Drug Administration (FDA) is required to assess the environmental impacts of its tobacco regulatory actions per the US National Environmental Policy Act (NEPA).MethodsWe determined the chemical constituents in CB leachate through analyses of 109 field-collected CB and literature compilation and characterized their ecotoxicity to aquatic organisms.ResultsOne-third of the 98 identified CB leachate chemicals were very toxic and 10% were toxic to aquatic organisms due to acute and chronic toxicity. Polycyclic aromatic hydrocarbons, metals, phthalates, nicotine and volatile organic compounds were the most hazardous CB leachate chemicals for aquatic organisms. Of the 98 CB leachate chemicals, 25 are included in FDA's list of harmful or potentially harmful constituents in tobacco products and tobacco smoke.ConclusionsOur study quantifies CB leachate constituents, characterizes their ecological hazard and identifies chemicals of concern. Thus, it aids in evaluating the environmental impacts of tobacco products per NEPA requirements. These results provide important information for strategies to prevent and reduce CB litter (eg, awareness programs, litter laws enforcement), thereby reducing environmental hazards from CB toxicants.
| S-EPMC7849351 | biostudies-literature
Project description:INTRODUCTION:Cigarette smoking is associated with many adverse health effects and is an important public health concern. Increased understanding of smokers' behavior is central to developing effective interventions. Cigarette scavenging, a behavior that involves smoking shared or previously used cigarettes has thus far only been shown to be prevalent among homeless or incarcerated populations. The current study examines whether cigarette scavenging is prevalent in a more general population of adult smokers enrolling in a smoking cessation clinical trial, and whether engagement in this behavior is associated with demographic or smoking-related psychosocial factors. METHODS:Baseline data was obtained from adult smokers (N=227) enrolling in a randomized clinical trial for smoking cessation. Cigarette scavenging was assessed using three items: a) sharing a cigarette with a stranger; b) smoking a "found" cigarette and c) smoking a previously used cigarette "butt". Participants who endorsed engaging in at least one of these three behaviors were categorized as a scavenger. RESULTS:Approximately 32% of participants endorsed at least one cigarette scavenging behavior. A multiple logistic regression analysis found that scavengers were more likely to be: men (p<0.001), of younger age at smoking onset (p=0.012), unemployed (p=0.003), more likely to have used marijuana in the past 30days (p=0.005), single or living alone (p=0.003), and to have experienced higher withdrawal symptoms during previous quit attempts (p=0.044) as compared to non-scavengers. CONCLUSIONS:Scavenging is common among adult smokers. Interventions that address cigarette scavenging behaviors may better meet the needs of this unique smoking subgroup.
| S-EPMC5783780 | biostudies-literature
Project description:Microalgal-based remediation is an ecofriendly and cost-effective system for wastewater treatment. This study evaluated the capacity of microalgae in the remediation of wastewater from cleaning process of smoked cigarette butts (CB). At laboratory scale, six strains (one from the family Scenedesmaceae, two Chlamydomonas&nbsp;debaryana and three Chlorella&nbsp;sorokiniana) were exposed to different CB wastewater dilutions to identify toxicity levels reflected in the alteration of microalgal physiological status and to determine the optimal conditions for an effective removal of contaminants. CB wastewater could impact on microalgal chlorophyll and carotenoid production in a concentration-dependent manner. Moreover, the resistance and remediation capacity did not only depend on the microalgal strain, but also on the chemical characteristics of the organic pollutants. In detail, nicotine was the most resistant pollutant to removal by the microalgae tested and its low removal correlated with the inhibition of photosynthetic pigments affecting microalgal growth. Concerning the optimal conditions for an effective bioremediation, this study demonstrated that the Chlamydomonas strain named F2 showed the best removal capacity to organic pollutants at 5% CB wastewater (corresponding to 25 butts L-1 or 5 g CB L-1) maintaining its growth and photosynthetic pigments at control levels.
| S-EPMC9269138 | biostudies-literature