Ligand-Controlled Cobalt-Catalyzed Regio-, Enantio-, and Diastereoselective Oxyheterocyclic Alkene Hydroalkylation.

Metal-hydride-catalyzed alkene hydroalkylation has been developed as an efficient method for C(sp3)-C(sp3) coupling with broad substrate availability and high functional group compatibility. However, auxiliary groups, a conjugated group or a chelation-directing group, are commonly required to attain high regio- and enantioselectivities. Herein, we reported a ligand-controlled cobalt-hydride-catalyzed regio-, enantio-, and diastereoselective oxyheterocyclic alkene hydroalkylation without chelation-directing groups. This reaction enables the hydroalkylation of conjugated and unconjugated oxyheterocyclic alkenes to deliver C2- or C3-alkylated tetrahydrofuran or tetrahydropyran in uniformly good yields and with high regio- and enantioselectivities. In addition, hydroalkylation of C2-substituted 2,5-dihydrofuran resulted in the simultaneous construction of 1,3-distereocenters, providing convenient access to polysubstituted tetrahydrofuran with multiple enantioenriched C(sp3) centers.

Nickel-Catalyzed Remote Asymmetric Hydroalkylation of Alkenyl Ethers to Access Ethers of Chiral Dialkyl Carbinols.

Site- and enantio-selective alkyl-alkyl bond formation is privileged in the retrosynthetic analysis due to the universality of sp3-hybridized carbon atoms in organic molecules. Herein, we report a nickel-catalyzed remote asymmetric hydroalkylation of alkenyl ethers via synchronous implementation of alkene isomerization and enantioselective C(sp3)-C(sp3) bond formation. Regression analysis of catalyst structure-activity relationships accelerates the rational ligand modification through modular regulation. This reaction has several advantages for synthesizing chiral dialkyl carbinols and their ether derivatives, including the broad substrate scope, good functional group tolerance, excellent regioselectivity (>20:1 regioisomeric ratio), and high enantioselectivity (up to 95% enantiomeric excess).

Ligand-Controlled Cobalt-Catalyzed Regiodivergent Alkyne Hydroalkylation.

Regiodivergent alkyne hydroalkylation to generate different isomers of an alkene from the same alkyne starting material would be beneficial; however, it remains a challenge. Herein, we report a ligand-controlled cobalt-catalyzed regiodivergent alkyne hydroalkylation. The sensible selection of bisoxazoline (L1) and pyridine-oxazoline (L8) ligands led to reliable and predictable protocols that provided (E)-1,2-disubstituted and 1,1-disubstituted alkenes with high E/Z stereoselectivity and regioisomeric ratio starting from identical terminal alkyne and alkyl halide substrates and produced trisubstituted alkenes in the case of internal alkynes. This method exhibits a broad scope for terminal and internal alkynes with a wide range of activated and unactivated alkyl halides and shows excellent functional group compatibility.

Opto-electrical and polarization performance of a mesa-structured InGaAs PIN detector integrated with subwavelength aluminum gratings.

Polarization detection in the short-wave infrared (SWIR) region presents broad applications in target-background contrast enhancement, underwater imaging, material classification, etc. A mesa structure can prevent electrical cross talk due to its intrinsic advantages, making it potentially suited to meet the need for manufacturing smaller-sized devices to save cost and shrink volume. In this Letter, mesa-structured InGaAs PIN detectors with a spectral response ranging from 900 nm to 1700 nm and a detectivity of 6.28 × 1011 cm·Hz1/2/W at 1550 nm and -0.1 V bias (room temperature) have been demonstrated. Furthermore, the devices with subwavelength gratings in four orientations show obvious polarization performance. Their extinction ratios (ERs) can reach 18:1 at 1550 nm and their transmittances are over 90%. Such a polarized device with a mesa structure could realize miniaturized SWIR polarization detection.

Facile assembly and excellent elimination behavior of porous BiOBr-g-C3N4 heterojunctions for organic pollutants.

Photocatalysis can be an effective technique for eliminating organic contaminants from water. In this study, BiOBr flower-spheres coupled with porous graphite carbon nitride (g-C3N4) were synthesized by controlling the dosage of cetyltrimethylammonium bromide (CTAB). Various characterization techniques were then applied to elucidate the structure-performance relationships of the resulting heterojunction photocatalysts in degrading organic dyes. Experimental results established an optimal molar ratio for KBr to CTAB of 5:1. Benefiting from a remarkable porous structure and tight coupling between porous g-C3N4 and BiOBr, the optimal BiOBr-g-C3N4(2%) exhibited enhanced visible light absorption capability and promoted the separation of photoinduced carriers. Total removal efficiency for rhodamine B (RhB, 25.0 mL, 20.0 mg L-1) reached 87% within 30 min in the presence of BiOBr-g-C3N4(2%) (20.0 mg) (i.e., 1.51 µmol (gphotocatalyst min)-1), which is superior to the performance of BiOBr (72%) (i.e., 1.25 µmol (gphotocatalyst min)-1), g-C3N4 (21%) (i.e., 0.37 µmol (gphotocatalyst min)-1). Furthermore, the photocatalytic reaction rate constant over the optimal heterojunction was 0.034 min-1, which is significantly larger than those of porous g-C3N4 (0.003 min-1) and BiOBr (0.015 min-1). Moreover, this type II heterojunction showed good universality for other organic dyes (such as methyl violet, methylene blue, and crystal violet), highlighting a promising potential role in the elimination of environmental pollutants.

Silencing of Tenascin-C Inhibited Inflammation and Apoptosis Via PI3K/Akt/NF-κB Signaling Pathway in Subarachnoid Hemorrhage Cell Model.

OBJECTIVES: Tenascin-C (TNC) is upregulated in serum and cerebrospinal fluid after subarachnoid hemorrhage (SAH) and the deficiency of TNC could alleviate neuronal apoptosis and neuroinflammation after SAH. However, the specific mechanism of TNC regulating neuronal apoptosis and neuroinflammation after SAH is not well recognized. The aim of this study was to investigate whether PI3K/Akt/ NF-κB signaling pathway is involved in the regulation of TNC on early brain injury after SAH. METHODS: Oxygen hemoglobin (OxyHb) was used to induce SAH models in PC12 cells, and classified into control, SAH, LY294002, SAH+TNC-siRNA and SAH+TNC-siRNA+LY groups. Western blotting was applied to examine the protein expression of TNC, Caspase-3, Bax, Bcl-2, PI3K, p-Akt, and p-NF-κB. Reverse transcription quantitative polymerase chain reaction was applied to examine the TNC mRNA expression. Cholecystokinin (CCK)-8 and flow cytometry were used to examine cell proliferation and apoptosis, respectively. ELISA was applied to examine the content of interleukin 6, interleukin 1ß, and tumor necrosis factor α. We showed that the TNC protein was highly expressed in SAH cell model. RESULTS: OxyHb inhibited cell proliferation, promoted cell apoptosis and the expression of proapoptotic protein, and promoted proinflammatory cytokine secretion in PC12 cells, which were restored following TNC gene silencing. Moreover, OxyHb decreased the expression of PI3K and p-Akt and increased the expression of p-NF-κB p65 in PC12 cells, which were activated following TNC gene silencing. The LY294002 weakened the effect of TNC gene silencing. CONCLUSIONS: The TNC gene silencing relieved neuronal apoptosis and neuroinflammation by activating the PI3K/Akt/ NF-κB signaling pathway. TNC-induced neuroinflammation would be a new target to improve outcome after SAH.

Effect of short-term exercise intervention on cardiovascular functions and quality of life of chronic heart failure patients: A meta-analysis.

OBJECTIVE: The purpose of this study was to comprehensively evaluate the effect of short-term exercise intervention on the cardiovascular functions and quality of life (QoL) of patients with chronic heart failure (CHF). METHODS: This meta-analysis was analyzed using RevMan5.3 and Stata 13.0. The parameters of cardiovascular functions and QoL were assessed. Weighted mean differences and their corresponding 95% confidence intervals (CIs) were computed for continuous variables. RESULTS: Data from 2533 CHF patients enrolled in 28 published studies of randomized controlled trials (RCTs) were collated. There were significant differences in VO2 max prior to and after exercise intervention in CHF patients who are 50-55 years old (5 RCTs; 95% CI, -4.86 to -2.29; I2 = 50.5%), 60-65 years old (10 RCTs; 95% CI, -2.66 to -2.04; I2 = 0%), and 69-75 years old (5 RCTs; 95% CI, -1.88 to -0.34; I2 = 38.5%). VO2 max was significantly increased by aerobic exercise (9 RCTs; 95% CI, -3.45 to -1.92; I2 = 37.7%) and combined aerobic resistance exercise (4 RCTs; 95% CI, -4.41 to -0.26; I2 = 76.6%). There were significant differences in cardiac output (n = 303; 95% CI, -0.25 to -0.02; I2 = 12%) and QoL (n = 299; 95% CI, 3.19 to 9.70; I2 = 17%) prior to and after short-term exercise. CONCLUSION: Aerobic exercise and aerobic with resistance exercise can significantly improve the aerobic capacity of CHF patients, whereas resistance exercise cannot. The improvement in aerobic capacity caused by aerobic exercise and aerobic with resistance exercise decreases with age. Systolic blood pressure and ventricle structures and functions of CHF patients show no significant changes after the short-term exercise intervention.

Dietary diversity and possible cataract among Chinese elderly population.

Background: While cataracts, the vision-clouding eye disease associated with aging, have long presumed dietary underpinnings, the relationship between dietary variety and cataract risk in developing nations has been nebulous. This research aims to investigate the association between dietary diversity scores (DDS) and the risk of cataracts, while considering various dietary diversity patterns. Methods: This research utilized cross-sectional data from 2008 to 2018 extracted from the Chinese Longitudinal Healthy Longevity Survey (CLHLS), implementing the Visual Function Index-14 (VF-14) to gauge cataract probability. The researchers captured participants' diet diversity by using the DDS metric and categorized it into total, animal-based, and plant-based diet patterns. To explore associations between dietary variety and cataract potential, a generalized estimating equation (GEE) was statistically modeled using the data, with adjustments made to account for potentially confounding factors. Additionally, sensitivity analyses were conducted, excluding individuals with assorted eye conditions, to isolate cataract relationships. Results: The study sample comprised 47,395 participants with a mean age of 86.1 years. The study found that a lower likelihood of developing cataract was correlated with both total diet (OR = 0.74; 95% CI: 0.69-0.79) and plant-based diet (OR = 0.65; 95% CI: 0.61-0.71), whereas a slightly higher risk was associated with animal-based diet (OR = 0.90; 95% CI = 0.84-0.96). The results remained unchanged in the sensitivity analysis. Conclusion: The diversified diets are linked to a decreased likelihood of developing cataracts, but animal-based diet faced heightened cataract odds. The implementation of a varied dietary regimen has the potential to serve as a cost-effective and efficient intervention strategy for the prevention of cataracts.

Construction of 2D/0D Graphene Oxide/Copper(I) Oxide-Incorporated Titanium Dioxide Mixed-Dimensional Membranes with Ultrafast Water Transport and Enhanced Antifouling Properties.

Graphene oxide (GO) membranes are emerging for water treatment. Meanwhile, challenges remain due to membrane fouling and their instability in aqueous solutions. Herein, a novel GO-based mixed-dimensional membrane with superior antifouling and nonswelling properties was prepared by assembling two-dimensional (2D) GO nanosheets and zero-dimensional (0D) copper(I) oxide-incorporated titanium dioxide photocatalyst (CT). The decoration of CT in GO nanosheets tuned the microstructure and surface hydrophilicity while creating more transport channels in CT/GO membranes. This resulted in a high water permeance of 171.5 L m-2 h-1 bar-1 and improved selectivity to various dye molecules (96.2-98.6%). Due to the significantly enhanced antibacterial properties of the CT nanoparticles, the growth of bacteria on the surface of the CT/GO membrane was suppressed (threefold less than that on the GO membrane). Moreover, the embedding of photocatalysts also allowed CT/GO membranes to exhibit ∼9-fold improvement in antibacterial activity and organic dye degradation performance under visible-light irradiation. This study offers a powerful solution to enhance the nanofiltration performance and antibacterial properties of GO membranes toward practical applications.

Cytidine Alleviates Dyslipidemia and Modulates the Gut Microbiota Composition in ob/ob Mice.

Cytidine and uridine are endogenous metabolites in the pyrimidine metabolism pathway, and cytidine is a substrate that can be metabolized into uridine via cytidine deaminase. Uridine has been widely reported to be effective in regulating lipid metabolism. However, whether cytidine could ameliorate lipid metabolism disorder has not yet been investigated. In this research, ob/ob mice were used, and the effect of cytidine (0.4 mg/mL in drinking water for five weeks) on lipid metabolism disorder was evaluated in terms of an oral glucose tolerance test, serum lipid levels, liver histopathological analysis and gut microbiome analysis. Uridine was used as a positive control. Our findings reveal that cytidine could alleviate certain aspects of dyslipidemia and improve hepatic steatosis via modulating the gut microbiota composition in ob/ob mice, especially increasing the abundance of short-chain fatty acids-producing microbiota. These results suggest that cytidine supplementation could be a potential therapeutic approach for dyslipidemia.

Microplastic effects on soil system parameters: a meta-analysis study.

Microplastics are generally considered as an emerging contaminant in the environment due to their toxic additives and transport of other contaminants. However, the potential threats of microplastics in soil should be concerned due to inconsistent research results. In this study, a meta-analysis based on 32 recent relevant studies was conducted to compare the response of soil system parameters including microbial community, aggregate structure, soil nutrient contents, and crop growth to the presence of microplastics. The results showed that microplastics presented no significant effects on soil dissolved organic carbon contents and the amounts of available phosphate, nitrate, and ammonium. Although microplastics would not significantly influence the diversity of soil microorganisms, they could significantly increase soil microorganism amounts with a standard mean difference at 19.32. We also found that microplastics tended to significantly decrease soil water stable macro-aggregate (> 0.25 mm) contents with a significantly negative standard mean difference (- 0.90) in meta-analysis. Moreover, soil microplastics seemed not to affect crop growth by having non-significant effects on both crop under-ground and above-ground biomasses. These results indicate that up to date, the main negative impacts caused by microplastics on soil systems could be their negative functions on soil aggregation.

High performance visible-SWIR flexible photodetector based on large-area InGaAs/InP PIN structure.

Mechanically flexible optoelectronic devices and systems can enable a much broader range of applications than what their rigid counterparts can do, especially for novel bio-integrated optoelectronic systems, flexible consumer electronics and wearable sensors. Inorganic semiconductor could be a good candidate for the flexible PD when it can keep its high performance under the bending condition. Here, we demonstrate a III-V material-based flexible photodetector operating wavelength from 640 to 1700 nm with the high detectivity of 5.18 × 1011 cm‧Hz1/2/W and fast response speed @1550 nm by using a simply top-to-down fabrication process. The optoelectrical performances are stable as the PDs are exposed to bending cycles with a radius of 15 mm up to 1000 times. Furthermore, the mechanical failure mode of the PD is also investigated, which suggests that the cracking and delamination failure mode are dominant in bending up and bending down direction, respectively. Such a flexible III-V material-based PD and design with stable and high performance could be a promising strategy for the application of the flexible broad spectrum detection.

Stem cells from human exfoliated deciduous teeth attenuate trigeminal neuralgia in rats by inhibiting endoplasmic reticulum stress.

Background: The treatment of trigeminal neuralgia remains a challenging issue. Stem cells from human exfoliated deciduous teeth (SHED) provide optimized therapy for chronic pain. This study aimed to investigate the mechanisms underlying the attenuation of trigeminal neuralgia by SHED. Methods: Trigeminal neuralgia was induced by chronic constriction injury of the infraorbital nerve. The mechanical threshold was assessed after model establishment and local SHED transplantation. Endoplasmic reticulum (ER) morphology and Caspase12 expression in trigeminal ganglion (TG) was evaluated as well. BiP expression was observed in PC12 cells induced by tunicamycin. Results: The local transplantation of SHED could relieve trigeminal neuralgia in rats. Further, transmission electron microscopy revealed swelling of the ER in rats with trigeminal neuralgia. Moreover, SHED inhibited the tunicamycin-induced up-regulated expression of BiP mRNA and protein in vitro. Additionally, SHED decreased the up-regulated expression of Caspase12 mRNA and protein in the TG of rats caused by trigeminal neuralgia after chronic constriction injury of the infraorbital nerve mode. Conclusions: This findings demonstrated that SHED could alleviate pain by relieving ER stress which provide potential basic evidence for clinical pain treatment.

Integrated photocatalysis-adsorption-membrane separation in rotating reactor for synergistic removal of RhB.

A synergistic system of integrated photocatalysis-adsorption-membrane separation in a rotating reactor was designed. The composite membrane was prepared via filtration process under vacuum, and it was composed of graphene oxide (GO) acted as the separation membrane, activated carbon (AC) as the adsorbent and Ag@BiOBr as the photocatalyst, respectively. In this Ag@BiOBr/AC/GO membrane system, rotation of the membrane could avoid the light-shielding effect from organic color pollutants to achieve the complete removal of pollutants. More importantly, the synergistic effect among photocatalysis, adsorption and membrane separation in rotating reactor was significant for the efficient removal of rhodamine B (RhB). In the Ag@BiOBr/AC/GO composite membrane, GO membrane layer could reject the organic molecular by the assistance of AC layer with efficient adsorption capacity, and Ag@BiOBr at outer layer could photodegrade the organics under visible light irradiation. The photocatalysis process could solve the problem of membrane fouling and adsorption could assist GO membrane for stopping the permeation of pollutants. Meanwhile, GO membrane was not only beneficial for catalyst recovery, but also could concentrate the pollutants via the membrane separation to accelerate the photocatalytic degradation. At the same time, both the photocatalysis degradation and membrane separation could promote the adsorption ability of AC. This synergistic system showed the significant potential for the practical application in the future.

Novel mutations and hot-spots in patients with purine nucleoside phosphorylase deficiency.

Purine nucleoside phosphorylase (PNP) deficiency results in severe immune dysfunction and early death from infections. Lymphopenia, reduced serum uric acid, and abnormal PNP enzymatic activity assist in the diagnosis of PNP-deficient patients. Analysis of the gene encoding PNP in these patients reveals several recurring mutations. Identification of these hot-spots for mutation may allow faster confirmation of the diagnosis in suspected cases.