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Environmental Science & Technology Apr 2022Volatile chemical products (VCPs) have recently been identified as potentially important unconventional sources of secondary organic aerosol (SOA), in part due to the...
Volatile chemical products (VCPs) have recently been identified as potentially important unconventional sources of secondary organic aerosol (SOA), in part due to the mitigation of conventional emissions such as vehicle exhaust. Here, we report measurements of SOA production in an oxidation flow reactor from a series of common VCPs containing oxygenated functional groups and at least one oxygen within the molecular backbone. These include two oxygenated aromatic species (phenoxyethanol and 1-phenoxy-2-propanol), two esters (butyl butyrate and butyl acetate), and four glycol ethers (carbitol, methyl carbitol, butyl carbitol, and hexyl carbitol). We measured gas- and particle-phase products with a suite of mass spectrometers and particle-sizing instruments. Only the aromatic VCPs produce SOA with substantial yields. For the acyclic VCPs, ether and ester functionality promotes fragmentation and hinders autoxidation, whereas aromatic rings drive SOA formation in spite of the presence of ether groups. Therefore, our results suggest that a potential strategy to reduce urban SOA from VCPs would be to reformulate consumer products to include less oxygenated aromatic compounds.
Topics: Aerosols; Air Pollutants; Ether; Organic Chemicals; Vehicle Emissions
PubMed: 35394777
DOI: 10.1021/acs.est.1c07354 -
Journal of the American Chemical Society Oct 2021Challenges in the selective manipulation of functional groups (chemoselectivity) in organic synthesis have historically been overcome either by using reagents/catalysts...
Challenges in the selective manipulation of functional groups (chemoselectivity) in organic synthesis have historically been overcome either by using reagents/catalysts that tunably interact with a substrate or through modification to shield undesired sites of reactivity (protecting groups). Although electrochemistry offers precise redox control to achieve unique chemoselectivity, this approach often becomes challenging in the presence of multiple redox-active functionalities. Historically, electrosynthesis has been performed almost solely by using direct current (DC). In contrast, applying alternating current (AC) has been known to change reaction outcomes considerably on an analytical scale but has rarely been strategically exploited for use in complex preparative organic synthesis. Here we show how a square waveform employed to deliver electric current-rapid alternating polarity (rAP)-enables control over reaction outcomes in the chemoselective reduction of carbonyl compounds, one of the most widely used reaction manifolds. The reactivity observed cannot be recapitulated using DC electrolysis or chemical reagents. The synthetic value brought by this new method for controlling chemoselectivity is vividly demonstrated in the context of classical reactivity problems such as chiral auxiliary removal and cutting-edge medicinal chemistry topics such as the synthesis of PROTACs.
Topics: Organic Chemicals
PubMed: 34596395
DOI: 10.1021/jacs.1c06572 -
International Journal of Biological... Jun 2024This Review presents an overview of all-organic nanocomposites, a sustainable alternative to organic-inorganic hybrids. All-organic nanocomposites contain nanocellulose,... (Review)
Review
This Review presents an overview of all-organic nanocomposites, a sustainable alternative to organic-inorganic hybrids. All-organic nanocomposites contain nanocellulose, nanochitin, and aramid nanofibers as highly rigid reinforcing fillers. They offer superior mechanical properties and lightweight characteristics suitable for diverse applications. The Review discusses various methods for preparing the organic nanofillers, including top-down and bottom-up approaches. It highlights in situ polymerization as the preferred method for incorporating these nanomaterials into polymer matrices to achieve homogeneous filler dispersion, a crucial factor for realizing desired performance. Furthermore, the Review explores several applications of all-organic nanocomposites in diverse fields including food packaging, performance-advantaged plastics, and electronic materials. Future research directions-developing sustainable production methods, expanding biomedical applications, and enhancing resistance against heat, chemicals, and radiation of all-organic nanocomposites to permit their use in extreme environments-are explored. This Review offers insights into the potential of all-organic nanocomposites to drive sustainable growth while meeting the demand for high-performance materials across various industries.
Topics: Nanocomposites; Polymers; Organic Chemicals; Food Packaging; Nanofibers; Inorganic Chemicals
PubMed: 38718994
DOI: 10.1016/j.ijbiomac.2024.132129 -
Indoor Air Mar 2022Cleaning products contain numerous individual chemicals, which can be liberated on use. These species can react in air to form new chemical species, some of which are...
Cleaning products contain numerous individual chemicals, which can be liberated on use. These species can react in air to form new chemical species, some of which are harmful to health. This paper uses a detailed chemical model for indoor air chemistry, to understand the chemical reactions that can occur following cleaning, assuming cleaning products with different proportions of limonene, α-pinene, and β-pinene are used. The tests included the pure compounds, 50:50 mixtures and mixtures in proportion to the rates of reaction with ozone and the hydroxyl radical. For the 3 h following cleaning, pure α-pinene was most efficient at producing particles, pure limonene for nitrated organic material, and a 50:50 mixture of β-pinene and limonene for formaldehyde, leading to enhancements of 1.1 μg/m , 400 ppt, and 1.8 ppb, respectively, compared to no cleaning. Cleaning in the afternoon enhanced concentrations of secondary pollutants for all the mixtures, owing to higher outdoor and hence indoor ozone compared to the morning. These enhancements in concentrations lasted several hours, despite the cleaning emissions only lasting for 10 min. Doubling the air exchange rate enhanced concentrations of formaldehyde and particulate matter by ~15% while reducing that of nitrated organic material by 13%. Changing product formulations has the potential to change the resulting indoor air quality and consequently, impacts on health.
Topics: Air Pollutants; Air Pollution, Indoor; Formaldehyde; Limonene; Nitrogen Oxides; Organic Chemicals; Ozone
PubMed: 35347794
DOI: 10.1111/ina.13021 -
International Journal of Molecular... Nov 2022Persistent organic pollutants (POPs) are organic chemical substances that are widely distributed in environments around the globe. POPs accumulate in living organisms... (Review)
Review
Persistent organic pollutants (POPs) are organic chemical substances that are widely distributed in environments around the globe. POPs accumulate in living organisms and are found at high concentrations in the food chain. Humans are thus continuously exposed to these chemical substances, in which they exert hepatic, reproductive, developmental, behavioral, neurologic, endocrine, cardiovascular, and immunologic adverse health effects. However, considerable information is unknown regarding the mechanism by which POPs exert their adverse effects in humans, as well as the molecular and cellular responses involved. Data are notably lacking concerning the consequences of acute and chronic POP exposure on changes in gene expression, protein profile, and metabolic pathways. We conducted a systematic review to provide a synthesis of knowledge of POPs arising from proteomics-based research. The data source used for this review was PubMed. This study was carried out following the PRISMA guidelines. Of the 742 items originally identified, 89 were considered in the review. This review presents a comprehensive overview of the most recent research and available solutions to explore proteomics datasets to identify new features relevant to human health. Future perspectives in proteomics studies are discussed.
Topics: Humans; Persistent Organic Pollutants; Proteomics; Environmental Pollutants; Organic Chemicals; Reproduction
PubMed: 36430748
DOI: 10.3390/ijms232214271 -
PloS One 2021Industrial waste salt is classified as hazardous waste to the environment. The organic impurity and its occurrence in industrial waste salt affect the salt resource...
Industrial waste salt is classified as hazardous waste to the environment. The organic impurity and its occurrence in industrial waste salt affect the salt resource utilization. In this paper, composition quantitative analysis, XRD, TG-DSC, SEM/FIB-SEM coupled with EDS, FTIR, XPS and GC-Ms were chosen to investigate the organic impurity and its occurrence in industrial waste salt. The organic impurities owe small proportion (1.77%) in the specimen and exhibit weak thermal stability within the temperature of 600°C. A clear definition of organic impurity, including 11 kinds of organic compounds, including aldehyde, benzene and its derivatives etc., were detected in the industrial waste salt. These organic impurities, owing (C-O/C-O-C, C-OH/C = O, C-C/CHx/C = C etc.)-containing function group substance, are mainly distributed both on the surface and inside of the salt particles. Meanwhile, the organic substance may combine with metal cations (Ni2+, Mg2+, Cu2+ etc.) through functional groups, such as hydroxide, carbonyl etc., which increases its stability in the industrial waste salt. These findings provide comprehensive information for the resource utilization of industrial waste salt from chemical industry etc.
Topics: Chemical Phenomena; China; Hazardous Waste; Industrial Waste; Organic Chemicals; Salts; Sodium Chloride
PubMed: 34415952
DOI: 10.1371/journal.pone.0256101 -
Accounts of Chemical Research Jan 2020For many years, we have been looking at electrochemistry as a tool for exploring, developing, and implementing new synthetic methods for the construction of organic... (Review)
Review
For many years, we have been looking at electrochemistry as a tool for exploring, developing, and implementing new synthetic methods for the construction of organic molecules. Those efforts examined electrochemical methods and mechanisms and then exploited them for synthetic gain. Chief among the tools utilized was the fact that in a constant current electrolysis the working potential at the electrodes automatically adjusted to the oxidation (anode) or reduction (cathode) potential of the substrates in solution. This allowed for a systematic examination of the radical cation intermediates that are involved in a host of oxidative cyclization reactions. The result has been a series of structure-activity studies that have led to far greater insight into the behavior of radical cation intermediates and in turn an expansion in our capabilities of using those intermediates to trigger interesting synthetic reactions. With that said, the relationship between synthetic organic chemistry and electrochemistry is not a "one-way" interaction. For example, we have been using modern synthetic methodology to construct complex addressable molecular surfaces on electroanalytical devices that in turn can be used to probe biological interactions between small molecules and biological receptors in "real-time". Synthetic chemistry can then be used to recover the molecules that give rise to positive signals so that they can be characterized. The result is an analytical method that both gives accurate data on the interactions and provides a unique level of quality control with respect to the molecules giving rise to that data. Synthetic organic chemistry is essential to this task because it is our ability to synthesize the surfaces that defines the nature of the biological problems that can be studied. But the relationship between the fields does not end there. Recently, we have begun to show that work to expand the scope of microelectrode arrays as bioanalytical devices is teaching us important lessons for preparative synthetic chemistry. These lessons come in two forms. First, the arrays have taught us about the on-site generation of chemical reagents, a lesson that is being used to expand the use of paired electrochemical strategies for synthesis. Second, the arrays have taught us that reagents can be generated and then confined to the surface of the electrode used for that generation. This has led to a new approach to taking advantage of molecular recognition events that occur on the surface of an electrode for controlling the selectivity of a preparative reaction. In short, the confinement strategy developed for the arrays is used to ensure that the chemistry in a preparative electrolysis happens at the electrode surface and not in the bulk solution. This Account details the interplay between synthetic chemistry and electrochemistry in our group through the years and highlights the opportunities that interplay has provided and will continue to provide in the future.
Topics: Electrochemical Techniques; Molecular Structure; Organic Chemicals; Particle Size; Surface Properties
PubMed: 31891254
DOI: 10.1021/acs.accounts.9b00578 -
Molecules (Basel, Switzerland) Jul 2021Aggregation-induced emission (AIE) compounds display a photophysical phenomenon in which the aggregate state exhibits stronger emission than the isolated units. The... (Review)
Review
Aggregation-induced emission (AIE) compounds display a photophysical phenomenon in which the aggregate state exhibits stronger emission than the isolated units. The common term of "AIEgens" was coined to describe compounds undergoing the AIE effect. Due to the recent interest in AIEgens, the search for novel hybrid organic-inorganic compounds with unique luminescence properties in the aggregate phase is a relevant goal. In this perspective, the abundant, inexpensive, and nontoxic d zinc cation offers unique opportunities for building AIE active fluorophores, sensing probes, and bioimaging tools. Considering the novelty of the topic, relevant examples collected in the last 5 years (2016-2021) through scientific production can be considered fully representative of the state-of-the-art. Starting from the simple phenomenological approach and considering different typological and chemical units and structures, we focused on zinc-based AIEgens offering synthetic novelty, research completeness, and relevant applications. A special section was devoted to Zn(II)-based AIEgens for living cell imaging as the novel technological frontier in biology and medicine.
Topics: Fluorescence; Fluorescent Dyes; Ionophores; Ions; Luminescence; Optical Imaging; Organic Chemicals; Zinc
PubMed: 34299451
DOI: 10.3390/molecules26144176 -
Scientific Reports May 2020Vascular calcification occurs in various diseases including atherosclerosis, chronic kidney disease and type 2 diabetes but the mechanism underlying mineral deposition...
Vascular calcification occurs in various diseases including atherosclerosis, chronic kidney disease and type 2 diabetes but the mechanism underlying mineral deposition remains incompletely understood. Here we examined lower limb arteries of type 2 diabetes subjects for the presence of ectopic calcification and mineral particles using histology, electron microscopy and spectroscopy analyses. While arteries of healthy controls showed no calcification following von Kossa staining, arteries from 83% of diabetic individuals examined (19/23) revealed microscopic mineral deposits, mainly within the tunica media. Mineralo-organic particles containing calcium phosphate and proteins such as albumin, fetuin-A and apolipoprotein-A1 were detected in calcified arteries. Ectopic calcification and mineralo-organic particles were observed in a majority of diabetic patients and predominantly in arteries showing hyperplasia. While a low number of subjects was examined and information about disease severity and patient characteristics is lacking, these calcifications and mineralo-organic particles may represent signs of tissue dysfunction.
Topics: Arteries; Arteriosclerosis; Calcinosis; Calcium Phosphates; Case-Control Studies; Diabetes Mellitus, Type 2; Humans; Minerals; Organic Chemicals
PubMed: 32444654
DOI: 10.1038/s41598-020-65276-7 -
Free Radical Biology & Medicine Aug 2019Here we discuss the early geological record of preserved organic carbon and the criteria that must be applied to distinguish biological from non-biological origins.... (Review)
Review
Here we discuss the early geological record of preserved organic carbon and the criteria that must be applied to distinguish biological from non-biological origins. Sedimentary graphite, irrespective of its isotopic composition, does not constitute a reliable biosignature because the rocks in which it is found are generally metamorphosed to the point where convincing signs of life have been erased. Rather, multiple lines of evidence, including sedimentary textures, microfossils, large accumulations of organic matter and isotopic data for co-existing carbon, nitrogen and sulfur are required before biological origin can be convincingly demonstrated.
Topics: Carbon; Carbon Isotopes; Evolution, Chemical; Geologic Sediments; Nitrogen; Organic Chemicals; Sulfur
PubMed: 30858060
DOI: 10.1016/j.freeradbiomed.2019.03.005