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Hydroperoxides are formed in the atmospheric oxidation of volatile organic compounds, in the combustion autoxidation of fuel, in the cold environment of the interstellar medium, and also in some catalytic reactions. They play crucial roles in the formation and aging of secondary organic aerosols and in fuel autoignition. However, the concentration of organic hydroperoxides is seldom measured, and typical estimates have large uncertainties. In this work, we developed a mild and environmental-friendly method for the synthesis of alkyl hydroperoxides (ROOH) with various structures, and we systematically measured the absolute photoionization cross-sections (PICSs) of the ROOHs using synchrotron vacuum ultraviolet-photoionization mass spectrometry (SVUV-PIMS). A chemical titration method was combined with an SVUV-PIMS measurement to obtain the PICS of 4-hydroperoxy-2-pentanone, a typical molecule for combustion and atmospheric autoxidation ketohydroperoxides (KHPs). We found that organic hydroperoxide cations are largely dissociated by loss of OOH. This fingerprint was used for the identification and accurate quantification of the organic peroxides, and it can therefore be used to improve models for autoxidation chemistry. The synthesis method and photoionization dataset for organic hydroperoxides are useful for studying the chemistry of hydroperoxides and the reaction kinetics of the hydroperoxy radicals and for developing and evaluating kinetic models for the atmospheric autoxidation and combustion autoxidation of the organic compounds.
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Based on quantum mechanically guided experiments that observed elusive intermediates in the domain of inception that lies between large molecules and soot particles, we provide a new mechanism for the formation of carbonaceous particles from gas-phase molecular precursors. We investigated the clustering behavior of resonantly stabilized radicals (RSRs) and their interactions with unsaturated hydrocarbons through a combination of gas-phase reaction experiments and theoretical calculations. Our research directly observed a sequence of covalently bound clusters (CBCs) as key intermediates in the evolution from small RSRs, such as benzyl (C7H7), indenyl (C9H7), 1-methylnaphthyl (1-C11H9), and 2-methylnaphthyl (2-C11H9), to large polycyclic aromatic hydrocarbons (PAHs) consisting of 28 to 55 carbons. We found that hydrogen abstraction and RSR addition drive the formation and growth of CBCs, leading to progressive H-losses, the generation of large PAHs and PAH radicals, and the formation of white smoke (incipient carbonaceous particles). This mechanism of progressive H-losses from CBCs (PHLCBC) elucidates the crucial relationship among RSRs, CBCs, and PAHs, and this study provides an unprecedentedly seamless path of observed assembly from small RSRs to large nanoparticles. Understanding the PHLCBC mechanism over a wide temperature range may enhance the accuracy of multiscale models of soot formation, guide the synthesis of carbonaceous nanomaterials, and deepen our understanding of the origin and evolution of carbon within our galaxy.
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In this study, a simple, green, and low-cost room temperature synthesis of broccoli-like silver nanoflowers (AgNF) with a particle size of about 300-500 nm was developed using plant-derived caffeic acid as a reducing agent and polyvinylpyrrolidone as a dispersant under ultrasound assistance. The flower clusters covered by small nanocrystals of 20-50 nm significantly enhance the electromagnetic field signals. AgNF was deposited on the surface of silicon wafers as a surface-enhanced Raman spectroscopy sensor for the detection of probe molecules such as rhodamine 6G (R6G) and malachite green with high sensitivity, homogeneity, and reproducibility. AgNF was deposited on cotton fabrics in the form of composites to catalyze the degradation of dye pollutants such as R6G, MG, and methyl orange in the presence of sodium borohydride. 0.1 g of AgNF/cotton fabric could assist 15 mmol/L NaBH4 to achieve over 90% degradation of various dyes as well as a high concentration of dyes in 12 min with good reusability and recyclability. The AgNF synthesized in this work can not only monitor the type and amounts of pollutants (dyes) in wastewater but also catalyze the rapid degradation of dyes, which is expected to be valuable for industrial applications.
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The build-up of lactate in solid tumors stands as a crucial and early occurrence in malignancy development, and the concentration of lactate in the tumor microenvironment may be a more sensitive indicator for analyzing primary tumors. In this study, we designed a self-powered lactate sensor for the rapid analysis of tumor samples, utilizing the coupling between the piezoelectric effect and enzymatic reaction. This lactate sensor is fabricated using a ZnO nanowire array modified with lactate oxidase (LOx). The sensing process does not require an external power source or batteries. The device can directly output electric signals containing lactate concentration information when subjected to external forces. The lactate concentration detection upper limit of the sensor is at least 27 mM, with a limit of detection (LOD) of approximately 1.3 mM and a response time of around 10 s. This study innovatively applied self-powered technology to the in situ detection of the tumor microenvironment and used the results to estimate the growth period of the primary tumor. The availability of this application has been confirmed through biological experiments. Furthermore, the sensor data generated by the device offer valuable insights for evaluating the likelihood of remote tumor metastasis. This study may expand the research scope of self-powered technology in the field of medical diagnosis and offer a novel perspective on cancer diagnosis.
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Nanofios , Neoplasias , Humanos , Ácido Láctico , Neoplasias/diagnóstico , Fontes de Energia Elétrica , Eletricidade , Microambiente TumoralRESUMO
Self-powered wearable sensing systems have attracted great attention for their application in continuous health monitoring, which can reveal real-time physiological information on the body. Here, an innovative self-powered sound-driven humidity sensor for wearable intelligent dehydration monitoring system has been proposed. The sensor is primarily comprised of PTFE membrane, ZnO nanoarrays and Ti thin film. The piezoelectric/triboelectric effect of ZnO nanoarrays/PTFE membrane is coupled with the humidity sensing process. Sound wave can drive PTFE membrane to vibrate, and the contact and separation between PTFE and ZnO can generate electrical signals through piezoelectric/triboelectric effect. At the same time, the surface of the nanostructures can absorb the water molecules, which will influence the electrical output of the device. The device can convert sound energy into electrical output without any external electricity power supply, and the outputting voltage decreases with increasing relative humidity, acting as the sensing signal. The sensor has been integrated with data processing unit and wireless transmission module to form a self-powered wearable intelligent dehydration monitoring system, which can actively monitor the humidity of exhaled breath and transmit the information to the mobile phone. The results can open a possible new direction for the development of sound-driven gas sensors and will further expand the scope for self-powered nanosystems.
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Dispositivos Eletrônicos Vestíveis , Óxido de Zinco , Humanos , Umidade , Desidratação , PolitetrafluoretilenoRESUMO
The interaction of fuel with NOx chemistry is important for the construction of the reaction mechanism and engine application. In this work, the reaction pathways of nC5H12 + NO2 were studied by high-level electronic structure calculations (DLPNO-CCSD(T)-F12/cc-pVTZ-F12//B2PLYPD3/cc-pVTZ). The rate constants were calculated by using the multistructural canonical transition-state theory with the Eckart tunneling method (TST/MS-T/ET). The studied condition is in a wide temperature range of 298-2400 K. The influence of MS-T anharmonicity and tunneling effect will be clarified for these site-specific H-abstraction pathways. The result reflects the large deviation introduced by the treatment of MS-T anharmonicity, especially at a high temperature. For the same type of reactions, the rate constants of H-abstraction both occurring at the secondary carbon are not almost identical. The branching ratios show that abstraction from the secondary site forming cis-HONO (R2c) contributes 36-78% to nC5H12 consumption in the temperature range of 298-2400 K. The current results show that the multistructural torsional anharmonicity has a crucial influence on the accurate estimation of branching ratios.
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The sea cucumber Apostichopus japonicus has important nutritional and medicinal value. Unfortunately, we know little of the source of active chemicals in this animal, but the plentiful pigments of these animals are thought to function in intriguing ways for translation into clinical and food chemistry usage. Here, we found key cell groups with the gene activity predicted for the color morphology of sea cucumber body using single-cell RNA-seq. We refer to these cell populations as melanocytes and quinocytes, which are responsible for the synthesis of melanin and quinone pigments, respectively. We integrated analysis of pigment biochemistry with the transcript profiles to illuminate the molecular mechanisms regulating distinct pigment formation in echinoderms. In concert with the correlated pigment analysis from each color morph, this study expands our understanding of medically important pigment production, as well as the genetic mechanisms for color morphs, and provides deep datasets for exploring advancements in the fields of bioactives and nutraceuticals.
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Pepinos-do-Mar , Stichopus , Animais , Transcriptoma , Pepinos-do-Mar/genética , Stichopus/genéticaRESUMO
Ketohydroperoxides (KHPs) are oxygenates with carbonyl and hydroperoxy functional groups, and they are generated under combustion and atmospheric conditions. Their fate is crucial for secondary organic aerosol formation in the troposphere and for the ignition processes of biofuels in advanced combustion engines. We investigated the thermodynamics and kinetics of nine hydrogen abstraction reactions from four ether KHPs by OH. We find that the rate constants are strongly affected by entropic effects whose estimation requires a consideration of higher-energy conformers of the transition state. A density functional was selected for these reactions by comparison to coupled cluster calculations, and it was used for calculations by multistructural canonical transition-state theory with multidimensional tunneling over the temperature range of 200-2000 K. We find that the effect of multistructural torsional anharmonicity is very large and quite different for the various ether KHP reactions. A leading cause of the structural dependence is the dominance of entropic factors due to the lack of hydrogen bonding in some of the higher-energy conformers of the transition states. Four of the reactions involve abstraction from the α-carbon (the carbon vicinal to the hydroperoxide group); they exhibit nonmonotonic temperature dependence with complex fuel-specific dependence. The rate constants for abstraction from a non-α-carbon of a given KHP can be faster than the ones for abstraction from an α-carbon; in two cases, this is due to entropy, and in one case, the non-α-carbon abstraction has a lower energy barrier. Tunneling and recrossing effects are also found to be important.
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Biocombustíveis , Peróxido de Hidrogênio , Carbono/química , Éteres , Hidrogênio/química , Ligação de HidrogênioRESUMO
Apart from sharing common ancestry with chordates, sea cucumbers exhibit a unique morphology and exceptional regenerative capacity. Here we present the complete genome sequence of an economically important sea cucumber, A. japonicus, generated using Illumina and PacBio platforms, to achieve an assembly of approximately 805 Mb (contig N50 of 190 Kb and scaffold N50 of 486 Kb), with 30,350 protein-coding genes and high continuity. We used this resource to explore key genetic mechanisms behind the unique biological characters of sea cucumbers. Phylogenetic and comparative genomic analyses revealed the presence of marker genes associated with notochord and gill slits, suggesting that these chordate features were present in ancestral echinoderms. The unique shape and weak mineralization of the sea cucumber adult body were also preliminarily explained by the contraction of biomineralization genes. Genome, transcriptome, and proteome analyses of organ regrowth after induced evisceration provided insight into the molecular underpinnings of visceral regeneration, including a specific tandem-duplicated prostatic secretory protein of 94 amino acids (PSP94)-like gene family and a significantly expanded fibrinogen-related protein (FREP) gene family. This high-quality genome resource will provide a useful framework for future research into biological processes and evolution in deuterostomes, including remarkable regenerative abilities that could have medical applications. Moreover, the multiomics data will be of prime value for commercial sea cucumber breeding programs.
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Evolução Biológica , Genoma , Regeneração/genética , Pepinos-do-Mar/anatomia & histologia , Pepinos-do-Mar/genética , Vísceras/fisiologia , Animais , Osso e Ossos/anatomia & histologia , Calcificação Fisiológica/genética , Sequência Conservada/genética , Genes Homeobox , Família Multigênica , Sistema Nervoso/metabolismo , Filogenia , Pepinos-do-Mar/fisiologiaRESUMO
The OH radical plays an important role in combustion, and isopentanol (3-methylbutan-1-ol) is a promising sustainable fuel additive and second-generation biofuel. The abstractions of H atoms from fuel molecules are key initiation steps for chain branching in combustion chemistry. In comparison with the more frequently studied ethanol, isopentanol has a longer carbon chain that allows a greater number of products, and experimental work is unavailable for the branching fractions to the various products. However, the site-dependent kinetics of isopentanol with OH radicals are usually experimentally unavailable. Alcohol oxidation by OH is also important in the atmosphere, and in the present study we calculate the rate constants and branching fractions of the hydrogen abstraction reaction of isopentanol by OH radical in a broad temperature range of 298-2400 K, covering temperatures important for atmospheric chemistry and those important for combustion. The calculations are done by multipath variational transition state theory (MP-VTST). With a combination of electronic structure calculations, we determine previously missing thermochemical data. With MP-VTST, a multidimensional tunneling approximation, multiple-structure anharmonicity, and torsional potential anharmonicity, we carried out more realistic rate constant calculations than can be computed by conventional single-structure harmonic transition state theory or by the empirical relations that are currently used in atmospheric and combustion modeling. The roles of various factors in determining the rates are elucidated, and we show that recrossing, tunneling, and multiple structures are all essential for accurate work. We conclude that the multiple structure anharmonicity is the most important correction to conventional transition state theory for this reaction, although recrossing effects and tunneling are by no means insignificant and the tunneling depends significantly on the path. The thermodynamic and kinetics data determined in this work are indispensable for the gas-phase degradation of alcohols in the atmosphere and for the detailed understanding and prediction of ignition mechanisms of biofuels in combustion.
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Pyrolytic kinetics of indene was studied in a flow reactor at 30 and 760 Torr. Indene and its decomposition products, as well as polycyclic aromatic hydrocarbons (PAHs), were measured with synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS). Five literature models were selected to reproduce the experimental data and analyze the reaction kinetics of indene. The experimental and predicted results illustrate that an indenyl radical is the dominant decomposition intermediate and also the main contributor to the further growth of aromatic rings in the pyrolysis of indene. The indene consumption process needs further precise characterization, especially the subsequent dissociation reactions of indanyl and indenyl radicals. A self-recombination reaction of the indenyl radical and the combination reactions between indenyl and other radicals are found to be necessary for the efficient formation of large PAHs. The absence of these pathways leads to the underprediction of experimental measurements. In contrast, literature models adopting indenyl global reactions for PAH formation generally overestimate the system reactivity. Proper radical combination pathways proposed in a future model should consider not only the PAH formation efficiency but also its impact on system reactivity.
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Highly luminescent semiconductor with ultrasmall size is always desirable for biomedical applications. Here, we developed a novel solvent-directing strategy to prepare ultrasmall monodispersed Ag2S quantum dots (QDs) with strong luminescence in the second near infrared (NIR-II) range (1000â¼1400 nm). The particle size and luminescence of these Ag2S QDs could be desirably tuned by adjusting the solvents of the system. With further surface modification, the hydrophilic Ag2S QDs could be successfully utilised for cancerous cells imaging, indicating great potentials in biomedical fields.
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Self-powered piezoelectric-biosensing textiles for the physiological monitoring and time-motion analysis of individual sports have been developed. The material system is composed of tetrapod-shaped ZnO nanowires on common textiles. The mechanism is based on the coupling of enzymatic reaction (LOx and lactate) and piezoelectric effect. After conformably attaching the device to the athlete, the device can monitor in real-time the moving speed, frequency, joint angle, and sweat lactate concentration of the athlete. The whole monitoring/analysis process is battery-free. The motor skills and physiological state of two athletes are investigated using the textiles, and different lactate threshold times and maximum lactate release capacities have been obtained. This technique can help them develop distinct training programs. This research is a new direction for the scientific monitoring of kinematics and may also stimulate the development of self-powered wearable sports-related systems.
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Técnicas Biossensoriais , Monitorização Fisiológica , Nanofios/química , Esportes , Fontes de Energia Elétrica , Humanos , Movimento (Física) , Suor , Têxteis , Óxido de Zinco/químicaRESUMO
Hydroperoxyalkylperoxy species (OOQOOH) are important intermediates that are generated during the autoignition of transport fuels. A key reaction of hydroperoxyalkylperoxy radicals is a [1,5] hydrogen shift, for which kinetics data are experimentally unavailable. Here we study two typical OOQOOH reactions and compare their kinetics to one another and to a previous study to learn the effect of structural variations of the alkyl group on the competition between alternative [1,5] hydrogen shifts of hydroperoxyalkylperoxy species. We use electronic structure calculations to determine previously missing thermochemical data, and we use variational transition state theory with multidimensional tunneling, multiple structures, torsional potential anharmonicity, and high-frequency anharmonicity to obtain more accurate rate constants than the ones that can be computed by conventional single-structure harmonic transition state theory and than the empirically estimated rate constants that are currently used in combustion modeling. The calculated temperature range is 298-1500 K. The roles of various factors in determining the rates are elucidated, and we find an especially strong effect of multiple structure anharmonicity due to torsions. Thus, even though there is some cancellation between the anharmonicity of the reactant and the anharmonicity of the transition state, and even though the reactants are very similar in structure, differing only by a methyl group, the effect of multiple structure anharmonicity has a large effect on the relative rates, as large as a factor of 17 at room temperature and as large as a factor of 7 at 1500 K. This has broad implications for the estimation of reaction rates in many subfields of chemistry, including combustion chemistry and atmospheric chemistry, where rates of reaction of complex molecules are usually estimated without explicit consideration of this fundamental entropic effect. In addition, the pressure-dependence of the rate constants is modeled by system-specific quantum Rice-Ramsperger-Kassel theory for a reversible isomerization.
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The development of multifunctional electronic-skin that establishes human-machine interfaces, enhances perception abilities or has other distinct biomedical applications is the key to the realization of artificial intelligence. In this paper, a new self-powered (battery-free) flexible vision electronic-skin has been realized from pixel-patterned matrix of piezo-photodetecting PVDF/Ppy film. The electronic-skin under applied deformation can actively output piezoelectric voltage, and the outputting signal can be significantly influenced by UV illumination. The piezoelectric output can act as both the photodetecting signal and electricity power. The reliability is demonstrated over 200 light on-off cycles. The sensing unit matrix of 6 × 6 pixels on the electronic-skin can realize image recognition through mapping multi-point UV stimuli. This self-powered vision electronic-skin that simply mimics human retina may have potential application in vision substitution.
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Self-powered wearable sensing-textiles for real-time detecting environmental atmosphere and body motion have been presented. The textile is based on highly-stretchable conductive ecoflex fiber modified with multiwall carbon nanotube and polyaniline (PANI) derivatives (acting as one electrode). The surface of the fiber is twined with varnished wire (acting as the other electrode). Upon applied deformation of stretching or bending, the sensing-textile can harvest the mechanical energy and output electric signals through the triboelectrification effect between PANI and varnished wire. After being attached on the human body, the triboelectric output of the sensing-textile can be used to monitor body motion, including finger bending and body stretching. Interestingly, the triboelectric output of the sensing-textile is significantly dependent on the atmosphere, which can actively distinguish different gas species in the environment. The sensitivity, stability and selectivity against ethanol, ammonia, acetone and formaldehyde are high. The response against 400 ppm ethanol vapor at room temperature is up to 54.73%. The current density is 2.1 × 10-4 A m-2, and the power density is 4.2 × 10-5 W m-2. During both the motion detecting and gas sensing processes, no external electricity power is needed. The triboelectric signal can be treated as not only the sensing signal but also the power source for driving the device. The working mechanism is based on surface-triboelectric coupling effect. The present results can promote the development of self-powered wearable electronics.
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A new self-powered wearable gustation electronic skin for mimicking taste buds has been realized based on enzyme-modified/ZnO nanowire arrays on patterned-electrode flexible substrate. The e-skin can actively taste beverages or fruits without any external electric power. Through the piezoelectric-enzymatic reaction coupling effect, the nanowires can harvest the mechanical energy of body movement and output piezoelectric signal. The piezoelectric output is significantly dependent on the concentration of target analyte. The response for detecting 2 × 10-2 M ascorbic acid (ascorbate acid oxidase@ZnO) is up to 171.747, and the selectivity is high. The response for detecting 50% alcohol (alcohol oxidase@ZnO) is up to 45.867. Our results provide a new research direction for the development of multifunctional e-skin and expand the study scope for self-powered bionic systems.
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Oxirredutases do Álcool/metabolismo , Ascorbato Oxidase/metabolismo , Fontes de Energia Elétrica , Papilas Gustativas/fisiologia , Paladar/fisiologia , Dispositivos Eletrônicos Vestíveis , Técnicas Biossensoriais , Humanos , Óxido de Zinco/químicaRESUMO
Oxygenates with carbonyl and hydroperoxy functional groups are important intermediates that are generated during the autoxidation of organic compounds in the atmosphere and during the autoignition of transport fuels. In the troposphere, the degradation of carbonyl hydroperoxides leads to low-vapor-pressure polyfunctional species that may precipitate in clouds and fog droplets or to the formation of secondary organic aerosols (SOAs). In combustion, the fate of carbonyl hydroperoxides is important for the performance of advanced combustion engines, especially for autoignition. A key fate of the carbonyl hydroperoxides is reaction with OH radicals, for which kinetics data are experimentally unavailable. Here, we study 4-hydroperoxy-2-pentanone (CH3C(âO)CH2CH(OOH)CH3) as a model compound to clarify the kinetics of OH reactions with carbonyl hydroperoxides, in particular H atom abstraction and OH addition reactions. With a combination of electronic structure calculations, we determine previously missing thermochemical data, and with multipath variational transition state theory (MP-VTST), a multidimensional tunneling (MT) approximation, multiple-structure anharmonicity, and torsional potential anharmonicity, we obtained much more accurate rate constants than the ones that can computed by conventional single-structure harmonic transition state theory (TST) and than the empirically estimated rate constants that are currently used in atmospheric and combustion modeling. The roles of various factors in determining the rates are elucidated. The pressure-dependent rate constants for the addition reaction are computed using system-specific quantum RRK theory. The calculated temperature range is 298-2400 K, and the pressure range is 0.01-100 atm. The accurate thermodynamic and kinetics data determined in this work are indispensable in the global modeling of SOAs in atmospheric science and in the detailed understanding and prediction of ignition properties of hydrocarbons and alternative fuels.
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A wide range of hydroperoxides (C1-C3 alkyl hydroperoxides, C3-C7 alkenyl hydroperoxides, C7 ketohydroperoxides, and hydrogen peroxide (H2O2)), as well as ketene and diones, have been quantified during the gas-phase oxidation of n-heptane. Some of these species, as well as C10 alkenyl hydroperoxides and ketohydroperoxides, were also measured during the oxidation of n-decane. These experiments were performed using an atmospheric-pressure jet-stirred reactor at temperatures from 500 to 1100 K and one of three analytical methods, time-of-flight mass spectrometry combined with tunable synchrotron photoionization with a molecular beam sampling: time-of-flight mass spectrometry combined with laser photoionization with a capillary tube sampling, continuous wave cavity ring-down spectroscopy with sonic probe sampling. The experimental temperature at which the maximum mole fraction is observed increases significantly for alkyl hydroperoxides, alkenyl hydroperoxides, and then more so again for hydrogen peroxide, compared to ketohydroperoxides. The influence of the equivalence ratio from 0.25 to 4 on the formation of these peroxides has been studied during n-heptane oxidation. The up-to-date detailed kinetic oxidation models for n-heptane and for n-decane found in the literature have been used to discuss the possible pathways by which these peroxides, ketene, and diones are formed. In general, the model predicts well the reactivity of the two fuels, as well as the formation of major intermediates.
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Rational design of non-noble materials as highly efficient, economical, and durable bifunctional catalysts for oxygen evolution and reduction reactions (OER/ORR) is currently a critical obstacle for rechargeable metal-air batteries. A new route involving S was developed to achieve atomic dispersion of Fe-Nx species on N and S co-decorated hierarchical carbon layers, resulting in single-atom bifunctional OER/ORR catalysts for the first time. The abundant atomically dispersed Fe-Nx species are highly catalytically active, the hierarchical structure offers more opportunities for active sites, and the electrical conductivity is greatly improved. The obtained electrocatalyst exhibits higher limiting current density and a more positive half-wave potential for ORR, as well as a lower overpotential for OER under alkaline conditions. Moreover, a rechargeable Zn-air battery device comprising this hybrid catalyst shows superior performance compared to Pt/C catalyst. This work will open a new avenue to design advanced bifunctional catalysts for reversible energy storage and conversion devices.