Recent advances in organolead halide crystalline materials for photocatalytic H2 evolution and CO2 reduction applications.

The photocatalytic technique has been widely recognized as a feasible technological route for sustainable energy conversion of solar energy into chemical energy. Photocatalysts play a vital role in the whole catalytic process. In particular, organolead halide perovskites have become emerging photocatalysts, owing to their precisely tunable light absorption range, high carrier diffusion mobility, and longer carrier lifetime and diffusion length. Nevertheless, their intrinsic structural instability and high carrier recombination rate are the major bottlenecks for further development in photocatalytic applications. This Frontier is focused on the recent research about the instability mechanism of organolead halide perovskites. Then, we summarize the recently developed strategies to improve the structural stability and photocatalytic activity of organolead halide materials, with an emphasis on the construction of organolead halide crystalline catalysts with high intrinsic structural stability. Finally, an outlook and challenges of organometal halide photocatalysts are presented, demonstrating the irreplaceable role of this class of emergent materials in the field of photo-energy conversion.

Effects of hysteroscopic septum incision versus expectant management on IVF outcomes in women with complete septate uterus: a retrospective study.

OBJECTIVE: This retrospective study aimed to assess the impact of hysteroscopic septum incision on in vitro fertilization (IVF) outcomes among infertile women diagnosed with a complete septate uterus and no history of recurrent pregnancy loss. METHODS: The study was conducted at a tertiary reproductive center affiliated with a university hospital and involved 78 women with a complete septate uterus. Among them, 34 women underwent hysteroscopic septum incision, while 44 women opted for expectant management. The primary outcome measure was the live birth rate, while secondary outcomes included clinical pregnancy rate, preterm birth rate, miscarriage rate, and ongoing pregnancy rate. RESULTS: Women who underwent hysteroscopic septum incision demonstrated a comparable likelihood of achieving a live birth compared to those managed expectantly (25% vs. 25%, Relative Risk (RR): 1.000, 95% Confidence Interval (CI): 0.822 to 1.216). No preterm births occurred in either group. The clinical pregnancy rate, ongoing pregnancy rate, and miscarriage rate showed no significant differences between the surgical group and the expectant management group. Subgroup analyses based on the type of embryo transferred also revealed no significant differences in outcomes. CONCLUSIONS: Hysteroscopic septum incision does not appear to yield improved IVF outcomes compared to expectant management in infertile women with a complete septate uterus and no history of recurrent pregnancy loss.

Modulating Inorganic Dimensionality of Ultrastable Lead Halide Coordination Polymers for Photocatalytic CO2 Reduction to Ethanol.

Lead halide hybrids have shown great potentials in CO2 photoreduction, but challenging to afford C2+ reduced products, especially using H2O as the reductant. This is largely due to the trade-off problem between instability of the benchmark 3D structures and low carrier mobility of quasi-2D analogues. Herein, the lead halide dimensionality of robust coordination polymers (CP) was modulated by organic ligands differing in a single-atom change (NH vs. CH2), in which the NH groups coordinate with interlamellar [PbI2] clusters to achieve the important 2D→3D transition. This first CP based on 3D cationic lead iodide sublattice possesses both high aqueous stability and a low exciton binding energy of 25 meV that is on the level of ambient thermal energy, achieving artificial photosynthesis of C2H5OH. Photophysical studies combined with theoretical calculations suggest the bridging [PbI2] clusters in the 3D structure not only results in enhanced carrier transport, but also promotes the intrinsic charge polarization to facilitate the C-C coupling. With trace loading of Rh cocatalyst, the apparent quantum efficiency of the 3D CP reaches 1.4 % at 400 nm with a high C2H5OH selectivity of 89.4 % (product basis), which presents one of the best photocatalysts for C2 products to date.

An all-in-one FeOx-rGO sponge fabricated by solid-phase microwave thermal shock for water evaporation and purification.

Developing high-efficiency photothermal seawater desalination devices is of significant importance in addressing the shortage of freshwater. Despite much effort made into photothermal materials, there is an urgent need to design a rapidly synthesized photothermal evaporator for the comprehensive purification of complex seawater. Therefore, we report on all-in-one FeOx-rGO photothermal sponges synthesized via solid-phase microwave thermal shock. The narrow band gap of the semiconductor material Fe3O4 greatly reduces the recombination of electron-hole pairs, enhancing non-radiative relaxation light absorption. The abundant π orbitals in rGO promote electron excitation and thermal vibration between the lattices. Control of the surface hydrophilicity and hydrophobicity promotes salt resistance while simultaneously achieving the purification of various complex polluted waters. The optimized GFM-3 sponge exhibitedan enhanced photothermal conversion rate of 97.3% and a water evaporation rate of 2.04 kg/(m2·hr), showing promising synergistic water purification properties. These findings provide a highly efficient photothermal sponge for practical applicationsof seawater desalination and purification,as well as develop a super-rapid processing methodology for evaporation devices.

Effects of Infertility Drug Exposure on the Risk of Borderline Ovarian Tumors: A Systematic Review and Meta-Analysis.

Whether infertility drug exposure increases the risk of borderline ovarian tumors (BOTs) remains controversial. The present study was conducted with a comprehensive search for studies published from January 1990 to December 2021 in the online databases Cochrane Library, PubMed, Web of Science and EMBASE. We considered the first diagnosis of a BOT as the primary outcome. The odds ratio (OR) was calculated with corresponding 95% confidence intervals (CIs) for the risk of BOTs in patients who were treated with infertility drugs. Ten studies, a total of 2,779,511 women, qualified for inclusion in this meta-analysis. The pooled OR of 1.56 (95% CI: 1.09-2.22) revealed a significant positive association between infertility drugs and an increased risk for BOTs, but for specific drugs, only CC plus Gn had statistical significance. No publication bias was detected using the Egger and Begg tests (p > 0.05). A significant difference in BOT incidence was observed among infertile women and nulliparous women who were treated with or without infertility drugs. In conclusion, the use of infertility drugs may increase the risk of BOTs, but a dose-dependent relationship was not observed between the number of assisted reproduction technology cycles and the risk of BOTs, and infertile women who successfully became pregnant might have a reduced risk. Registration: PROSPERO, CRD42022330775.

Neurophysiological correlates for dynamic variability between vigilance and avoidance in test anxiety.

Attention bias (ABs) to threat is essential in the etiology and maintenance of test anxiety. However, little is known about the attention pattern of ABs in test anxiety. The stimulus duration affects the attention pattern in anxiety. Thus, the present research combined the dot-probe paradigm and event-related potentials (ERPs) and varied the stimulus duration (100 ms or 500 ms) to test the ABs in test anxiety. Consequently, both groups showed a threat N2pc in 100 ms and 500 ms duration, suggesting that both groups allocated attention to the test-related threat. However, in the 100 ms duration, the high test-anxious (HTA) group had smaller target-elicited P1 and greater target-elicited N2 in the threat-congruent condition than in the neutral condition. In the 500 ms duration, an earlier threat N2pc and a threat PD followed a greater target P1, and smaller target N2 were pronounced in the HTA group. The current results provided electrophysiological evidence that the HTA group kept a dynamic attention pattern that fluctuated shift between vigilance and avoidance in the 100 ms and 500 ms duration. The HTA group was more vigilant than the LTA group in the 500 ms duration when strategic attention was concerned, proposing that vigilance in test anxiety was not an automatic process.

Interface-Coupling of NiFe-LDH on Exfoliated Black Phosphorus for the High-Performance Electrocatalytic Oxygen Evolution Reaction.

Electrochemical oxygen evolution reaction (OER) always plays an important role in many electrochemical energy storage and conversion systems. Owing to the slow kinetics mainly brought from multiple proton-coupled electron transfer steps, the design and exploit low-cost, highly active, durable OER electrocatalysts are of significant importance. Although the black phosphorus (BP) shows good electrocatalytic OER performance, it still faces the problems of poor intrinsic activity and low stability due to its instability under ambient conditions. The NiFe-LDH was assembled onto the surfaces of exfoliated BP (EBP) nanoflakes to realize the interfacial coupling between them, achieving an effective improvement in electrocatalytic activity and stability. Benefitting from the interfacial P-O bonding, the NiFe-LDH@EBP hybrid shows high OER activity with a low overpotential of ∼240 mV@10 mA cm-2 toward OER under alkaline conditions, as well as the good stability. Density functional theory (DFT) calculations proved that the interface-coupling of NiFe-LDH on BP promotes charge transfer kinetics and balances the adsorption/desorption of reaction intermediates, ultimately imparting excellent OER electrocatalytic activity.

Efficient and reusable catalysis of benzylic C-H oxidation over layered [Co5(OH)6]4+ derivatives.

Aerobic oxidation of benzylic C(sp3)-H bonds in a green and heterogeneous manner is a major target in organic catalysis. Herein, we report the synthesis of 3D coordination polymers containing [Co5(OH)6]4+ layers, affording reusable and efficient oxidation of ethylbenezene and tetralin by using O2 as the oxidant. Moreover, the cleavage of CoII-carboxylate bonding renders atomically thin cobaltate nanosheets and enhanced catalytic performance. This is one of the top catalytic performances for CoII-catalyzed benzylic C(sp3)-H oxidation (∼0.02 mol% Co and 76% conversion for nanosheets), ascribed to the exposed, accessible and coordinatively unsaturated CoII species.

Complete mitochondrial genome analysis and molecular phylogenetic implications of Kennelia xylinana (Lepidoptera: Tortricidae).

Kennelia is a small genus in Tortricidae that is distributed in the Oriental and Palaearctic regions, and its taxonomic position within the subfamily Olethreutinae is controversial. For a comprehensive understanding of the genus, we sequenced the mitogenome of Kennelia xylinana, the type species of Kennelia, and Ancylis unculana, a species of Enarmoniini; analyzed the mitogenome characteristics of K. xylinana; and explored its phylogenetic position. Similar to other members of Lepidoptera, the mitogenome of K. xylinana is 15,762-bp long and consists of 13 protein-coding genes (PCGs), two ribosomal RNA genes, 22 transfer RNA genes, and a noncoding control region. In particular, we found a structure (TATAATTAATAA)11 in the middle of the AT-rich region. Based on the Bayesian inference and maximum likelihood analyses of the 13 PCGs of 40 tortricid species, representing 8 tribes of 2 subfamilies, K. xylinana was clustered with two members of Enarmoniini, A. unculana and Loboschiza koenigiana, and formed highly supported monophyly. The results indicate that Kennelia should be placed in the tribe Enarmoniini.

Lipid Metabolic Process Involved in Oocyte Maturation During Folliculogenesis.

Oocyte maturation is a complex and dynamic process regulated by the coordination of ovarian cells and numerous extraovarian signals. From mammal studies, it is learnt that lipid metabolism provides sufficient energy for morphological and cellular events during folliculogenesis, and numerous lipid metabolites, including cholesterol, lipoproteins, and 14-demethyl-14-dehydrolanosterol, act as steroid hormone precursors and meiotic resumption regulators. Endogenous and exogenous signals, such as gonadotropins, insulin, and cortisol, are the upstream regulators in follicular lipid metabolic homeostasis, forming a complex and dynamic network in which the key factor or pathway that plays the central role is still a mystery. Though lipid metabolites are indispensable, long-term exposure to a high-fat environment will induce irreversible damage to follicular cells and oocyte meiosis. This review specifically describes the transcriptional expression patterns of several lipid metabolism-related genes in human oocytes and granulosa cells during folliculogenesis, illustrating the spatiotemporal lipid metabolic changes in follicles and the role of lipid metabolism in female reproductive capacity. This study aims to elaborate the impact of lipid metabolism on folliculogenesis, thus providing guidance for improving the fertility of obese women and the clinical outcome of assisted reproduction.

Clinical Outcomes of In Vitro Maturation After Oocyte Retrieval With Gynecological Surgery for Refractory Polycystic Ovary Syndrome: A Retrospective Cohort Study.

Objective: To explore the clinical outcomes of unstimulated in vitro maturation (IVM) after oocyte retrieval with gynecological surgery (IVM-surgery) for refractory polycystic ovary syndrome (PCOS) and analyze the influencing factors. Methods: Patients with refractory PCOS who underwent unstimulated IVM-surgery from June 2014 to September 2018 were included in this retrospective cohort study. Matured IVM oocytes were freshly fertilized and subsequently frozen at the blastocyst stage. Frozen-thawed embryo transfer was then conducted according to the desire of patients. Oocytes and embryological outcomes, reproductive outcomes were evaluated. Influencing factors of oocytes and embryological outcomes were analyzed by univariate analysis and multivariate analysis. Receiver operating characteristic curves were used to evaluate the predict value of serum hormone levels for oocytes and embryological outcomes. Results: A total of 93 patients with refractory PCOS who underwent unstimulated IVM-surgery were included in this study.13 patients (13/85, 15.3%) had spontaneous pregnancy and live birth after surgery. 34 patients (34/93, 36.6%) obtained blastocysts and received embryo transfer, of which 13 patients (13/34, 38.2%) eventually achieved live birth by IVM. Higher anti-Mullerian hormone, antral follicle count and basal serum luteinizing hormone (LH) levels were strongly correlated with higher number of oocytes retrieved (P = 0.004, 0.004, 0.040, respectively). Higher basal serum follicle-stimulating hormone (FSH) and LH were significantly associated with higher oocyte maturation rate (P = 0.001 and P = 0.004, respectively) and blastocyst formation (P = 0.036 and P = 0.003, respectively). There was a significant linear correlation between basal serum FSH and LH (r = 0.500, P <0.001). What is more, basal serum FSH and LH had predictive value for oocytes and embryological outcomes. Conclusion: Unstimulated IVM-surgery provided the opportunity for both spontaneous pregnancy and assisted reproductive technology. Basal FSH and LH were significantly associated with oocyte maturation rate and blastocyst formation of unstimulated IVM-surgery.

The complete mitochondrial genome of Clepsis pallidana (Lepidoptera: Tortricidae) with phylogenetic implications.

The leaf roller, Clepsis pallidana (Fabricius, 1776) (Lepidoptera: Tortricidae), is an important pest of many crops in China. The circular genome is 15,679 bp in length, consisting of 13 protein-coding genes, 22 transfer RNA genes, two ribosomal RNA genes, and a non-coding AT-rich region. The base composition of the whole mitogenome is 41.2% A, 40.1% T, 11.1% C, and 7.7% G, which shows a strong AT bias. Phylogenetic analysis based on 13 PCGs showed that C. pallidana was closely related to Epiphyas postvittana and clustered within Archipini clade, which was consistent with the traditional classification.

Fabrication of Robust and Porous Lead Chloride-Based Metal-Organic Frameworks toward a Selective and Sensitive Smart NH3 Sensor.

Organolead halide materials have shown promising optoelectronic properties that are suitable for light-emitting diodes (e.g., strong photoluminescence, narrow emission width, and high charge carrier mobility). However, the vast majority of them have no open porosity or open metal sites for host-guest interactions and are therefore not widely applicable in intrinsic fluorescent sensing of small molecules. Herein, we report a lead chloride-based metal-organic framework (MOF) with high porosity and stability and promising photoluminescent characteristics, performing as a sensitive, selective, and long-term stable fluorescence probe for NH3. For the first time, a homemade dynamic real-time photoluminescence monitoring system was developed, which showed that our haloplumbate-based MOF has an immediate response and an extremely low limit of detection (12 ppm) toward NH3. A variety of experimental characterization and theoretical calculations evidenced that the photoluminescence quenching was ascribed to the coordination between NH3 guests and exposed Pb2+ centers in MOFs. Moreover, a portable on-site smart NH3 detector was designed based on this haloplumbate-MOF using a 3D printer, and the quantitative recovery experiment demonstrated the effective detection of NH3 in the range of 15-150 ppm. This study opens a new pathway to design organolead halide-based MOFs to perform on-site chemical sensing of small molecules and shows their high potential to monitor safety concentrations of NH3 in different industrial sites.

Lipid Metabolism Was Associated With Oocyte in vitro Maturation in Women With Polycystic Ovarian Syndrome Undergoing Unstimulated Natural Cycle.

OBJECTIVE: Hyperlipidemia are common polycystic ovarian syndrome (PCOS)-related metabolic dysfunctions and can adversely affect assisted reproductive technology (ART) outcomes in controlled ovarian hyperstimulation (COH) cycles. The objective of this study is to analyze the relationship between lipid metabolism and ART outcomes in unstimulated natural cycles without the utilization of ovarian induction drugs, which is still uncertain. METHODS: This retrospective study included infertile women with PCOS between 21 and 40 years old undergoing unstimulated natural cycles from January 01, 2006 to December 31, 2019. Lipid metabolism was measured by body mass index (BMI) and serum biochemical parameters including total cholesterol (TC), triglycerides (TG), high and low density lipoprotein cholesterol (HDL-C and LDL-C). ART outcomes were measured by number of oocytes retrieved, oocyte maturation quality and developmental potential, clinical pregnancy and live birth. RESULTS: A total of 586 patients were included in this study. Multivariate Poisson log-linear analysis showed that high TC (≥5.18 mmol/L), triglycerides (TG) (≥1.76 mmol/L), LDL-C (≥3.37 mmol/L) levelsand low HDL-C levels (≤1.04 mmol/L) were significantly (P TC = 0.001, P TG < 0.001, P HDL -C < 0.001, P LDL -C < 0.001) associated with increased number of oocytes retrieved. BMI was significantly negatively associated with maturation rate (P < 0.001), fertilization rate (P < 0.001) and transferrable embryo rate (P = 0.002). High TG levels and low HDL-C levels were also associated with decreased maturation rate (P TG < 0.001, P HDL-C = 0.026). Logistic regression analysis showed statistically significant association between obesity (≥28.0 kg/m2) and decreased live birth rate (P = 0.004) as well as cumulative live birth rate (P = 0.007). CONCLUSION: This is the first study that focused on the relationship between basal lipid metabolism and ART outcomes in women with PCOS undergoing unstimulated natural cycles. The results showed that high levels of lipid metabolic parameters were associated with increased number of oocytes retrieved and obesity was closely associated with impaired oocyte maturation quality and developmental potential as well as poor live birth outcomes.

Precise incorporation of transition metals into organolead oxyhalide crystalline materials for photocatalysis.

Organolead halide crystalline materials are an emerging class of high-performance photocatalysts. However, limited studies have been performed to tune their photoactive properties by precise introduction of transition metals. Herein, we report the successful incorporation of four different transition metal centers (Mn2+, Co2+, Ni2+ and Zn2+) into a lead oxyhalide crystalline matrix via isoreticular synthesis. Importantly, the precise control of the incoming transition metal positions has been achieved by its octahedral coordination with three organic ligands. Among them, the Zn2+-incorporated material exhibits the highest catalytic activity and recyclable activity in benzylamine oxidation under UV light, which is probably ascribed to the long carrier lifetime and efficient carrier transfer.

N-Heterocyclic Carbene-Stabilized Ultrasmall Gold Nanoclusters in a Metal-Organic Framework for Photocatalytic CO2 Reduction.

Ultrafine gold nanoclusters (Au-NCs) are susceptible to migrate and aggregate, even in the porosity of many crystalline solids. N-heterocyclic carbenes (NHCs) are a class of structurally diverse ligands for the stabilization of Au-NCs in homogeneous chemistry, showing catalytic reactivity in CO2 activation. Herein, for the first time, we demonstrate a heterogeneous nucleation approach to stabilize ultrasmall and highly dispersed gold nanoclusters in an NHC-functionalized porous matrix. The sizes of gold nanoclusters are tunable from 1.3 nm to 1.8 nm based on the interpenetration of the metal-organic framework (MOF) topology. Control experiments using amine or imidazolium-functionalized MOFs afforded the aggregation of Au species. The resultant Au-NC@MOF composite exhibits a steady and excellent activity in photocatalytic CO2 reduction, superior to control mixtures without NHC-ligand stabilization. Mechanistic studies reveal the synergistic catalytic effect of MOFs and Au-NCs through the MOF-NHC-Au covalent-bonding bridges.

OP-IVM: Combining In vitro Maturation after Oocyte Retrieval with Gynecological Surgery.

The use of in vitro maturation (IVM) before gynecological operation (OP-IVM) is an extension of conventional IVM that combines IVM following oocyte retrieval with routine gynecological surgery. OP-IVM is suitable for patients undergoing benign gynecological surgery who have the need for fertility preservation (FP) or infertility treatments such as in vitro fertilization and embryo transfer (IVF-ET). In the operating room, patients undergoing benign gynecological surgery are first anesthetized and receive ultrasound-guided immature follicle aspiration (IMFA) treatment. As the subsequent gynecological surgery is performed, the cumulus-oocyte complexes (COCs) are examined, and the immature COCs are transferred into the IVM medium and cultured for 28-32 hours in the IVF laboratory. After assessment, mature oocytes in the MII stage will be selected and cryopreserved in liquid nitrogen for FP or fertilized by intracytoplasmic sperm injection (ICSI) for IVF-ET. By combining IVM with gynecological surgery, immature oocytes that would have been discarded can be saved and used for assisted reproductive technology (ART). The procedure, significance and critical aspects of OP-IVM are described in this article.

The genus Syntozyga Lower (Lepidoptera, Tortricidae) in China, with descriptions of two new species.

Species of the genus Syntozyga Lower, 1901 (Lepidoptera, Tortricidae, Olethreutinae) from China are studied. Syntozyga apicispinata sp. nov. and S. similispirographa sp. nov. are described, S. pedias (Meyrick, 1920) is recorded for the first time from China, and S. spirographa (Diakonoff, 1968) is newly recorded from the Chinese mainland. Adults and genitalia are illustrated, and a distribution map of the Chinese species is given. Keys to identify the Chinese species of Syntozyga are provided. Species of the genus are well clustered in a neighbor-joining tree based on the sequence data of the COI gene. COI sequences corresponding to the new species and S. spirographa (Diakonoff, 1968) are submitted to BOLD.

Intrinsic self-trapped broadband emission from zinc halide-based metal-organic frameworks.

Organolead halide perovskites are an emerging class of intrinsic self-trapped broadband emitters, but suffer from lead toxicity and stability problems. Herein, we report a series of metal-organic frameworks (MOFs) based on 0-D zinc halide secondary building units (SBUs), which emit large Stokes shifted broadband bluish-white light. A variety of photophysics studies demonstrate that the broadband emission probably originates from self-trapped excitons, owing to the structurally deformable SBUs. Among the intrinsic self-trapped emitters, these MOFs are very rare examples that exhibit both long-term environmental stability and contain non-toxic elements. Moreover, the open porosity enables the MOF to serve as a host matrix for encapsulating green-emitting Alq3 molecules, exhibiting cold white-light chromatic coordinates of (0.27,0.36) and a correlated color temperature of 8321 K.

Efficient, broadband self-trapped white-light emission from haloplumbate-based metal-organic frameworks.

Metal-organic frameworks (MOFs) with low-dimensional, deformable haloplumbate secondary building units (SBUs) are an emerging class of intrinsic white-light emitters combining advantageous properties of both MOFs and lead perovskites. Herein, we have successfully synthesized two MOFs with haloplumbate SBUs occupying an extremely high degree of structural strain with local zigzag Pb-X-Pb-X (X = Cl/Br) connectivity located in single-stranded helices. Thus, the electron-phonon coupling in the deformable SBUs affords intrinsic white-light emission and moderately high external photoluminescence quantum efficiencies of 12-15%, superior to our previously reported MOFs. Moreover, the excellent photocarrier diffusion properties of lead perovskites have been successfully incorporated into the MOFs with high chemical robustness in moisture (up to 90% relative humidity, RH).