Sn(II)/PN@AC catalysts: synthesis, physical-chemical characterization, and applications.

In this study, the novel tin-based catalysts (Sn(II)/PN@AC) were prepared using the phosphorus and nitrogen dual-modified activated carbon as support and SnCl2 as active compounds, as well as then evaluated in acetylene hydrochlorination. Under the reaction temperature of 180 °C and an acetylene gas hourly space velocity (GHSV-C2H2) of 30 h-1, the 15%Sn(II)/PN@AC-550 showed the initial acetylene conversion of 100% and vinyl chloride selectivity over 98.5%. Additionally, the deactivation rate of 15%Sn(II)/PN@AC-550 reached 0.47% h-1, which was lower than that of 15%Sn(II)/AC-550 (1.02% h-1), suggesting that PN@AC-550 as novel support can retarded the deactivation of Sn(II)/AC-550 catalysts during acetylene hydrochlorination. Based on the catalytic tests and characterization results (XRD, Raman, BET surface area, TEM, C2H2-TPD, H2-TPR, XPS, FT-IR, TGA, and ICP), it demonstrated that PN@AC-550 as support could effectively improve the dispersion of tin species, retard the formation of coke deposition, lessen the oxidation of SnCl2 during the preparation process, as well as relatively inhibit the leach of tin species during the reaction. By combing the FTIR results and Rideal-Eley mechanism, we proposed that that HSnCl3 was transition state of SnCl2 in catalysis acetylene hydrochlorination and then adsorbed the acetylene to produce the vinyl chloride.

Synthesis of a New Water-Soluble Melatonin Derivative with Low Toxicity and a Strong Effect on Sleep Aid.

A new melatonin sulfonate derivative sodium 4-(3-(2-acetamidoethyl)-5-methoxy-1H-indol-1-yl) butane-1-sulfonate (MLTBS) with higher water solubility (695 times) and lower cytotoxicity than natural melatonin (MLT) was synthesized, yet with the same sleep aid function. The poor solubility of MLT in water has been improved with a simple chemical reaction, which solves the poor solubility of melatonin in water, overcoming the safety problem caused by adding organic reagents such as dimethyl sulfoxide (DMSO) and ethanol to increase the solubility. Moreover, the modified MLT still has the same sleep aid effect as the natural MLT and higher biological safety. As a novel potential drug for sleep aid, the new MLT derivative could also flourish the application and research of this molecule in medicine and biology.

Adaptive Kernel Value Caching for SVM Training.

Support vector machines (SVMs) can solve structured multioutput learning problems such as multilabel classification, multiclass classification, and vector regression. SVM training is expensive, especially for large and high-dimensional data sets. The bottleneck of the SVM training often lies in the kernel value computation. In many real-world problems, the same kernel values are used in many iterations during the training, which makes the caching of kernel values potentially useful. The majority of the existing studies simply adopt the least recently used (LRU) replacement strategy for caching kernel values. However, as we analyze in this article, the LRU strategy generally achieves high hit ratio near the final stage of the training but does not work well in the whole training process. Therefore, we propose a new caching strategy called EFU (less frequently used), which replaces the EFU kernel values that enhance least frequently used (LFU). Our experimental results show that EFU often has 20% higher hit ratio than LRU in the training with the Gaussian kernel. To further optimize the strategy, we propose a caching strategy called hybrid caching for the SVM training (HCST), which has a novel mechanism to automatically adapt the better caching strategy in different stages of the training. We have integrated the caching strategy into ThunderSVM, a recent SVM library on many-core processors. Our experiments show that HCST adaptively achieves high hit ratios with little runtime overhead among different problems including multilabel classification, multiclass classification, and regression problems. Compared with other existing caching strategies, HCST achieves 20% more reduction in training time on average.

Thermal decomposition mechanism of O-acetyl-4-O-methylglucurono-xylan.

O-acetyl-4-O-methylglucurono-xylan is selected as a model compound because of its abundant O-acetyl and 4-O-methylglucuronic acid groups as side chains of hemicellulose. The detailed decomposition pathways of O-acetyl-4-O-methylglucurono-xylan are investigated by using density functional theory (DFT) and transition state theory. In addition, the possible pyrolysis pathways of 4-O-methylglucuronic acid, based on the Mayer bond order values, are predicted. The results indicate that the most energetically favored initial reaction of O-acetyl-4-O-methylglucurono-xylan is the cleavage of the 4-O-methylglucuronic acid unit. Furfural can be obtained through the ring-opening of 4-O-methylglucuronic acid in three different pathways. The O-methyl group is predominantly responsible for the generation of CH3OH. In addition, the formation pathways of a special furan-derived product 2-hydroxymethylene-tetrahydrofuran-3-one are first validated by DFT calculation. The rate-determining steps to form 2-hydroxymethylene-tetrahydrofuran-3-one are the cyclization reaction and enol-keto tautomerization. Anhydroxylopyranose and dianhydroxylopyranose can be produced through intramolecular dehydration and glycosidic bond cleavage reactions. Graphical abstract The main pyrolysis products distribution of O-acetyl-4-O-methylglucurono-xylan.

Thermal degradation behavior of pectin in citrus wastes with density functional theory study.

Citrus wastes contain large amounts of pectin as the main constituent in addition to cellulose, lignin and hemicellulose. The thermal degradation behaviors and products distribution from the fast pyrolysis of citrus wastes are different from lignocellulosic biomass due to the high content of pectin. In view of this, the detailed decomposition behaviors of pectin are investigated by using density functional theory (DFT). The calculation results indicate that the most energetically favored initial reaction of pectin is the cleavage of α-1,4-glycoside bond (C1O bond) with an energy barrier of 126.4 kJ/mol. In addition, compared with the reaction energy barriers, it can be seen that the formation of CO, CH4 and furan are more difficult than that of CO2, methanol and furfural, respectively. The comprehensive kinetic analysis indicates that Path-A2-2 should be the most favorable pathway for the formation of acetaldehyde. The rate-determining steps of the formation of furan and furfural are dehydration reactions while decarbonylation reaction is the result of the rate-determining step of the formation of methyl 2-furoate and propanone.

Impact of air pollution control policies on future PM2.5 concentrations and their source contributions in China.

To investigate the impact of air pollutant control policies on future PM2.5 concentrations and their source contributions in China, we developed four future scenarios for 2030 based on a 2013 emission inventory, and conducted air quality simulations for each scenario using the chemical transport model GEOS-Chem (version 9.1.3). Two energy scenarios i.e., current legislation (CLE) and with additional measures (WAM), were developed to project future energy consumption, reflecting, respectively, existing legislation and implementation status as of the end of 2012, and new energy-saving policies that would be released and enforced more stringently. Two end-of-pipe control strategies, i.e., current control technologies (until 2017) and more stringent control technologies (until 2030), were also developed. The combinations of energy scenarios and end-of-pipe control strategies constitute four emission scenarios (2017-CLE, 2030-CLE, 2017-WAM, and 2030-WAM) evaluated in simulations. PM2.5 concentrations at national level were estimated to be 57 µg/m3 in the base year 2013, and 58 µg/m3, 42 µg/m3, 42 µg/m3, and 30 µg/m3 under the 2017-CLE, 2030-CLE, 2017-WAM, and 2030-WAM scenarios in 2030, respectively. Large PM2.5 reductions between 2013 and 2030 were estimated for heavily polluted regions (Sichuan Basin, Middle Yangtze River, North China). The energy-saving policies show similar effects to the end-of-pipe emission control measures, but the relative importance of these two groups of policies varies in different regions. Absolute contributions to PM2.5 concentrations from most major sources declined from 2017-CLE to 2030-WAM. With respect to fractional contributions, most coal-burning sectors (including power plant, industrial and residential coal burning) increased from 2017-CLE to 2030-WAM, due to larger reductions from non-coal sources, including transportation and biomass open burning. Residential combustion and open burning had much lower fractional contribution to ambient PM2.5 concentrations in the 2017-WAM/2030-WAM compared to the 2017-CLE/2030-CLE scenarios. Fractional contributions from transportation were reduced dramatically in 2030-CLE and 2030-WAM compared to 2017-CLE/2017-WAM, due to the enforcement of stringent end-of-pipe emission controls. Across all scenarios, coal combustion remained the single largest contributor to PM2.5 concentrations in 2030. Reducing PM2.5 emissions from coal combustion remains a strategic priority for air quality management in China.

Impact of aerosols on ice crystal size.

The interactions between aerosols and ice clouds represent one of the largest uncertainties in global radiative forcing from pre-industrial time to the present. In particular, the impact of aerosols on ice crystal effective radius (R ei), which is a key parameter determining ice clouds' net radiative effect, is highly uncertain due to limited and conflicting observational evidence. Here we investigate the effects of aerosols on R ei under different meteorological conditions using 9-year satellite observations. We find that the responses of R ei to aerosol loadings are modulated by water vapor amount in conjunction with several other meteorological parameters. While there is a significant negative correlation between R ei and aerosol loading in moist conditions, consistent with the "Twomey effect" for liquid clouds, a strong positive correlation between the two occurs in dry conditions. Simulations based on a cloud parcel model suggest that water vapor modulates the relative importance of different ice nucleation modes, leading to the opposite aerosol impacts between moist and dry conditions. When ice clouds are decomposed into those generated from deep convection and formed in situ, the water vapor modulation remains in effect for both ice cloud types, although the sensitivities of R ei to aerosols differ noticeably between them due to distinct formation mechanisms. The water vapor modulation can largely explain the difference in the responses of R ei to aerosol loadings in various seasons. A proper representation of the water vapor modulation is essential for an accurate estimate of aerosol-cloud radiative forcing produced by ice clouds.

Enhanced PM2.5 pollution in China due to aerosol-cloud interactions.

Aerosol-cloud interactions (aerosol indirect effects) play an important role in regional meteorological variations, which could further induce feedback on regional air quality. While the impact of aerosol-cloud interactions on meteorology and climate has been extensively studied, their feedback on air quality remains unclear. Using a fully coupled meteorology-chemistry model, we find that increased aerosol loading due to anthropogenic activities in China substantially increases column cloud droplet number concentration and liquid water path (LWP), which further leads to a reduction in the downward shortwave radiation at surface, surface air temperature and planetary boundary layer (PBL) height. The shallower PBL and accelerated cloud chemistry due to larger LWP in turn enhance the concentrations of particulate matter with diameter less than 2.5 µm (PM2.5) by up to 33.2 µg m-3 (25.1%) and 11.0 µg m-3 (12.5%) in January and July, respectively. Such a positive feedback amplifies the changes in PM2.5 concentrations, indicating an additional air quality benefit under effective pollution control policies but a penalty for a region with a deterioration in PM2.5 pollution. Additionally, we show that the cloud processing of aerosols, including wet scavenging and cloud chemistry, could also have substantial effects on PM2.5 concentrations.

The adjoint of CMAQ.

An adjoint model for the internationally used Community Multiscale Air Quality (CMAQ) modeling platform of the U.S. EPA is developed. The adjoint version for CMAQ (CMAQ-ADJ) provides the user community with forward (decoupled direct method or DDM) and backward (adjoint) sensitivity analysis capabilities. Current implementation is for gas-phase processes. Discrete adjoints are implemented for all processes with the exception of horizontal advection, for which, because of inherent discontinuities in the advection scheme, the continuous approach is superior. The adjoint of chemistry is constructed by interfacing CMAQ with the kinetic pre-processor, which provides for increased flexibility in the choice of chemical solver and facilitates the implementation of new chemical mechanisms. The adjoint implementation is evaluated both on a process-by-process basis and for the full model. In general, adjoint results show good agreement with brute-force and DDM sensitivities. As expected for a continuous adjoint implementation in a nonlinear scheme, the agreement is not perfect for horizontal transport. Sensitivities of various air quality, public health, and environmental metrics with respect to emissions are calculated using the adjoint method. In order to show applicability to regional climate studies, as an example, the sensitivities of these metrics with respect to local temperatures are calculated.