Identification of Novel Sphydrofuran-Derived Derivatives with Lipid-Lowering Activity from the Active Crude Extracts of Nocardiopsis sp. ZHD001.

Lipid-lowering is one of the most effective methods of prevention and treatment for cardiovascular diseases. However, most clinical lipid-lowering drugs have adverse effects and cannot achieve the desired efficacy in some complex hyperlipidemia patients, so it is of great significance to develop safe and effective novel lipid-lowering drugs. In the course of our project aimed at discovering the chemical novelty and bioactive natural products of marine-derived actinomycetes, we found that the organic crude extracts (OCEs) of Nocardiopsis sp. ZHD001 exhibited strong in vivo efficacies in reducing weight gain, lowering LDL-C, TC, and TG levels, and improving HDL-C levels in high-fat-diet-fed mice models. Chemical investigations of the active OCEs led to identifying two new sphydrofuran-derived compounds (1-2) and one known 2-methyl-4-(1-glycerol)-furan (3). Their structures were elucidated by the analysis of HRESIMS, 1D and 2D NMR spectroscopic data, and ECD calculations. Among these compounds, compound 1 represents a novel rearranged sphydrofuran-derived derivative. Bioactivity evaluations of these pure compounds showed that all the compounds exhibited significant lipid-lowering activity with lower cytotoxicity in vitro compared to simvastatin. Our results demonstrate that sphydrofuran-derived derivatives might be promising candidates for lipid-lowering drugs.

Investigating Changes in Ozone Formation Chemistry during Summertime Pollution Events over the Northeastern United States.

Understanding the local-scale spatial and temporal variability of ozone formation is crucial for effective mitigation. We combine tropospheric vertical column densities (VCDTrop) of formaldehyde (HCHO) and nitrogen dioxide (NO2), referred to as HCHO-VCDTrop and NO2-VCDTrop, retrieved from airborne remote sensing and the TROPOspheric Monitoring Instrument (TROPOMI) with ground-based measurements to investigate changes in ozone precursors and the inferred chemical production regime on high-ozone days in May-August 2018 over two Northeast urban domains. Over New York City (NYC) and Baltimore/Washington D.C. (BAL/DC), HCHO-VCDTrop increases across the domain, but higher NO2-VCDTrop occurs mainly in urban centers on ozone exceedance days (when maximum daily 8 h average (MDA8) ozone exceeds 70 ppb at any monitor in the region). The ratio of HCHO-VCDTrop to NO2-VCDTrop, proposed as an indicator of the sensitivity of local surface ozone production rates to its precursors, generally increases on ozone exceedance days, implying a transition toward a more NOx-sensitive ozone production regime that should lead to higher efficacy of NOx controls on the highest ozone days in NYC and BAL/DC. Warmer temperatures and enhanced influence from emissions in the local boundary layer on the high-ozone days are accompanied by slower wind speeds in BAL/DC but stronger, southwesterly winds in NYC.

Atroposelective Construction of Nine-Membered Carbonate-Bridged Biaryls.

We herein demonstrated an efficient method for the atroposelective construction of nine-membered carbonate-bridged biaryls through vinylidene ortho-quinone methide (VQM) intermediates. Diverse products with desirable pharmacological features were synthesized in satisfying yields and good to excellent enantioselectivities. In subsequent bioassays, several agents showed considerable antiproliferative activity via the mitochondrial-related apoptosis mechanism. Further transformations produced more structural diversity and may inspire new ideas for developing functional molecules.

Organocatalytic Enantioselective Construction of Chiral Azepine Skeleton Bearing Multiple-Stereogenic Elements.

Enantioselective construction of molecules bearing multiple stereogenic elements is increasingly related to the synthesis of enantiopure natural products, pharmaceuticals, and functional materials. However, atom-economical and enantioselective approaches to install multiple stereogenic elements in a small molecular template by limited chemical transformation remain challenging. We describe an organocatalytic enantioselective method for the preparation of polychiral molecules bearing four types of stereogenic elements in fused azepines via vinylidene ortho-quinone methide (VQM)-mediated intramolecular electrophilic aromatic substitution. This method was proved robust with a wide range of substrate scope (46-92 % yield), with excellent diastereoselectivity (>20:1 dr) and enantioselectivity achieved (up to 97 % ee). Optical properties and Ru3+ -induced fluorescence responses of these compounds suggest their potential applications in optoelectronic materials and heavy metal ion detection.

Widespread decline of Congo rainforest greenness in the past decade.

Tropical forests are global epicentres of biodiversity and important modulators of climate change, and are mainly constrained by rainfall patterns. The severe short-term droughts that occurred recently in Amazonia have drawn attention to the vulnerability of tropical forests to climatic disturbances. The central African rainforests, the second-largest on Earth, have experienced a long-term drying trend whose impacts on vegetation dynamics remain mostly unknown because in situ observations are very limited. The Congolese forest, with its drier conditions and higher percentage of semi-evergreen trees, may be more tolerant to short-term rainfall reduction than are wetter tropical forests, but for a long-term drought there may be critical thresholds of water availability below which higher-biomass, closed-canopy forests transition to more open, lower-biomass forests. Here we present observational evidence for a widespread decline in forest greenness over the past decade based on analyses of satellite data (optical, thermal, microwave and gravity) from several independent sensors over the Congo basin. This decline in vegetation greenness, particularly in the northern Congolese forest, is generally consistent with decreases in rainfall, terrestrial water storage, water content in aboveground woody and leaf biomass, and the canopy backscatter anomaly caused by changes in structure and moisture in upper forest layers. It is also consistent with increases in photosynthetically active radiation and land surface temperature. These multiple lines of evidence indicate that this large-scale vegetation browning, or loss of photosynthetic capacity, may be partially attributable to the long-term drying trend. Our results suggest that a continued gradual decline of photosynthetic capacity and moisture content driven by the persistent drying trend could alter the composition and structure of the Congolese forest to favour the spread of drought-tolerant species.

Repellent, Insecticidal and Antimicrobial Activities of Leaf Essential Oils from Three Eucalyptus Species.

Developing effective and eco-friendly antimicrobials and pesticides has become a highly important issue. The repellent, insecticidal and antimicrobial activity of essential oils (EOs) isolated by hydrodistillation from dried leaves of the three Eucalyptus species (E. cloeziana, E. umbellata and E. benthamii) were investigated. During GC/MS analysis, α-pinene (47.36 %), 1,8-cineol (38.53 %) and α-pinene (35.31 %) were identified as major components of E. cloeziana, E. umbellata and E. benthamii, respectively. The EOs from E. cloeziana exhibited the longest effective protection time (465 min, at 50.0 % w/w) for humans among the EOs studied. The effective protection time was 30 min and 300 min at concentrations of 12.5 % (w/w) and 25.0 % (w/w), respectively. Fumigating insecticidal activity of EOs from three Eucalyptus species was tested by airtight fumigation in conical flask, which indicated that essential oils had a highly and rapidly insecticidal activity on Culex pipiens quinquefasciatus. The antimicrobial activity of EOs was evaluated by using disc diffusion and agar dilution methods. There was no significant difference in the antibacterial activity of EOs from E. cloeziana and E. umbellate and they had the same MICs (20 mL/L) on Staphylococcus aureus, Salmonella typhi, Bacillus subtilis and Escherichia coli. E. benthamii had the worst microbial inhibitory effect among the three Eucalyptus essential oils and the MIC value for the test species is 40 mL/L except for Rhodotorula Harrison (10 mL/L).

Uneven winter snow influence on tree growth across temperate China.

Winter snow is an important driver of tree growth in regions where growing-season precipitation is limited. However, observational evidence of this influence at larger spatial scales and across diverse bioclimatic regions is lacking. Here, we investigated the interannual effects of winter (here defined as previous October to current February) snow depth on tree growth across temperate China over the period of 1961-2015, using a regional network of tree ring records, in situ daily snow depth observations, and gridded climate data. We report uneven effects of winter snow depth on subsequent growing-season tree growth across temperate China. There shows little effect on tree growth in drier regions that we attribute mainly to limited snow accumulation during winter. By contrast, winter snow exerts important positive influence on tree growth in stands with high winter snow accumulation (e.g., in parts of cold arid regions). The magnitude of this effect depends on the proportion of winter snow to pre-growing-season (previous October to current April) precipitation. We further observed that tree growth in drier regions tends to be increasingly limited by warmer growing-season temperature and early growing-season water availability. No compensatory effect of winter snow on the intensifying drought limitation of tree growth was observed across temperate China. Our findings point toward an increase in drought vulnerability of temperate forests in a warming climate.

Purification of angiotensin I-converting enzyme (ACE) inhibitory peptides from casein hydrolysate by IMAC-Ni2.

Casein proteins were hydrolyzed by papain to identify inhibitory peptides of angiotensin I-converting enzyme (ACE). The hydrolysate was fractionized by immobilized metal affinity chromatography (IMAC-Ni2+). The fraction with high ACE inhibitory activity was enriched and further chromatographed on a reverse-phase column to yield four fractions. Among the fractions, the L4 fraction exhibited the highest ACE inhibitory activity and was identified by sequence analysis as Trp-Tyr-Leu-His-Tyr-Ala (WYLHYA), with IC50 value of 16.22 ± 0.83 µM in vitro. This peptide was expected to be applied as an ingredient for preventing hypertension and IMAC-Ni2+ may provide a simple method for purification of ACE inhibitory peptides.

Investigation into the ring-substituted polyanilines and their application for the detection and adsorption of sulfur dioxide.

It has been demonstrated in this study that the substituents on the monomer aniline benzene ring are able to introduce the significant differences to the resulting polyaniline's collective properties. We systematically evaluated the structural perturbation effects of two substituents (methyl and methoxy) of aniline monomer through the electrochemical method. Our results showed that the methoxy group induces the less structural perturbation than the methyl counterpart, because of its partial double bond restriction. The morphologies are different for the polyaniline and the ring-substituted polyanilines, in which substituted polyanilines feature the larger porosities with the addition of these side groups. The influential effects of the methoxy side group have been further illustrated and amplified by its superior sensing performance towards the environmentally-significant sulfur dioxide gas, evaluated through the construction of the quartz crystal microbalance (QCM)-based gas sensor with these polyaniline materials. The as-constructed gas sensor's sensitivity, selectivity and stability in terms of its SO2 responses have been evaluated in details. The methoxy-substituted polyaniline was tested to show the unique gas sensing properties for the sulfur dioxide at the low concentrations (50-250 ppm) and function as the adsorbing material at the high concentrations (500-1250 ppm). Thus it can be used both as sensing material as well as a novel filter and/or storage reservoir for the removal of sulfur dioxide pollutant from the environments.

[Study on Microwave Co-Pyrolysis of Low Rank Coal and Circulating Coal Gas].

The pyrolysis of low rank coal to produce bluecoke, coal tar and gas is considered to be the optimal method to realize its clean and efficient utilization. However, the current mainstream pyrolysis production technology generally has a certain particle size requirements for raw coal, resulting in lower yield and poorer quality of coal tar, lower content of effective components in coal gas such as H2, CH4, CO, etc. To further improve the yield of coal tar obtained from the pyrolysis of low rank coal and explore systematically the effect of microwave power, pyrolysis time and particle size of coal samples on the yield and composition of microwave pyrolysis products of low rank coal through the analysis and characterization of products with FTIR and GC-MS, introducing microwave pyrolysis of low rank coal into the microwave pyrolysis reactor circularly was suggested to carry out the co-pyrolysis experiment of the low rank coal and coal gas generated by the pyrolysis of low rank coal. The results indicated that the yield of the bluecoke and liquid products were up to 62.2% and 26.8% respectively when the optimal pyrolysis process conditions with the microwave power of 800W, pyrolysis time of 40 min, coal samples particle size of 5-10 mm and circulating coal gas flow rate of 0.4 L · min⁻¹ were selected. The infrared spectrogram of the bluecoke under different microwave power and pyrolysis time overlapped roughly. The content of functional groups with -OH, C==O, C==C and C−O from the bluecoke through the pyrolysis of particle size coal samples had a larger difference. To improve microwave power, prolonging pyrolysis time and reducing particle size of coal samples were conducive to converting heavy component to light one into coal tar.

Effective enrichment and separation of three flavonoids from Ohwia caudata (Thunberg) H. Ohashi using magnetic layered double hydroxide/ZIF-8 composites and pCEC.

In this study, Fe3O4@ZnCr-layered double hydroxide/zeolitic imidazolate frameworks-8 (MLDH/ZIF-8) magnetically functionalized composites were synthesized by co-precipitation and in situ growth based on the advantages of LDHs and ZIF-8 using Fe3O4 nanoparticles as a magnetic substrate to obtain adsorbents with excellent performance. Moreover, the composite was used for the efficient enrichment of flavonoids in Chinese herbal medicines. The internal structures and surface properties were characterized by SEM, Fourier transform infrared spectroscopy, X-ray diffraction and so on. MLDH/ZIF-8 exhibited a large specific surface area and good paramagnetic properties. The MLDH/ZIF-8 magnetic composite was used as a magnetic solid-phase extraction (MSPE) adsorbent, and a MLDH/ZIF-8 MSPE-pressurized capillary electrochromatography coupling method was developed for the separation and detection of flavonoids (luteolin, kaempferol and apigenin) in a sample of the Chinese herb Ohwia caudata (Thunberg) H. Ohashi. The relevant parameters affecting the extraction efficiency were optimized to determine the ideal conditions for MSPE. 5 mg of adsorbent in sample solution at pH 6, vortex extraction for 5 min, elution with 1.5 mL of ethyl acetate for 15 min. The method showed good linearity in the concentration range of 3-50 µg mL-1 with correlation coefficients of 0.9934-0.9981, and displayed a relatively LODs of 0.07-0.09 µg mL-1. The spiked recoveries of all analytes ranged from 84.5% to 122.0% with RSDs (n=3) between 4.5% and 7.7%. This method is straightforward and efficient, with promising potential in the separation and analysis of active ingredients in various Chinese herbal medicines.

Fabrication and Characterization of Carbon Nanotube Filled PDMS Hybrid Membranes for Enhanced Ethanol Recovery.

Ethanol separation via the pervaporation process has shown growing application potential in solvent recovery and the bioethanol industry. In the continuous pervaporation process, polymeric membranes such as hydrophobic polydimethylsiloxane (PDMS) have been developed to enrich/separate ethanol from dilute aqueous solutions. However, its practical application remains largely limited due to the relatively low separation efficiency, especially in selectivity. In view of this, hydrophobic carbon nanotube (CNT) filled PDMS mixed matrix membranes (MMMs) aimed at high-efficiency ethanol recovery were fabricated in this work. The filler K-MWCNTs was prepared by functionalizing MWCNT-NH2 with epoxy-containing silane coupling agent (KH560) to improve the affinity between fillers and PDMS matrix. With K-MWCNT loading increased from 1 wt % to 10 wt %, membranes showed higher surface roughness and water contact angle was improved from 115° to 130°. The swelling degree of K-MWCNT/PDMS MMMs (2 wt %) in water were also reduced from 10 wt % to 2.5 wt %. Pervaporation performance for K-MWCNT/PDMS MMMs under varied feed concentrations and temperatures were evaluated. The results supported that the K-MWCNT/PDMS MMMs at 2 wt % K-MWCNT loading showed the optimum separation performance (compared with pure PDMS membranes), with the separation factor improved from 9.1 to 10.4, and the permeate flux increased by 50% (40-60 °C, at 6 wt % feed ethanol concentration). This work provides a promising method for preparing a PDMS composite with both high permeate flux and selectivity, which showed great potential for bioethanol production and alcohol separation in industry.

Assessing Spatial Accessibility of Community Hospitals for the Elderly in Beijing, China.

Accessibility of health services signifies the quality and equitability of universal health provision. The hierarchical medical system recently implemented in China offers the policy instruments to improve medical services to the elderly in an aging society. As the critical primary care gateway, accessibility to community hospitals has significant impacts on people's health. However, current research has paid little attention to spatial accessibility within walking distance of community hospitals, especially for the elderly. This study selected four districts with different urbanization levels in the rapidly developing Beijing metropolis. The spatial interaction model was applied to measure the accessibility of community hospitals for the elderly at the community level. An attractiveness index was computed based on key hospital traits. The results showed that: (1) community hospitals could cover 82.66% of elderly residents, and 77.63% of the communities were within walking distance. The served elderly proportion was relatively high in central urban areas and low in the suburbs. (2) The attractiveness indices of hospitals varied notably between districts, with higher values in more urbanized areas. (3) The spatial accessibility for the elderly of hospitals differed significantly between the four districts, with a descending gradient from central to suburban and rural areas, as indicated by the Gini coefficients and Lorenz curves. (4) The accessibility index was strongly related to the served elderly population and the hospital-residence distance. The findings provide policy directions to the government, including providing more primary-care resources to suburban and rural areas, building new community hospitals in identified provision gaps, upgrading some clinics to hospitals in rural areas, and planning hospitals according to the projected trend of the elderly population in terms of quantity and distribution. The considerable provision disparity between core urban, suburban and rural areas can be addressed by refined spatial health planning informed by research.

[Determination of 16 elements in the different pine pollen by TXRF].

After microwave digestion, 16 elements in pine pollen were simultaneously determined by TXRF. The results show that all the 16 elements were found in all pine pollens. There was a significant difference in the average content of the element such as Ca, Ti, Mn, Zn and Rb between different groups of pine pollen (P < or = 0.01). There was a difference in the average content of the element such as K, V, Fe, Co, Cu and Sr between them (P < or = 0.05). And there was no difference in the average content of the element such as Cr, Ni, As, Pb and Se between them. The results also show that pine pollen has the spectral characteristics of warm property or cold property drug. They were closely related to the tree species and the growth environment or the growth area.

Yeast-Based Porous Carbon with Superior Electrochemical Properties.

Biomass is a promising carbon source for supercapacitor electrode materials due to its abundant source, diversity, and low-cost. Yeast is an elliptic unicellular fungal organism that is widespread in nature. In this work, we used yeast as the carbon source and Na2SiO3 as the activator to prepare a honeycomb porous carbon with higher surface area. The yeast and Na2SiO3 were directly mixed and ground without any solvent, which is simple and characterized by large-scale application. The prepared porous carbon shows a good specific capacity of 313 F/g in 6 M KOH at a density of 0.5 A/g and an excellent rate capability of 85.9% from 0.5 to 10 A/g. The results suggest that the yeast-derived porous carbon may be a promising sustainable bio-material for the preparation of supercapacitor carbon electrode materials. This study provides an economical and practical avenue for yeast resource utilization and develops a simple approach to prepare porous carbon materials.

Organocatalytic Asymmetric Construction of Tetrasubstituted Carbon Stereocenters Bearing Three Heteroatoms via Intramolecular Cyclization of Vinylidene ortho-Quinone Methide with Imidates.

We report herein an organocatalytic asymmetric protocol for the construction of tetrasubstituted carbon stereocenters bearing three heteroatoms. The reaction proceeded via the enantioselective intramolecular cyclization reaction of vinylidene ortho-quinone methide (VQM) with imidates to form pentacyclic heterocycles. The formed tetrasubstituted carbon center was stable under a high temperature and the conditions for further transformations.

Effects of Self-Rated Health Status on Residents' Social-Benefit Perceptions of Urban Green Space.

Urban green spaces (UGS) provide many social benefits and improves residents' wellbeing. Studying residents' perceptions of UGS's social benefits and driving factors could promote public health and environmental justice. A questionnaire survey of 432 Beijing residents and statistical tests assessed the impacts of residents' living environments and self-rated health status on UGS perceptions. The results showed: (1) perceptions of UGS' physical health benefits were subdued, with an inclination towards other social benefits. Respondents more highly perceived accelerating patient recovery and reducing morbidity and mortality rates. Perceptions of bearing larger-head babies with higher weight were relatively low. For other social benefits, perceptions of improving the environment and life quality were higher, but reducing anger outbursts and resolving conflicts were lower. (2) Childhood living environments did not affect perceptions of social benefits, but current living environments did. Suburb residents understood reducing pain-relief medication demands and bearing larger-head babies better than city residents. City residents understood UGS' investments considerable and sustained returns better than village residents. City residents agreed with accelerating patient recovery higher than village ones. (3) Respondents with "poor" self-rated health status had better perceptions of other social benefits. Those with "excellent" ratings did not fully understand UGS' physical health benefits. "Poor" ratings understood improving a city's image and making cities livable and sustainable better than "good" or "fair" ratings. "Excellent" ratings had less understanding of larger-head babies than "good" or "fair" ratings. The study could enhance appreciation of UGS' social benefits to facilitate planning and management to meet residents' expectations.

Numerical Analysis of Fiber/Air-Coupling Field for Annular Jet.

Melt-blowing technology is an important method for directly preparing micro-nanofiber materials by drawing polymer melts with high temperature and high velocity air flow. During the drawing process, the melt-blowing fiber not only undergoes a phase change, but also has an extremely complex coupling effect with the drawing airflow. Therefore, in the numerical calculation of the flow field, the existence of melt-blowing fibers is often ignored. In this paper, based on the volume of fluid method, a numerical study of the flexible fiber/air-coupling flow field of an annular melt-blowing die is carried out with the aid of computational fluid dynamics software. The results show that the pressure distribution in the different central symmetry planes of the ring die at the same time was basically the same. However, the velocity distribution may have been different; the velocity on the spinning line varied with time; the pressure changes on the spinning line were small; and velocity fluctuations around the spinning line could cause whiplash of the fibers.

Organocatalytic cascade reactions for multi-functionalized chiral cyclic ethers through vinylidene ortho-quinone methides.

An organocatalytic approach to installing various alcohols into the carbonyl of α,ß-unsaturated ketones mediated by VQM intermediates was achieved, followed by dearomatization to provide the stereo-defined cyclic ethers via a cascade process. Along with the transformations, this strategy affords efficient access to the underexplored chiral cyclic ether chemospace.

Impact of vegetation removal and soil aridation on diurnal temperature range in a semiarid region: application to the Sahel.

Increased clouds and precipitation normally decrease the diurnal temperature range (DTR) and thus have commonly been offered as explanation for the trend of reduced DTR observed for many land areas over the last several decades. Observations show, however, that the DTR was reduced most in dry regions and especially in the West African Sahel during a period of unprecedented drought. Furthermore, the negative trend of DTR in the Sahel appears to have stopped and may have reversed after the rainfall began to recover. This study develops a hypothesis with climate model sensitivity studies showing that either a reduction in vegetation cover or a reduction in soil emissivity would reduce the DTR by increasing nighttime temperature through increased soil heating and reduced outgoing longwave radiation. Consistent with empirical analyses of observational data, our results suggest that vegetation removal and soil aridation would act to reduce the DTR during periods of drought and human mismanagement over semiarid regions such as the Sahel and to increase the DTR with more rainfall and better human management. Other mechanisms with similar effects on surface energy balance, such as increased nighttime downward longwave radiation due to increased greenhouse gases, aerosols, and clouds, would also be expected to have a larger impact on DTR over drier regions.