Construction of Cs2AgBiCl6/COF Heterojunction for Boosted Photocatalytic Thioester Oxidation.

Lead-free halide perovskites as a new kind of potential candidate for photocatalytic organic synthesis have attracted much attention recently. The rational heterojunction construction is regarded as an efficient strategy to delicately regulate their catalytic performances. Herein, a semi-conductive covalent organic framework (COF) nanosheet, C4N, is employed as the functional component to construct Cs2AgBiCl6/C4N (CABC/C4N) heterojunction. It is found that the C4N nanosheets with rich surface functional groups can serve as heterogeneous nucleation sites to manipulate the growth of CABC nanocrystals and afford close contact between each other, therefore facilitate the transfer and spatial separation of photogenerated charge carriers, as verified by in situ X-ray photoelectronic spectroscopy and Kelvin probe force microscopy. Moreover, the oxygen affinity of C4N endows the heterojunctions with outstanding aerobic reactivity, thus improving the photocatalytic performance largely. The optimal CABC/C4N heterojunction delivers a thioanisole conversion efficiency of 100% after 6 h, which is 2.2 and 7.7-fold of that of CABC and C4N. This work provides a new ideal for the design and application of lead-free perovskite heterojunction photocatalysts for organic reactions.

Nucleophilic Aromatic Substitution of Heteroaryl Halides with Thiols.

The nucleophilic aromatic substitution (SNAr) between heteroaryl halides (Cl, Br) and thiols proceeds smoothly in DMAc under the action of K2CO3 at rt-100 °C. For most electron-deficient heteroarenes, reaction takes place without introducing an additional electron-withdrawing group. For electron-rich heteroarenes, an additional electron-withdrawing group such as a simple ester, keto, cyano, and nitro group is required to ensure the reaction completes. The reactivity trend of heteroaryl halides is highly dependent on the electronic nature of the heteroarenes and orientation of halogens. Besides thiols, a couple of functionalized thioureas and thioamides are compatible with these conditions, providing the corresponding heteroaryl thioethers in good yields.

Effect of fine particulate matter exposure on gestational diabetes mellitus risk: a retrospective cohort study.

BACKGROUND: The literature on the association between fine particulate matter (PM2.5) exposure and gestational diabetes mellitus (GDM) risk has focused mainly on exposure during the first and second trimesters, and the research results are inconsistent. Therefore, this study aimed to investigate the associations between PM2.5 exposure during preconception, the first trimester and second trimester and GDM risk in pregnant women in Guangzhou. METHODS: A retrospective cohort study of 26 354 pregnant women was conducted, estimating PM2.5, particulate matter with a diameter >10 µm (PM10), sulphur dioxide (SO2), carbon monoxide (CO) and ozone (O3) exposure during preconception and the first and second trimesters. Analyses were performed using Cox proportional hazards models and nonlinear distributed lag models. RESULTS: The study found that exposure to PM2.5 or a combination of two pollutants (PM2.5+PM10, PM2.5+SO2, PM2.5+CO and PM2.5+O3) was found to be significantly associated with GDM risk (P < 0.05). In the second trimester, with significant interactions found for occupation and anaemia between PM2.5 and GDM. When the PM2.5 concentrations were ≥19.56, ≥25.69 and ≥23.87 µg/m3 during preconception and the first and second trimesters, respectively, the hazard ratio for GDM started to increase. The critical window for PM2.5 exposure was identified to be from 9 to 11 weeks before conception. CONCLUSIONS: Our study results suggest that PM2.5 exposure during preconception and the first and second trimesters increases the risk of GDM, with the preconception period appearing to be the critical window for PM2.5 exposure.

Filter design and color correction for the X-cube prism 3CCD camera.

For the X-cube prism three-charge-coupled-device (3CCD) camera, the spectra of the designed dichroic films in the X-cube prism shift with changes in the angle of incident light, producing non-uniformity of color on the image plane. We considered the influence of the incident angle on color performance in filter design and directly optimized the thin film to improve color consistency. An optical model was constructed to calculate the distribution of camera spectral sensitivity and independently correct the non-uniform color on the image plane. Results showed that the optimization and correction methods could significantly improve the color performance of the X-cube prism 3CCD camera.

Effects of heterospecific pollen on stigma behavior in Campsis radicans: Causes and consequences.

PREMISE: Pollinator sharing of co-flowering plants may result in interspecific pollen receipt with a fitness cost. However, the underlying factors that determine the effects of heterospecific pollen (HP) are not fully understood. Moreover, the cost of stigma closure induced by HP may be more severe for plants with special touch-sensitive stigmas than for plants with non-touch-sensitive stigmas. Very few studies have assessed HP effects on stigma behavior. METHODS: We conducted hand-pollination experiments with 10 HP donors to estimate HP effects on stigma behavior and stigmatic pollen germination in Campsis radicans (Bignoniaceae) at low and high pollen loads. We assessed the role of phylogenetic distance between donor and recipient, pollen size, and pollen aperture number in mediating HP effects. Additionally, we observed pollen tube growth to determine the conspecific pollen-tube-growth advantage. RESULTS: Stigma behavior differed significantly with HP of different species. Pollen load increased, while pollen size decreased, the percentage of permanent closure and stigmatic germination of HP. Stigmatic HP germination increased with increasing aperture number. However, HP effects did not depend on phylogenetic distance. In addition, conspecific pollen had a pollen-tube-growth advantage over HP. CONCLUSIONS: Our results provide a good basis for understanding the stigma-pollen recognition process of plant taxa with touch-sensitive stigmas. We concluded that certain flowering traits drive the HP effects on the post-pollination period. To better understand the impact of pollinator sharing and interspecific pollen transfer on plant evolution, we highlight the importance of evaluating more factors that determine HP effects at the community level.

Enhanced Catalytic Ozonation for Eliminating CH3SH via Stable and Circular Electronic Metal-Support Interactions of Si-O-Mn Bonds with Low Mn Loading.

Catalytic ozonation of methyl mercaptan (CH3SH) can effectively control this unbearable odorous sulfur-containing volatile organic compound (S-VOC). The construction of an electronic metal-support interaction (EMSI) coordination structure to maximize the number of active sites and increase the intrinsic activity of active sites is an effective means to improve catalytic performance. In this work, the abundant Si-OH groups on PSBA-15 (SBA-15 before calcination) were used to anchor Mn to form a Si-O-Mn-based EMSI coordination structure. Detailed characterizations and theoretical simulations reveal that the strong EMSI effect significantly adjusts and stabilizes the electronic structure of Mn 3d states, resulting in an electron-rich center on the Si-O-Mn bond to promote the specific adsorption/activation of ozone (O3) and an electron-poor center on the (Si-O-)Mn-O bond to adsorb a large amount of CH3SH accompanied by its own oxidative degradation. In situ Raman and in situ Fourier transform infrared (FTIR) analyses identify that catalytic ozonation over 3.0Mn-PSBA generates atomic oxygen species (AOS/*O) and reactive oxygen species (ROS/•O2-) to achieve efficient decomposition of CH3SH into CO2/SO42-. Furthermore, the electrons obtained from CH3SH in electron-poor centers are transferred to maintain the redox cycle of Mn2+/3+ → Mn4+ → Mn2+/3+ through the internal bond bridge, thus accomplishing the efficient and stable degradation of CH3SH prolonged to 180 min. Therefore, the rational design of catalysts with abundant active sites and optimized inherent activity via the EMSI effect can provide significant potential to improve catalytic performance and eliminate odorous gases.

Reactive Nitrogen Species Mediated Inactivation of Pathogenic Microorganisms during UVA Photolysis of Nitrite at Surface Water Levels.

UVA photolysis of nitrite (NO2-) occurs in a number of natural and engineered aquatic systems. This study reports for the first time that pathogenic microorganisms can be effectively inactivated during the coexposure of UVA irradiation and NO2- under environmentally relevant conditions. The results demonstrated that more than 3 log inactivation of Escherichia coli K-12, Staphylococcus aureus, and Spingopyxis sp. BM1-1 was achieved by UVA photolysis of 2.0 mg-N L-1 of NO2- in synthetic drinking water and real surface water. The inactivation was mainly attributed to the reactive species generated from UVA photolysis of NO2- rather than UVA irradiation or NO2- oxidation alone. The inactivation was predominantly contributed by the reactive nitrogen species (NO2• and ONOO-/HOONO) instead of the reactive oxygen species (HO• or O2•-). A kinetic model to simulate the reactive species generation from UVA photolysis of NO2- was established, validated, and used to predict the contributions of different reactive species to the inactivation under various environmental conditions. Several advanced tools (e.g., D2O - labeling with Raman spectroscopy) were used to demonstrate that the inactivation by the UVA/NO2- treatment was attributed to the DNA destruction by the reactive nitrogen species, which completely suppressed the viable but nonculturable (VBNC) states and the reactivation of bacteria. This study highlights a novel process for the inactivation of pathogenic microorganisms in water and emphasizes the critical role of reactive nitrogen species in water disinfection and purification.

Design of Compact Mid-Infrared Cooled Echelle Spectrometer Based on Toroidal Uniform-Line-Spaced (TULS) Grating.

A traditional flat-panel spectrometer does not allow high-resolution observation and miniaturization simultaneously. In this study, a compact, high-resolution cross-dispersion spectrometer was designed based on the theoretical basis of echelle grating for recording an infrared spectrum. To meet the high-resolution observation and miniaturization design requirements, a reflective immersion grating was used as the primary spectroscopic device. To compress the beam aperture of the imaging system, the order-separation device of the spectrometer adopted toroidal uniform line grating, which had both imaging and dispersion functions in the spectrometer. The aberration balance condition of the toroidal uniform line grating was analyzed based on the optical path difference function of the concave grating, and dispersion characteristics of the immersed grating and thermal design of the infrared lens were discussed based on the echelle grating. An immersion echelle spectrometer optical system consisting of a culmination system, an immersed echelle grating, and a converged system was used. The spectrometer was based on the asymmetrical Czerny-Turner and Littrow mount designs, and it was equipped with a 320 × 256 pixel detector array. The designed wavelength range was 3.7-4.8 µm, the F-number was 4, and the central wavelength resolution was approximately 30,000. An infrared cooling detector was used. The design results showed that, in the operating band range, the root implied that the square diameter of the spectrometer spot diagram was less than 30 µm, the energy was concentrated in a pixel size range, and the spectrometer system design met the requirements.

Gadolinium Changes the Local Electron Densities of Nickel 3d Orbitals for Efficient Electrocatalytic CO2 Reduction.

Generally, in terms of electrocatalytic CO2 reduction, single-atom catalysts show high selectivities yet low current densities whereas conventional nanoparticle catalysts exhibit relatively high current densities but low selectivities. This work combines the advantages of the two classes of catalysts by constructing a Ni-Gd-N-doped carbon black electrocatalyst within which NiI active sites are exposed outside the carbon layers and Ni nanoparticles are encapsulated inside the carbon layers. The Gd atoms can not only influence the local electron densities of Ni 3d orbitals, thus strengthening the electronic activity, but also tailor the sizes of the Ni nanoparticles, thereby minimizing the activity toward hydrogen evolution. Accordingly, this electrocatalyst yields both a high CO faradaic efficiency (97 %) and a large current density (308 mA cm-2 ), alongside an outstanding stability (100 h).

Enhanced Catalytic Ozonation for Eliminating CH3SH via Graphene-Supported Positively Charged Atomic Pt Undergoing Pt2+/Pt4+ Redox Cycle.

Constructing catalysts with electronic metal-support interaction (EMSI) is promising for catalytic reactions. Herein, graphene-supported positively charged (Pt2+/Pt4+) atomically dispersed Pt catalysts (AD-Pt-G) with PtxC3 (x = 1, 2, and 4)-based EMSI coordination structures are achieved for boosting the catalytic ozonation for odorous CH3SH removal. A CH3SH removal efficiency of 91.5% can be obtained during catalytic ozonation using optimum 0.5AD-Pt-G within 12 h under a gas hourly space velocity of 60,000 mL h-1 g-1, whereas that of pure graphene is 40.4%. Proton transfer reaction time-of-flight mass spectrometry, in situ diffuse reflectance infrared Fourier transform spectroscopy/Raman, and electron spin resonance verify that the PtxC3 coordination structure with atomic Pt2+ sites on AD-Pt-G can activate O2 to generate peroxide species (*O2) for partial oxidation of CH3SH during the adsorption period and trigger O3 into surface atomic oxygen (*Oad), *O2, and superoxide radicals (·O2-) to accomplish a stable, high-efficiency, and deeper oxidation of CH3SH during the catalytic ozonation stage. Moreover, the results of XPS and DFT calculation imply the occurrence of Pt2+ → Pt4+ → Pt2+ recirculation on PtxC3 for AD-Pt-G to maintain the continuous catalytic ozonation for 12 h, i.e., Pt2+ species devote electrons in 5d-orbitals to activate O3, while Pt4+ species can be reduced back to Pt2+ via capturing electrons from CH3SH. This study can provide novel insights into the development of atomically dispersed Pt catalysts with a strong EMSI effect to realize excellent catalytic ozonation for air purification.

Maternal risk factors and pregnancy complications associated with low birth weight neonates in preterm birth.

AIM: To explore the association between common pregnancy complications and low birth weight (LBW) neonates in preterm birth. METHODS: The study included 1764 pregnant women who experienced a single birth prematurely at a city hospital in Guangzhou, China between January 1, 2017 and December 31, 2019. A total of 874 normal birth weight neonates and 890 LBW neonates were included. Multivariate logistic regression analysis was conducted to identify and measure risk factors; two-tailed test was applied, with a p ≤ 0.05 considered statistically significant. RESULTS: Hypertension was the primary risk factor of LBW in preterm neonates, odds ratio (OR) = 2.912 (p < 0.001; 95% confidence interval [CI], 2.044-4.149), followed by hypothyroidism, OR = 1.807 (p = 0.046; 95% CI, 1.012-3.226), placental abruption, OR = 1.759 (p = 0.049; 95% CI, 1.002-3.087), reproductive tract infection, OR = 1.746 (p < 0.001; 95% CI, 1.325-2.301), abnormal amniotic fluid volume, OR = 1.737 (p = 0.003; 95% CI, 1.202-2.501), and fetal distress OR = 1.690 (p = 0.012; 95% CI, 1.120-2.551). CONCLUSION: Preventing risk factors, such as hypertension, hypothyroidism, and reproductive tract infections, during pregnancy may reduce the incidence of LBW neonates.

Improving the Performance of Continuous-Variable Measurement-Device-Independent Quantum Key Distribution via a Noiseless Linear Amplifier.

In the continuous variable measurement-device-independent quantum key distribution (CV-MDI-QKD) protocol, both Alice and Bob send quantum states to an untrusted third party, Charlie, for detection through the quantum channel. In this paper, we mainly study the performance of the CV-MDI-QKD system using the noiseless linear amplifier (NLA). The NLA is added to the output of the detector at Charlie's side. The research results show that NLA can increase the communication distance and secret key rate of the CV-MDI-QKD protocol. Moreover, we find that the more powerful the improvement of the performance with the longer gain of NLA and the optimum gain is given under different conditions.

High-energy square-wave pulses generated in a 1/1.5-µm dual-band mode-locked fiber laser.

The generation of square-wave pulses in a 1/1.5-µm dual-band mode-locked fiber laser is experimentally demonstrated. The laser is based upon a peculiar "figure-θ" architecture that exploits a single active fiber to realize dual-band operation. High-energy square-wave pulses are simultaneously generated in both the 1-µm and the 1.5-µm spectral band using the laser. The 1-µm pulse maintains wave-breaking-free operation during the increase of the pump power and finally achieves energy as high as 88.6 nJ, while the 1.5-µm pulse achieves energy up to 1.5 µJ before it ultimately collapses into second-order mode locking. To the best of our knowledge, this is the first report on the formation of square-wave pulses in dual-band mode-locked fiber lasers.

Acrylamide aggravates cognitive deficits at night period via the gut-brain axis by reprogramming the brain circadian clock.

Imbalance of the circadian rhythm leads to pathologies including obesity, neurodegenerative diseases, and even cancer. Acrylamide (ACR) is a chronic neurotoxin which can lead to carcinogenicity, reproduction toxicity, teratogenicity, and neurotoxicity. The aim of this study was to reveal a potential mechanism of ACR-triggered neurotoxicity related to circadian clock in mice brain. For this purpose, 80 3-month-old C57/BL6J mice were randomly divided into two groups (n = 40/group): the control group was fed a standard diet (AIN-93M) with pure water, and the ACR group was fed a standard diet (AIN-93M) with 0.003% ACR in drinking water for 16 weeks. In the current study, ACR treatment induced circadian disorder and suppressed the circadian-related protein expressions in mice brain. Furthermore, ACR diet aggravated the cognitive dysfunction and spatial memory loss at night phase. Consistent with these results, ACR caused cognitive defects in the night period by down-regulating the ERK/cAMP response element-binding protein (CREB)/brain-derived neurotrophic factor (BDNF) signaling pathways and the expression of synaptosomal-related protein SNAP-25 and PSD-95. Moreover, excessive autophagy phenomenon also occurred in mice hippocampus in the night phase under ACR administration. Of note, ACR stimulated the brain inflammatory reaction via affecting the intestinal barrier integrity and increasing the levels of circulating LPS, IL-1ß and TNF-α. Above all, the present research discovered that ACR is a potential circadian-depressing compound that influences cognitive function in mice brain.

CRISPR-Cas9 knockout of qseB induced asynchrony between motility and biofilm formation in Escherichia coli.

Generally, cell motility and biofilm formation are tightly regulated. The QseBC two-component system (TCS) serves as a bridge for bacterial signal transmission, in which the protein QseB acts as a response regulator bacterial motility, biofilm formation, and virulence. The mechanisms that govern the interaction between QseBC and their functions have been studied in general, but the regulatory role of QseB on bacterial motility and biofilm formation is unknown. In this study, the CRISPR-Cas9 system was used to construct the Escherichia coli MG1655ΔqseB strain (strain ΔqseB), and the effects of the qseB gene on changes in motility and biofilm formation in the wild type (WT) were determined. The motility assay results showed that the ΔqseB strain had higher (p < 0.05) motility than the WT strain. However, there was no difference in the formation of biofilm between the ΔqseB and WT strains. Real-time quantitative PCR illustrated that deletion of qseB in the WT strain downregulated expression of the type I pili gene fimA. Therefore, we might conclude that the ΔqseB induced the downregulation of fimA, which led to asynchrony between motility and biofilm formation in E. coli, providing new insight into the functional importance of QseB in regulating cell motility and biofilm formation.

High key rate continuous-variable quantum key distribution with a real local oscillator.

Continuous-variable quantum key distribution (CVQKD) with a real local oscillator (LO) has been extensively studied recently due to its security and simplicity. In this paper, we propose a novel implementation of a high-key-rate CVQKD with a real LO. Particularly, with the help of the simultaneously generated reference pulse, the phase drift of the signal is tracked in real time and then compensated. By utilizing the time and polarization multiplexing techniques to isolate the reference pulse and controlling the intensity of it, not only the contamination from it is suppressed, but also a high accuracy of the phase compensation can be guaranteed. Besides, we employ homodyne detection on the signal to ensure the high quantum efficiency and heterodyne detection on the reference pulse to acquire the complete phase information of it. In order to suppress the excess noise, a theoretical noise model for our scheme is established. According to this model, the impact of the modulation variance and the intensity of the reference pulse are both analysed theoretically and then optimized according to the experimental data. By measuring the excess noise in the 25km optical fiber transmission system, a 3.14Mbps key rate in the asymptotic regime proves to be achievable. This work verifies the feasibility of the high-key-rate CVQKD with a real LO within the metropolitan area.

Monitoring of continuous-variable quantum key distribution system in real environment.

How to guarantee the practical security of continuous-variable quantum key distribution (CVQKD) system has been an important issue in the quantum cryptography applications. In contrast to the previous practical security strategies, which focus on the intercept-resend attack or the Gaussian attack, we investigate the practical security strategy based on a general attack, i.e., an arbitrated individual attack or collective attack on the system by Eve in this paper. The low bound of intensity disturbance of the local oscillator signal for eavesdropper successfully concealing herself is obtained, considering all noises can be used by Eve in the practical environment. Furthermore, we obtain an optimal monitoring condition for the practical CVQKD system so that legitimate communicators can monitor the general attack in real-time. As examples, practical security of two special systems, i.e., the Gaussian modulated coherent state CVQKD system and the middle-based CVQKD system, are investigated under the intercept-resend attacks.

Development of an immersive virtual reality head-mounted display with high performance.

To resolve the contradiction between large field of view and high resolution in immersive virtual reality (VR) head-mounted displays (HMDs), an HMD monocular optical system with a large field of view and high resolution was designed. The system was fabricated by adopting aspheric technology with CNC grinding and a high-resolution LCD as the image source. With this monocular optical system, an HMD binocular optical system with a wide-range continuously adjustable interpupillary distance was achieved in the form of partially overlapping fields of view (FOV) combined with a screw adjustment mechanism. A fast image processor-centered LCD driver circuit and an image preprocessing system were also built to address binocular vision inconsistency in the partially overlapping FOV binocular optical system. The distortions of the HMD optical system with a large field of view were measured. Meanwhile, the optical distortions in the display and the trapezoidal distortions introduced during image processing were corrected by a calibration model for reverse rotations and translations. A high-performance not-fully-transparent VR HMD device with high resolution (1920×1080) and large FOV [141.6°(H)×73.08°(V)] was developed. The full field-of-view average value of angular resolution is 18.6 pixels/degree. With the device, high-quality VR simulations can be completed under various scenarios, and the device can be utilized for simulated trainings in aeronautics, astronautics, and other fields with corresponding platforms. The developed device has positive practical significance.

Myeloperoxidase-derived hypochlorous acid promotes ox-LDL-induced senescence of endothelial cells through a mechanism involving ß-catenin signaling in hyperlipidemia.

Myeloperoxidase (MPO)-derived product hypochlorous acid (HOCl) is able to induce cellular senescence and MPO is also expressed in endothelial cells besides the well-recognized immune cells. This study aims to clarify the association of endothelium-derived MPO with endothelial senescence in hyperlipidemia. The rats were fed with high-fat diet for 8 weeks to establish a hyperlipidemic model, which showed an increase in plasma lipids, endothelium-derived MPO expression, endothelial senescence and endothelial dysfunction concomitant with a reduction in glycogen synthase kinase 3 beta (GSK-3ß) activity and phosphorylated ß-catenin (p-ß-catenin) level as well as an increase in ß-catenin and p53 levels within the endothelium. Next, human umbilical vein endothelial cells (HUVECs) were incubated with oxidized low density lipoprotein (ox-LDL, 100 µg/ml) for 24 h to establish a senescent cell model in vitro. Consistent with the finding in vivo, ox-LDL-induced MPO expression and HUVECs senescence, accompanied by a decrease in GSK-3ß activity and p-ß-catenin level as well as an increase in HOCl content, ß-catenin and p53 levels; these phenomena were attenuated by MPO inhibitor. Replacement of ox-LDL with HOCl could also induce HUVECs senescence and activate the ß-catenin/p53 pathway. Based on these observations, we conclude that endothelium-derived MPO is upregulated in hyperlipidemic rats, which may contribute to the accelerated vascular endothelial senescence through a mechanism involving the ß-catenin/p53 pathway.

Continuous-variable quantum key distribution with 1 Mbps secure key rate.

We report the first continuous-variable quantum key distribution (CVQKD) experiment to enable the creation of 1 Mbps secure key rate over 25 km standard telecom fiber in a coarse wavelength division multiplexers (CWDM) environment. The result is achieved with two major technological advances: the use of a 1 GHz shot-noise-limited homodyne detector and the implementation of a 50 MHz clock system. The excess noise due to noise photons from local oscillator and classical data channels in CWDM is controlled effectively. We note that the experimental verification of high-bit-rate CVQKD in the multiplexing environment is a significant step closer toward large-scale deployment in fiber networks.