Projections of air pollutant emissions and its impacts on regional air quality in China in 2020

Anthropogenic emissions of air pollutants in China influence not only local and regional environments but also the global atmospheric environment; therefore, it is important to understand how China's air pollutant emissions will change and how they will affect regional air quality in the future. Emission scenarios in 2020 were projected using forecasts of energy consumption and emission control strategies based on emissions in 2005, and on recent development plans for key industries in China. We developed four emission scenarios: REF[0] (current control legislations and implementation status), PC[0] (improvement of energy efficiencies and current environmental legislation), PC[1] (improvement of energy efficiencies and better implementation of environmental legislation), and PC[2] (improvement of energy efficiencies and strict environmental legislation). Under the REF[0] scenario, the emission of SO2, NOx, VOC and NH3 will increase by 17%, 50%, 49% and 18% in 2020, while PM10 emissions will be reduced by 10% over East China, compared to that in 2005. In PC[2], sustainable energy polices will reduce SO2, NOx and PM10 emissions by 4.1 Tg, 2.6 Tg and 1.8 Tg, respectively; better implementation of current control policies will reduce SO2, NOx and PM10 emission by 2.9 Tg, 1.8 Tg, and 1.4 Tg, respectively; strict emission standards will reduce SO2, NOx and PM10 emissions by 3.2 Tg, 3.9 Tg, and 1.7 Tg, respectively. Under the PC[2] scenario, SO2 and PM10 emissions will decrease by 18% and 38%, while NOx and VOC emissions will increase by 3% and 8%, compared to that in 2005. Future air quality in China was simulated using the Community Multi-scale Air Quality Model (CMAQ). Under RE[0] emissions, compared to 2005, the surface concentrations of SO2, NO2, hourly maximum ozone in summer, PM2.5, total sulfur and nitrogen depositions will increase by 28%, 41%, 8%, 8%, 19% and 25%, respectively, over east China. Under the PC[2] emission scenario, the surface concentrations of SO2, M2.5, total sulfur depositions will decrease by 18%, 16% and 15%, respectively, and the surface concentrations of NO2, nitrate, hourly maximum ozone in summer, total nitrogen depositions will be kept as 2005 level, over east China. The individual impacts of SO2, NOx, NH3, NMVOC and primary PM emission changes on ozone and PM.5 concentrations have been analyzed using sensitivity analysis. The results suggest that NOx emission control need to be enhanced during the summertime to obtain both ozone and PM2.5 reduction benefits. NH3 emission controls should also be considered in order to reduce both nitrate concentration and total nitrogen deposition in the future

Two-Dimensional Infrared Spectroscopy of Antiparallel β-Sheet Secondary Structure

We investigate the sensitivity of femtosecond Fourier transform two-dimensional infrared spectroscopy to protein secondary structure with a study of antiparallel β-sheets. The results show that 2D IR spectroscopy is more sensitive to structural differences between proteins than traditional infrared spectroscopy, providing an observable that allows comparison to quantitative models of protein vibrational spectroscopy. 2D IR correlation spectra of the amide I region of poly-L-lysine, concanavalin A, ribonuclease A, and lysozyme show cross-peaks between the IR-active transitions that are characteristic of amide I couplings for polypeptides in antiparallel hydrogen-bonding registry. For poly-L-lysine, the 2D IR spectrum contains the eight-peak structure expected for two dominant vibrations of an extended, ordered antiparallel β-sheet. In the proteins with antiparallel β-sheets, interference effects between the diagonal and cross-peaks arising from the sheets, combined with diagonally elongated resonances from additional amide transitions, lead to a characteristic “Z”-shaped pattern for the amide I region in the 2D IR spectrum. We discuss in detail how the number of strands in the sheet, the local configurational disorder in the sheet, the delocalization of the vibrational excitation, and the angle between transition dipole moments affect the position, splitting, amplitude, and line shape of the cross-peaks and diagonal peaks.

Outcome of radiotherapy in T1 glottic carcinoma: A population-based study

We evaluated the radiation outcome and prognostic factors in a population-based study of early (T1N0M0) glottic carcinoma. Survival parameters and prognostic factors were evaluated by uni- and multivariate analysis in 316 consecutive irradiated patients with T1 glottic carcinoma in the Comprehensive Cancer Center West region of the western Netherlands. Median follow-up was 70 months (range 1-190 months). Five and ten-year local control was 86 and 84%. Disease specific survival was 97% at 5 and 10 years. In multivariate analysis, pre-existent laryngeal hypertrophic laryngitis was the only predictive factor for local control (relative risk = 3.0, P = 0.02). Comorbidity was prognostic for overall survival. No factor was predictive for disease specific survival. Pre-existent laryngeal hypertrophic laryngitis is a new risk factor associated with reduced local control in T1 glottic carcinoma treated with radiotherapy

The correlation of RNase A enzymatic activity with the changes in the distance between Nepsilon2-His12 and N delta1-His119 upon addition of stabilizing and destabilizing salts.

The effect of stabilizing and destabilizing salts on the catalytic behavior of ribonuclease A (RNase A) was investigated at pH 7.5 and 25 degrees C, using spectrophotometric, viscometric and molecular dynamic methods. The changes in the distance between N(epsilon2) of His(12) and N(delta1) of His(119) at the catalytic center of RNase A upon the addition of sodium sulfate, sodium hydrogen sulfate and sodium thiocyanate were evaluated by molecular dynamic methods. The compactness and expansion in terms of Stokes radius of RNase A upon the addition of sulfate ions as kosmotropic salts, and thiocyanate ion as a chaotropic salt, were estimated by viscometric measurements. Enzyme activity was measured using cytidine 2', 3'-cyclic monophosphate as a substrate. The results from the measurements of distances between N(epsilon2) of His(12) and N(delta1) of His(119) and Stokes radius suggest (i) that the presence of sulfate ions decreases the distance between the catalytic His residues and increases the globular compactness, and (ii) that there is an expansion of the enzyme surface as well as elongation of the catalytic center in the presence of thiocyanate ion. These findings are in agreement with activity measurements

Direct Functionalization of Nitrogen Heterocycles via Rh-Catalyzed C−H Bond Activation

Nitrogen heterocycles are present in many compounds of enormous practical importance, ranging from pharmaceutical agents and biological probes to electroactive materials. Direct functionalization of nitrogen heterocycles through C−H bond activation constitutes a powerful means of regioselectively introducing a variety of substituents with diverse functional groups onto the heterocycle scaffold. Working together, our two groups have developed a family of Rh-catalyzed heterocycle alkylation and arylation reactions that are notable for their high level of functional-group compatibility. This Account describes our work in this area, emphasizing the relevant mechanistic insights that enabled synthetic advances and distinguished the resulting transformations from other methods. We initially discovered an intramolecular Rh-catalyzed C-2 alkylation of azoles by alkenyl groups. That reaction provided access to a number of di-, tri-, and tetracyclic azole derivatives. We then developed conditions that exploited microwave heating to expedite these reactions. While investigating the mechanism of this transformation, we discovered that a novel substrate-derived Rh−N-heterocyclic carbene (NHC) complex was involved as an intermediate. We then synthesized analogous Rh−NHC complexes directly by treating precursors to the intermediate [RhCl(PCy3)2] with N-methylbenzimidazole, 3-methyl-3,4-dihydroquinazoline, and 1-methyl-1,4-benzodiazepine-2-one. Extensive kinetic analysis and DFT calculations supported a mechanism for carbene formation in which the catalytically active RhCl(PCy3)2 fragment coordinates to the heterocycle before intramolecular activation of the C−H bond occurs. The resulting Rh−H intermediate ultimately tautomerizes to the observed carbene complex. With this mechanistic information and the discovery that acid cocatalysts accelerate the alkylation, we developed conditions that efficiently and intermolecularly alkylate a variety of heterocycles, including azoles, azolines, dihydroquinazolines, pyridines, and quinolines, with a wide range of functionalized olefins. We demonstrated the utility of this methodology in the synthesis of natural products, drug candidates, and other biologically active molecules. In addition, we developed conditions to directly arylate these heterocycles with aryl halides. Our initial conditions that used PCy3 as a ligand were successful only for aryl iodides. However, efforts designed to avoid catalyst decomposition led to the development of ligands based on 9-phosphabicyclo[4.2.1]nonane (phoban) that also facilitated the coupling of aryl bromides. We then replicated the unique coordination environment, stability, and catalytic activity of this complex using the much simpler tetrahydrophosphepine ligands and developed conditions that coupled aryl bromides bearing diverse functional groups without the use of a glovebox or purified reagents. With further mechanistic inquiry, we anticipate that researchers will better understand the details of the aforementioned Rh-catalyzed C−H bond functionalization reactions, resulting in the design of more efficient and robust catalysts, expanded substrate scope, and new transformations

Revisiting in vivo staining with alizarin red S - a valuable approach to analyse zebrafish skeletal mineralization during development and regeneration

Background The correct evaluation of mineralization is fundamental for the study of skeletal development, maintenance, and regeneration. Current methods to visualize mineralized tissue in zebrafish rely on: 1) fixed specimens; 2) radiographic and μCT techniques, that are ultimately limited in resolution; or 3) vital stains with fluorochromes that are indistinguishable from the signal of green fluorescent protein (GFP)-labelled cells. Alizarin compounds, either in the form of alizarin red S (ARS) or alizarin complexone (ALC), have long been used to stain the mineralized skeleton in fixed specimens from all vertebrate groups. Recent works have used ARS vital staining in zebrafish and medaka, yet not based on consistent protocols. There is a fundamental concern on whether ARS vital staining, achieved by adding ARS to the water, can affect bone formation in juvenile and adult zebrafish, as ARS has been shown to inhibit skeletal growth and mineralization in mammals. Results Here we present a protocol for vital staining of mineralized structures in zebrafish with a low ARS concentration that does not affect bone mineralization, even after repetitive ARS staining events, as confirmed by careful imaging under fluorescent light. Early and late stages of bone development are equally unaffected by this vital staining protocol. From all tested concentrations, 0.01 % ARS yielded correct detection of bone calcium deposits without inducing additional stress to fish. Conclusions The proposed ARS vital staining protocol can be combined with GFP fluorescence associated with skeletal tissues and thus represents a powerful tool for in vivo monitoring of mineralized structures. We provide examples from wild type and transgenic GFP-expressing zebrafish, for endoskeletal development and dermal fin ray regeneration

Historical and future anthropogenic warming effects on droughts, fires and fire emissions of CO2 and PM2.5 in equatorial Asia when 2015-like El Niño events occur

In 2015, El Niño contributed to severe droughts in equatorial Asia (EA). The severe droughts enhanced fire activity in the dry season (June–November), leading to massive fire emissions of CO2 and aerosols. Based on large event attribution ensembles of the MIROC5 atmospheric global climate model, we suggest that historical anthropogenic warming increased the chances of meteorological droughts exceeding the 2015 observations in the EA area. We also investigate changes in drought in future climate simulations, in which prescribed sea surface temperature data have the same spatial patterns as the 2015 El Niño with long-term warming trends. Large probability increases of stronger droughts than the 2015 event are projected when events like the 2015 El Niño occur in the 1.5 and 2.0&thinsp;∘C warmed climate ensembles according to the Paris Agreement goals. Further drying is projected in the 3.0&thinsp;∘C ensemble according to the current mitigation policies of nations. We use observation-based empirical functions to estimate burned area, fire CO2 emissions and fine (&lt;2.5&thinsp;µm) particulate matter (PM2.5) emissions from these simulations of precipitation. There are no significant increases in the chances of burned area and CO2 and PM2.5 emissions exceeding the 2015 observations due to past anthropogenic climate change. In contrast, even if the 1.5 and 2.0&thinsp;∘C goals are achieved, there are significant increases in the burned area and CO2 and PM2.5 emissions. If global warming reaches 3.0&thinsp;∘C, as is expected from the current mitigation policies of nations, the chances of burned areas and CO2 and PM2.5 emissions exceeding the 2015 observed values become approximately 100&thinsp;%, at least in the single model ensembles. We also compare changes in fire CO2 emissions due to climate change and the land-use CO2 emission scenarios of five shared socioeconomic pathways, where the effects of climate change on fire are not considered. There are two main implications. First, in a national policy context, future EA climate policy will need to consider these climate change effects regarding both mitigation and adaptation aspects. Second is the consideration of fire increases changing global CO2 emissions and mitigation strategies, which suggests that future climate change mitigation studies should consider these factors.</p

Breakdown of supersaturation barrier links protein folding to amyloid formation

The thermodynamic hypothesis of protein folding, known as the “Anfinsen’s dogma” states that the native structure of a protein represents a free energy minimum determined by the amino acid sequence. However, inconsistent with the Anfinsen’s dogma, globular proteins can misfold to form amyloid fibrils, which are ordered aggregates associated with diseases such as Alzheimer’s and Parkinson’s diseases. Here, we present a general concept for the link between folding and misfolding. We tested the accessibility of the amyloid state for various proteins upon heating and agitation. Many of them showed Anfinsen-like reversible unfolding upon heating, but formed amyloid fibrils upon agitation at high temperatures. We show that folding and amyloid formation are separated by the supersaturation barrier of a protein. Its breakdown is required to shift the protein to the amyloid pathway. Thus, the breakdown of supersaturation links the Anfinsen’s intramolecular folding universe and the intermolecular misfolding universe

Clinical practice guideline on the optimal radiotherapeutic management of brain metastases

BACKGROUND: An evidence-based clinical practice guideline on the optimal radiotherapeutic management of single and multiple brain metastases was developed. METHODS: A systematic review and meta-analysis was performed. The Supportive Care Guidelines Group formulated clinical recommendations based on their interpretation of the evidence. External review of the report by Ontario practitioners was obtained through a mailed survey, and final approval was obtained from Cancer Care Ontario's Practice Guidelines Coordinating Committee (PGCC). RESULTS: One hundred and nine Ontario practitioners responded to the survey (return rate 44%). Ninety-six percent of respondents agreed with the interpretation of the evidence, and 92% agreed that the report should be approved. Minor revisions were made based on feedback from external reviewers and the PGCC. The PGCC approved the final practice guideline report. CONCLUSIONS: For adult patients with a clinical and radiographic diagnosis of brain metastases (single or multiple) we conclude that, • Surgical excision should be considered for patients with good performance status, minimal or no evidence of extracranial disease, and a surgically accessible single brain metastasis. • Postoperative whole brain radiotherapy (WBRT) should be considered to reduce the risk of tumour recurrence for patients who have undergone resection of a single brain metastasis. • Radiosurgery boost with WBRT may improve survival in select patients with unresectable single brain metastases. • The whole brain should be irradiated for multiple brain metastases. Standard dose-fractionation schedules are 3000 cGy in 10 fractions or 2000 cGy in 5 fractions. • Radiosensitizers are not recommended outside research studies. • In select patients, radiosurgery may be considered as boost therapy with WBRT to improve local tumour control. Radiosurgery boost may improve survival in select patients. • Chemotherapy as primary therapy or chemotherapy with WBRT remains experimental. • Supportive care is an option but there is a lack of Level 1 evidence as to which subsets of patients should be managed with supportive care alone. Qualifying statements addressing factors to consider when applying these recommendations are provided in the full report. The rigorous development, external review and approval process has resulted in a practice guideline that is strongly endorsed by Ontario practitioners

Photochemical roles of rapid economic growth and potential abatement strategies on tropospheric ozone over South and East Asia in 2030

A regional air quality simulation framework including the Weather Research and Forecasting modeling system (WRF), the Community Multi-scale Air Quality modeling system (CMAQ), and precursor emissions to simulate tropospheric ozone over South and East Asia is introduced. Concentrations of tropospheric ozone and related species simulated by the framework are validated by comparing with observation data of surface monitoring, ozonesondes, and satellites obtained in 2010. The simulation demonstrates acceptable performance on tropospheric ozone over South and East Asia at regional scale. Future energy consumption, carbon dioxide (CO2), nitrogen oxides (NOx), and volatile organic compound (VOC) emissions in 2030 under three future scenarios are estimated. One of the scenarios assumes a business-as-usual (BAU) pathway, and other two scenarios consider implemenation of additional energy and environmental strategies to reduce energy consumption, CO2, NOx, and VOC emissions in China and India. Future surface ozone under these three scenarios is predicted by the simulation. The simulation indicates future surface ozone significantly increases around India for a whole year and around northeastern China in summer. NOx is a main driver on significant seasonal increase of surface ozone, whereas VOC as well as increasing background ozone and methane is also an important factor on annual average of surface ozone in East Asia. Warmer weather around India is also preferable for significant increase of surfac ozone. Additional energy and environmental strategies assumed in future scenarios are expected to be effective to reduce future surface ozone over South and East Asia