Controllable p- and n-type behaviours in emissive perovskite semiconductors.

Reliable control of the conductivity and its polarity in semiconductors is at the heart of modern electronics1-7, and has led to key inventions including diodes, transistors, solar cells, photodetectors, light-emitting diodes and semiconductor lasers. For archetypal semiconductors such as Si and GaN, positive (p)- and negative (n)-type conductivities are achieved through the doping of electron-accepting and electron-donating elements into the crystal lattices, respectively1-6. For halide perovskites, which are an emerging class of semiconductors, mechanisms for reliably controlling charge conduction behaviours while maintaining high optoelectronic qualities are yet to be discovered. Here we report that the p- and n-type characteristics in a wide-bandgap perovskite semiconductor can be adjusted by incorporating a phosphonic acid molecular dopant with strong electron-withdrawing abilities. The resultant carrier concentrations were more than 1013 cm-3 for the p- and n-type samples, with Hall coefficients ranging from -0.5 m3 C-1 (n-type) to 0.6 m3 C-1 (p-type). A shift of the Fermi level across the bandgap was observed. Importantly, the transition from n- to p-type conductivity was achieved while retaining high photoluminescence quantum yields of 70-85%. The controllable doping in the emissive perovskite semiconductor enabled the demonstration of ultrahigh brightness (more than 1.1 × 106 cd m-2) and exceptional external quantum efficiency (28.4%) in perovskite light-emitting diodes with a simple architecture.

Lizards exploit the changing optics of developing chromatophore cells to switch defensive colors during ontogeny.

Many animals undergo changes in functional colors during development, requiring the replacement of integument or pigment cells. A classic example of defensive color switching is found in hatchling lizards, which use conspicuous tail colors to deflect predator attacks away from vital organs. These tail colors usually fade to concealing colors during ontogeny. Here, we show that the ontogenetic blue-to-brown tail color change in Acanthodactylus beershebensis lizards results from the changing optical properties of single types of developing chromatophore cells. The blue tail colors of hatchlings are produced by incoherent scattering from premature guanine crystals in underdeveloped iridophore cells. Cryptic tail colors emerge during chromatophore maturation upon reorganization of the guanine crystals into a multilayer reflector concomitantly with pigment deposition in the xanthophores. Ontogenetic changes in adaptive colors can thus arise not via the exchange of different optical systems, but by harnessing the timing of natural chromatophore development. The incoherent scattering blue color here differs from the multilayer interference mechanism used in other blue-tailed lizards, indicating that a similar trait can be generated in at least two ways. This supports a phylogenetic analysis showing that conspicuous tail colors are prevalent in lizards and that they evolved convergently. Our results provide an explanation for why certain lizards lose their defensive colors during ontogeny and yield a hypothesis for the evolution of transiently functional adaptive colors.

Global airborne bacterial community-interactions with Earth's microbiomes and anthropogenic activities.

Airborne bacteria are an influential component of the Earth's microbiomes, but their community structure and biogeographic distribution patterns have yet to be understood. We analyzed the bacterial communities of 370 air particulate samples collected from 63 sites around the world and constructed an airborne bacterial reference catalog with more than 27 million nonredundant 16S ribosomal RNA (rRNA) gene sequences. We present their biogeographic pattern and decipher the interlacing of the microbiome co-occurrence network with surface environments of the Earth. While the total abundance of global airborne bacteria in the troposphere (1.72 × 1024 cells) is 1 to 3 orders of magnitude lower than that of other habitats, the number of bacterial taxa (i.e., richness) in the atmosphere (4.71 × 108 to 3.08 × 109) is comparable to that in the hydrosphere, and its maximum occurs in midlatitude regions, as is also observed in other ecosystems. The airborne bacterial community harbors a unique set of dominant taxa (24 species); however, its structure appears to be more easily perturbed, due to the more prominent role of stochastic processes in shaping community assembly. This is corroborated by the major contribution of surface microbiomes to airborne bacteria (averaging 46.3%), while atmospheric conditions such as meteorological factors and air quality also play a role. Particularly in urban areas, human impacts weaken the relative importance of plant sources of airborne bacteria and elevate the occurrence of potential pathogens from anthropogenic sources. These findings serve as a key reference for predicting planetary microbiome responses and the health impacts of inhalable microbiomes with future changes in the environment.

Development of High-Performance and Multifunctional Nanoparticles Powered the Integrated Diagnosis and Treatment of Escherichia coli O157:H7.

Pathogenic diseases that trigger food safety remain a noteworthy concern due to substantial public health, economic, and social burdens worldwide. It is vital for developing an integrated diagnosis and treatment strategy for bacteria, which could achieve quick detection of pathogenic bacteria and the inhibition of multidrug-resistant bacteria. Herein, we reported an organic molecule (M-3) possessed strong light capture capacity, emerging a low energy gap and ΔEST. Subsequently, M-3 was integrated into a nanostructured system (BTBNPs) with excellent ROS generation, light absorption capability, and photothermal performance. Reactive oxygen species (ROS) generated by BTBNPs were mainly free radicals from a type I mechanism, and the high photothermal conversion efficiency of BTBNPs was 41.26%. Benefiting from these advantages of BTBNPs, BTBNPs could achieve a ∼99% antibacterial effect for Escherichia coli O157:H7 with 20 µM dosage and 5 min of irradiation. Furthermore, the limit of detection (LoD) of the proposed BTBNPs-LFIA (colorimetric and photothermal modalities) for detecting E. coli O157:H7 was 4105 and 419 CFU mL-1, respectively. Overall, this work is expected to provide a new and sophisticated perspective for integrated diagnosis and treatment systems regarding pathogenic bacteria.

Efficient Photothermal Sensor Based on Coral-Like Hollow Gold Nanospheres for the Sensitive Detection of Sulfonamides.

Gold nanoparticles (AuNPs), universally regarded as colorimetric signal reporters, are widely employed in lateral flow immunoassays (LFIAs). However, it is difficult for AuNPs-LFIA to achieve a wide range and sensitive detection. Herein, novel coral-like hollow gold nanospheres (CHGNPs) are synthesized. The growth of gold nanospheres can be regulated to obtain a multibranched and hollow construction. The obtained CHGNPs possess intense broadband absorption across the visible to near-infrared region, exhibiting a high molar extinction coefficient of 14.65 × 1011 M-1 cm-1 and a photothermal conversion efficiency of 79.75%. Thus, the photothermal/colorimetric dual-readout LFIA is developed based on CHGNPs (CHGNPs-PT-LFIA and CHGNPs-CM-LFIA) to effectively improve the detection sensitivity and broaden the detection range in regard to sulfonamides (SAs). The limits of detection of the CHGNPs-PT-LFIA and CHGNPs-CM-LFIA reached 1.9 and 2.8 pg mL-1 for the quantitative detection of sulfaquinoxaline, respectively, which are 6.3-fold and 4.3-fold lower than that of the AuNPs-LFIA. Meanwhile, the CHGNPs-PT-LFIA broadened the detection range to three orders of magnitude, which ranged from 2.5 to 5000 pg mL-1. The synthesized photothermal CHGNPs have been proven effective in improving the performance of the LFIA and provide a potential option for the construction of sensing platforms.

Determination of soil phenanthrene degradation through a fungal-bacterial consortium.

Fungal-bacterial consortia enhance organic pollutant removal, but the underlying mechanisms are unclear. We used stable isotope probing (SIP) to explore the mechanism of bioaugmentation involved in polycyclic aromatic hydrocarbon (PAH) biodegradation in petroleum-contaminated soil by introducing the indigenous fungal strain Aspergillus sp. LJD-29 and the bacterial strain Pseudomonas XH-1. While each strain alone increased phenanthrene (PHE) degradation, the simultaneous addition of both strains showed no significant enhancement compared to treatment with XH-1 alone. Nonetheless, the assimilation effect of microorganisms on PHE was significantly enhanced. SIP revealed a role of XH-1 in PHE degradation, while the absence of LJD-29 in 13C-DNA indicated a supporting role. The correlations between fungal abundance, degradation efficiency, and soil extracellular enzyme activity indicated that LJD-29, while not directly involved in PHE assimilation, played a crucial role in the breakdown of PHE through extracellular enzymes, facilitating the assimilation of metabolites by bacteria. This observation was substantiated by the results of metabolite analysis. Furthermore, the combination of fungus and bacterium significantly influenced the diversity of PHE degraders. Taken together, this study highlighted the synergistic effects of fungi and bacteria in PAH degradation, revealed a new fungal-bacterial bioaugmentation mechanism and diversity of PAH-degrading microorganisms, and provided insights for in situ bioremediation of PAH-contaminated soil.IMPORTANCEThis study was performed to explore the mechanism of bioaugmentation by a fungal-bacterial consortium for phenanthrene (PHE) degradation in petroleum-contaminated soil. Using the indigenous fungal strain Aspergillus sp. LJD-29 and bacterial strain Pseudomonas XH-1, we performed stable isotope probing (SIP) to trace active PHE-degrading microorganisms. While inoculation of either organism alone significantly enhanced PHE degradation, the simultaneous addition of both strains revealed complex interactions. The efficiency plateaued, highlighting the nuanced microbial interactions. SIP identified XH-1 as the primary contributor to in situ PHE degradation, in contrast to the limited role of LJD-29. Correlations between fungal abundance, degradation efficiency, and extracellular enzyme activity underscored the pivotal role of LJD-29 in enzymatically facilitating PHE breakdown and enriching bacterial assimilation. Metabolite analysis validated this synergy, unveiling distinct biodegradation mechanisms. Furthermore, this fungal-bacterial alliance significantly impacted PHE-degrading microorganism diversity. These findings advance our understanding of fungal-bacterial bioaugmentation and microorganism diversity in polycyclic aromatic hydrocarbon (PAH) degradation as well as providing insights for theoretical guidance in the in situ bioremediation of PAH-contaminated soil.

Tire Wear Chemicals in the Urban Atmosphere: Significant Contributions of Tire Wear Particles to PM2.5.

Tire wear particles (TWPs) containing tire wear chemicals (TWCs) are of global concern due to their large emissions and potential toxicity. However, TWP contributions to urban fine particles are poorly understood. Here, 72 paired gas-phase and PM2.5 samples were collected in the urban air of the Pearl River Delta, China. The concentrations of 54 compounds were determined, and 28 TWCs were detected with total concentrations of 3130-317,000 pg/m3. Most p-phenylenediamines (PPDs) were unstable in solvent, likely leading to their low detection rates. The TWCs were mainly (73 ± 26%) in the gas phase. 2-OH-benzothiazole contributed 82 ± 21% of the gas-phase TWCs and benzothiazole-2-sulfonic acid contributed 74 ± 18% of the TWCs in PM2.5. Guangzhou and Foshan were "hotspots" for atmospheric TWCs. Most TWC concentrations significantly correlated with the road length nearby. More particulate TWCs were observed than model predictions, probably due to the impacts of nonexchangeable portion and sampling artifacts. Source apportionment combined with characteristic molecular markers indicated that TWPs contributed 13 ± 7% of urban PM2.5. Our study demonstrates that TWPs are important contributors to urban air pollution that could pose risks to humans. There is an urgent need to develop strategies to decrease TWP emissions, along with broader urban air quality improvement strategies.

Increase in Agricultural-Derived NHx and Decrease in Coal Combustion-Derived NOx Result in Atmospheric Particulate N-NH4+ Surpassing N-NO3- in the South China Sea.

The atmospheric deposition of anthropogenic active nitrogen significantly influences marine primary productivity and contributes to eutrophication. The form of nitrogen deposition has been evolving annually, alongside changes in human activities. A disparity arises between observation results and simulation conclusions due to the limited field observation and research in the ocean. To address this gap, our study undertook three field cruises in the South China Sea in 2021, the largest marginal sea of China. The objective was to investigate the latest atmospheric particulate inorganic nitrogen deposition pattern and changes in nitrogen sources, employing nitrogen-stable isotopes of nitrate (δ15N-NO3-) and ammonia (δ15N-NH4+) linked to a mixing model. The findings reveal that the N-NH4+ deposition generally surpasses N-NO3- deposition, attributed to a decline in the level of NOx emission from coal combustion and an upswing in the level of NHx emission from agricultural sources. The disparity in deposition between N-NH4+ and N-NO3- intensifies from the coast to the offshore, establishing N-NH4+ as the primary contributor to oceanic nitrogen deposition, particularly in ocean background regions. Fertilizer (33 ± 21%) and livestock (20 ± 6%) emerge as the primary sources of N-NH4+. While coal combustion continues to be a significant contributor to marine atmospheric N-NO3-, its proportion has diminished to 22 (Northern Coast)-35% (background area) due to effective NOx emission controls by the countries surrounding the South China Sea, especially the Chinese Government. As coal combustion's contribution dwindles, the significance of vessel and marine biogenic emissions grows. The daytime higher atmospheric N-NO3- concentration and lower δ15N-NO3- compared with nighttime further underscore the substantial role of marine biogenic emissions.

Temporal Variations in Fire Impacts on Characteristics and Composition of Soil-Derived Dissolved Organic Matter at Qipan Mountain, China.

Dissolved organic matter (DOM), the most reactive fraction of forest soil organic matter, is increasingly impacted by wildfires worldwide. However, few studies have quantified the temporal changes in soil DOM quantity and quality after fire. Here, soil samples were collected after the Qipan Mountain Fire (3-36 months) from pairs of burned and unburned sites. DOM contents and characteristics were analyzed using carbon quantification and various spectroscopic and spectrometric techniques. Compared with the unburned sites, burned sites showed higher contents of bulk DOM and most DOM components 3 months after the fire but lower contents of them 6-36 months after the fire. During the sharp drop of DOM from 3 to 6 months after the fire, carboxyl-rich alicyclic molecule-like and highly unsaturated compounds had greater losses than condensed aromatics. Notably, the burned sites had consistently higher abundances of oxygen-poor dissolved black nitrogen and fluorescent DOM 3-36 months after the fire, particularly the abundance of pyrogenic C2 (excitation/emission maxima of <250/∼400 nm) that increased by 150% before gradually declining. This study advances the understanding of temporal variations in the effects of fire on different soil DOM components, which is crucial for future postfire environmental management.

Occurrence and fate of current-use pesticides in Chinese forest soils.

Pesticides play a crucial role in securing global food production to meet increasing demands. However, because of their pervasive use, they are now ubiquitous environmental pollutants that have adverse effects on both ecosystems and human health. In this study, the environmental occurrence and fate of 16 current-use pesticides (CUPs) were investigated in 93 forest soil samples obtained from 11 distinct mountains in China. The concentrations of the target pesticides ranged from 0.36 to 55 ng/g dry weight. Cypermethrin, dicofol, chlorpyrifos, chlorothalonil, and trifluralin were the most frequently detected CUPs. The CUP concentrations were generally higher in the O-horizon than in the A-horizon. Chlorpyrifos, chlorothalonil, and dicofol were detected in most deep layers in soil profiles from three mountains selected to represent distinct climate zones. No clear altitudinal trend in organic carbon-normalized concentrations of CUPs was observed in the O- or A-horizons within individual mountains. A negative correlation was noted between the CUP concentrations and the altitudes across all sampling sites. This indicated that proximity to emission sources was a key factor affecting the spatial distribution of CUPs in mountain forest soil on a national scale. The ecological risk assessment showed that dicofol and cypermethrin pose potential risks to earthworms. This study emphasizes the importance of source control when setting management strategies for CUPs.

Association between non-high-density lipoprotein cholesterol to high-density lipoprotein cholesterol ratio (NHHR) and kidney stone: evidence from NHANES 2007-2018.

BACKGROUND: As an innovative lipid parameter, NHHR (the ratio of non-high-density lipoprotein cholesterol to high-density lipoprotein cholesterol) can serve as a valuable tool for assessing cardiovascular disease risk. Nevertheless, the relationship between NHHR and the risk of kidney stones remains unexplored. METHODS: A cross-sectional survey utilized data from the National Health and Population Survey (NHANES) database in the United States spanning from 2007 to 2018. Distinct statistical analyses were applied, including weighted logistic regression, stratified and interaction analysis and restricted cubic spline curve (RCS) models, to examine the correlation between NHHR and the incidence of kidney stones. RESULTS: This analysis encompassed 24,664 participants, with 9.63% reporting incidents of kidney stones. Following multivariate logistic regression and comprehensive adjustments, participants in NHHR quartile 4 (OR 1.34; 95% CI 1.12, 1.60, P < 0.01) exhibited a significantly increased risk of kidney stones compared to those in NHHR quartile 1 (Q1). The RCS result further illustrated a non-linear correlation between NHHR and the incidence of kidney stones. The result of subgroup analysis manifested that participants without diabetes had a higher risk of kidney stones when measured high NHHR levels compared those with diabetes (p for interaction < 0.05). CONCLUSION: Elevated NHHR levels were found to be associated with an increased risk of kidney stones. Based on these findings, NHHR appears to be a promising predictive indicator for the occurrence of kidney stones.

Prevalence and risk factors of training-related abdominal injuries: A multicenter survey study.

PURPOSE: This study aims to identify the prevalence and risk factors of military training-related abdominal injuries and help plan and conduct training properly. METHODS: This questionnaire survey study was conducted from October 2021 to May 2022 among military personnel from 6 military units and 8 military medical centers and participants' medical records were consulted to identify the training-related abdominal injuries. All the military personnel who ever participated in military training were included. Those who refused to participate in this study or provided an incomplete questionnaire were excluded. The questionnaire collected demographic information, type of abdominal injury, frequency, training subjects, triggers, treatment, and training disturbance. Chi-square test and t-test were used to compare baseline information. Univariate and multivariate regression analyses were used to explore the risk factors associated with military training-related abdominal injuries. RESULTS: A total of 3058 participants were involved in this study, among which 1797 (58.8%) had suffered training-related abdominal injuries (the mean age was 24.3 years and the service time was 5.6 years), while 1261 (41.2%) had no training-related abdominal injuries (the mean age was 23.1 years and the service time was 4.3 years). There were 546 injured patients (30.4%) suspended the training and 84 (4.6%) needed to be referred to higher-level hospitals. The most common triggers included inadequate warm-up, fatigue, and intense training. The training subjects with the most abdominal injuries were long-distance running (589, 32.8%). Civil servants had the highest rate of abdominal trauma (17.1%). Age ≥ 25 years, military service ≥ 3 years, poor sleep status, and previous abdominal history were independent risk factors for training-related abdominal injury. CONCLUSION: More than half of the military personnel have suffered military training-related abdominal injuries. Inadequate warm-up, fatigue, and high training intensity are the most common inducing factors. Scientific and proper training should be conducted according to the factors causing abdominal injuries.

[Inflammatory factors and prostate cancer: Two-sample Mendelian randomization analysis].

OBJECTIVE: To evaluate the potential causal relationship between inflammatory factors and PCa using the two-sample Mendelian randomization (MR) method. METHODS: We selected summary statistics of genome-wide association studies (GWAS) (n = 14 824) on 91 inflammatory factors, with PCa as the outcome in the latest 9th edition of FinnGen database for MR analysis. We evaluated the causal relationship between inflammatory factors and PCa using the odds ratio (OR) and 95% confidence interval (CI) of such regression models as inverse variance weighting (IVW), MR-Egger regression, simple mode (SM), weighted mode (WM) and weighted median estimator (WME), with IVW as the main statistical method for this study. We further verified the results of MR by Bayesian analysis, and evaluated the heterogeneity of genetic instrumental variables, pleiotropic effects and sensitivity of single nucleotide polymorphisms (SNP) as instrumental variables to the exposure-outcome relationship by Cochran's Q test, MR-Egger intercept test and leave-one-out cross validation. RESULTS: IVW showed that among the 91 inflammatory factors, interleukin-22 receptor A1 (IL-22RA1) and sulfotransferase 1A1 (ST1A1) were correlated positively with the risk of PCa； IL-22RA1：IVW（OR ［95% CI］: 1.12 ［1.00－1.25］, P = 0.04）；ST1A1：IVW（OR ［95% CI］: 1.08 (1.00－1.16), P = 0. 03）, while Chemokine ligand 11 (CXCL11) and interleukin 17 A (IL-17 A) negatively with the risk of PCa； CXCL11：IVW（OR ［95% CI］: 0.88 ［0.81－0.95］, P = 0.00）；IL-17A：IVW（OR ［95% CI］: 0.91 ［0.84－0.98］, P = 0.02）. No potential horizontal pleiotropy was detected by MR-Egger intercept analysis (P > 0.05, IL-22RA1 = 0.885, ST1A1 = 0.949, CXCL11 = 0.391, IL-17A = 0.884), nor biased SNPs in the MR pleiotropy residual sum and outlier (MR-PRESSO) test (P > 0.05, IL-22RA1 = 0.479, ST1A1 = 0.629, CXCL11 = 0.326, IL-17A = 0.444), or heterogeneity P > 0.05, IL-22RA1 = 0.543, ST1A1 = 0.677, CXCL11 = 0.336, IL-17A = 0.494). Leave-one-out sensitivity analysis indicated no significant impact of individual SNP sites on the overall causal relationship prediction, suggesting the reliable results of analysis. CONCLUSION: Among the 91 inflammatory factors, IL-22RA1 and ST1A1 have a positive causal relationship, while CXCL11 and IL-17A have a negative causal relationship with PCa.

High-Performance Fluorescent Microspheres Based on Fluorescence Resonance Energy Transfer Mode for Lateral Flow Immunoassays.

The label with a large Stokes shift and strong fluorescence properties could improve the sensitivity of the lateral flow immunoassay (LFIA). Herein, two aggregation-induced emission (AIE) luminogens with spectral overlap were encapsulated in polymers by using the microemulsion method as a label, and the construction of a fluorescence resonance energy transfer mode was further verified via theoretical calculation and spectral analysis. Satisfactorily, the doped AIE polymer microspheres (DAIEPMs) exhibited a large Stokes shift of 285 nm and a 10.8-fold fluorescence enhancement compared to those of the AIEPMs loaded with acceptors. Benefiting from the excellent optical performance, DAIEPMs were applied to the LFIA for sensitive detection of chlorothalonil, which is an organochlorine pesticide. The limit of detection of the proposed DAIEPMs-LFIA was 1.2 pg/mL, which was 4.8-fold and 11.6-fold lower than those of quantum dot bead LFIA and gold nanoparticle LFIA, respectively. This work provides a new strategy to improve the optical properties of fluorescent materials and construct a sensitive and reliable detection platform.

Lipids, Apolipoproteins, Statins, and Intracerebral Hemorrhage: A Mendelian Randomization Study.

OBJECTIVE: To investigate the causal role of lipid or apolipoprotein traits in intracerebral hemorrhage (ICH) and determine the effect of lipid-lowering interventions on the disease. METHODS: Two-sample Mendelian randomization (MR) analyses were conducted to evaluate the associations of high-density lipoprotein cholesterol, low-density lipoprotein cholesterol (LDL-C), triglycerides (TG), apolipoprotein (Apo)B and ApoA1 levels with risks for ICH, and those of LDL-C- (HMGCR, PCSK9, and NPC1L1) and TG-lowering targets (LPL and APOC3) with ICH. RESULTS: Increased levels of ApoB was associated with a decreased risk of overall ICH (OR 0.623, 95% CI 0.413-0.940; p = 0.024) and lobar ICH (OR 0.579, 95% CI 0.342-0.979; p = 0.042). The inverse relationship remained stable in multivariable MR. In addition, elevated TGs showed a causal effect on lobar ICH in multivariable MR (OR 1.600, 95% CI 1.009-2.537; p = 0.046). The LDL-C-reducing genetic variation alleles at or near the HMGCR gene (mimicking the effect of statins) were predicted to increase the overall and deep ICH risk. Additionally, genetic variation at or near the APOC3 gene suggested that genetically reducing the activity of APOC3 (mimicking antisense anti-apoC3 agents) was predicted to decrease lobar ICH. INTERPRETATION: Genetically predicted elevated ApoB may have a protective effect on overall ICH and lobar ICH, whereas elevated TG was associated with a higher risk of lobar ICH conditional on LDL-C and ApoB. MR analysis supports the conclusion that statins may increase the risk of overall and deep ICH independent of their lipid-lowering effect. More specific lipid-lowering targets may end up being the future. ANN NEUROL 2022;92:390-399.

Metal-Free Synthesis of 2H-Indazole Skeletons by Photochemistry or Thermochemistry.

A simple and tuned synthesis of a 2H-indazole skeleton under metal-free conditions was developed. Under visible-light irradiation at room temperature, 2-((aryl/alkyl/H)ethynyl))aryltriazenes reacted with arylsulfinic acids to afford 3-functionalized 2H-indazoles without extra photocatalyst via an electron donor-acceptor complex. In the presence of arylsulfinic acid, 2-(ethynyl)aryltriazenes underwent an intramolecular oxidation/cyclization to provide 2H-indazole-3-carbaldehydes at 50 °C in air.

Microwave-promoted radical addition/cyclization of biaryl vinyl ketones with diacyl peroxides in water under metal-free conditions.

This communication reports an efficient microwave-promoted radical addition/cyclization reaction of biaryl vinyl ketones with diacyl peroxides in water under metal-free conditions. A series of 10-methyl-10-benzyl(alkyl)phenanthren-9(10H)-ones were obtained in high yields with good functional group tolerance.

Visible light as a sole requirement for alkylation of α-C(sp3)-H of N-aryltetrahydroisoquinolines with alkylboronic acids.

An alkylation of α-C(sp3)-H at N-aryltetrahydroisoquinolines with alkylboronic acids was developed under visible-light irradiation in the absence of additional photocatalyst. The reaction proceeded well, tolerating a variety of functional groups, and featured low-cost and mild reaction conditions. A preliminary mechanistic study indicated that an electron donor-acceptor (EDA) complex between an electron-rich N-aryltetrahydroisoquinoline and an electron-poor alkylboronic acid was involved in the reaction.

In Situ Discrimination and Cultivation of Active Degraders in Soils by Genome-Directed Cultivation Assisted by SIP-Raman-Activated Cell Sorting.

The identification and in situ cultivation of functional yet uncultivable microorganisms are important to confirm inferences regarding their ecological functions. Here, we developed a new method that couples Raman-activated cell sorting (RACS), stable-isotope probing (SIP), and genome-directed cultivation (GDC)─namely, RACS-SIP-GDC─to identify, sort, and cultivate the active toluene degraders from a complex microbial community in petroleum-contaminated soil. Using SIP, we successfully identified the active toluene degrader Pigmentiphaga, the single cells of which were subsequently sorted and isolated by RACS. We further successfully assembled the genome of Pigmentiphaga based on the metagenomic sequencing of 13C-DNA and genomic sequencing of sorted cells, which was confirmed by gyrB gene comparison and average nucleotide identity determination. Additionally, the genotypes and phenotypes of this degrader were directly linked at the single-cell level, and its complete toluene metabolic pathways in petroleum-contaminated soil were reconstructed. Based on its unique metabolic properties uncovered by genome sequencing, we modified the traditional cultivation medium with antibiotics, amino acids, carbon sources, and growth factors (e.g., vitamins and metals), achieving the successful cultivation of RACS-sorted active degrader Pigmentiphaga sp. Our results implied that RACS-SIP-GDC is a state-of-the-art approach for the precise identification, targeted isolation, and cultivation of functional microbes from complex communities in natural habitats. RACS-SIP-GDC can be used to explore specific and targeted organic-pollution-degrading microorganisms at the single-cell level and provide new insights into their biodegradation mechanisms.

Sources of the Elevating Polycyclic Aromatic Hydrocarbon Pollution in the Western South China Sea and Its Environmental Implications.

The environmental implications of polycyclic aromatic hydrocarbons (PAHs) caused by the vigorous development of offshore oil exploitation and shipping on the marine ecosystem are unclear. In this study, the PAH concentrations were systematically characterized in multiple environmental media (i.e., atmosphere, rainwater, seawater, and deep-sea sediments) in the western South China Sea (WSCS) for the first time to determine whether PAH pollution increased. The average ∑15PAHs (total concentration of 15 US EPA priority controlled PAHs excluding naphthalene) in the water of WSCS has increased and is higher than the majority of the oceans worldwide due to the synergistic influence of offshore oil extraction, shipping, and river input. The systematic model comparison confirms that the Ksoot-air model can more accurately reflect the gas-particle partitioning of PAHs in the atmosphere of the WSCS. We also found that the vertical migration of the elevating PAHs is accelerated by particulate matter, driving the migration of atmospheric PAHs to the ocean through dry and wet deposition, with 16% being contributed by the particle phase. The particulate matter sinking alters the PAH distribution in the water column and generates variation in source apportionment, while the contribution of PAHs loaded on them (>20%) to the total PAH reserves cannot be ignored as before. Hence, the ecological threat of PAHs increases by the oil drilling and shipping industry, and the driving force of particulate matter deserves continuous attention.