Cl Groups Research Articles

Single-Atom Pt Loaded on MOF-Derived Porous TiO2 with Maxim-Ized Pt Atom Utilization for Selective Hydrogenation of Halonitro-benzene.

The location control of single atoms relative to supports is challenging for single-atom catalysts, leading to a large proportion of inaccessible single atoms buried under supports. Herein, a "sequential thermal transition" strategy is developed to afford single-atom Pt preferentially dispersed on the outer surface of TiO2. Specifically, a Ti-MOF confining Pt nanoparticles is converted to PtNPs and TiO2 composite coated by carbon (PtNPs&TiO2@C-800) at 800 °C in N2. Subsequent thermal-driven atomization of PtNPs at 600 °C in air produce single-atom Pt decorated TiO2 (Pt1/TiO2-600). The resulting Pt1/TiO2-600 exhibits superior p-chloroaniline (p-CAN) selectivity (99 %) to PtNPs/TiO2-400 (45 %) and much better activity than Pt1@TiO2-600 with randomly dispersed Pt1 both outside and inside TiO2 in the hydrogenation of p-chloronitrobenzene (p-CNB). Mechanism investigations reveal that Pt1/TiO2-600 achieves 100 % accessibility of Pt1 and preferably adsorbs the -NO2 group of p-CNB while weakly adsorbs -Cl group of p-CNB and p-CAN, promoting catalytic activity and selectivity.

Single‐Atom Pt Loaded on MOF‐Derived Porous TiO2 with Maxim‐Ized Pt Atom Utilization for Selective Hydrogenation of Halonitro‐benzene

AbstractThe location control of single atoms relative to supports is challenging for single‐atom catalysts, leading to a large proportion of inaccessible single atoms buried under supports. Herein, a “sequential thermal transition” strategy is developed to afford single‐atom Pt preferentially dispersed on the outer surface of TiO2. Specifically, a Ti‐MOF confining Pt nanoparticles is converted to PtNPs and TiO2 composite coated by carbon (PtNPs&TiO2@C‐800) at 800 °C in N2. Subsequent thermal‐driven atomization of PtNPs at 600 °C in air produce single‐atom Pt decorated TiO2 (Pt1/TiO2‐600). The resulting Pt1/TiO2‐600 exhibits superior p‐chloroaniline (p‐CAN) selectivity (99 %) to PtNPs/TiO2‐400 (45 %) and much better activity than Pt1@TiO2‐600 with randomly dispersed Pt1 both outside and inside TiO2 in the hydrogenation of p‐chloronitrobenzene (p‐CNB). Mechanism investigations reveal that Pt1/TiO2‐600 achieves 100 % accessibility of Pt1 and preferably adsorbs the –NO2 group of p‐CNB while weakly adsorbs –Cl group of p‐CNB and p‐CAN, promoting catalytic activity and selectivity.

Experimental and Computational Insights into the Effects of -NH2 and -Cl Functional Groups on the Copper Corrosion Inhibition by Benzotriazole

The influences of -NH2 and -Cl groups on the copper corrosion inhibition in 0.5 M H2SO4 solution by benzotriazole were studied using experimental methods and density functional theory calculations. Mass loss tests, potentiodynamic polarization, and surface morphology analyses revealed notable differences: while unmodified benzotriazole showed an inhibition efficiency of 76.6%, the -Cl derivative increased this to 87.6%, whereas the -NH2 derivative dropped it to 61.0% at the concentration of 5 × 10−4 M. Density functional theory calculations indicated these differences are not due to electronic properties or inhibitor-copper interaction energies but rather to the inhibitor’s influence on the oxygen reduction reaction, especially O2 and H2O adsorption. The -NH2 group formed strong hydrogen bonds with O2 and H2O, reducing oxygen reduction inhibition, while the -Cl group repelled O2, resulting in enhanced inhibition. Free energy analysis of the oxygen reduction reaction supported these findings. These new insights into benzotriazole derivatives’ copper corrosion inhibition mechanisms offer valuable guidance for developing next-generation corrosion inhibitors.

The kinetics of nucleolar precursor bodies clustering at the pronuclei interface: Positive correlations with the morphokinetic characteristics of cleaving embryos and euploidy in preimplantation genetic testing programs

Objective: This study investigated potential relationships between the kinetics of nucleolar precursor bodies (NPBs) in the pronucleus and developmental morphokinetics and euploidy in human preimplantation genetic testing for aneuploidy (PGT-A) cycles.Methods: The morphokinetic analysis of 200 blastocysts obtained from 53 PGT-A cycles was performed retrospectively in a time-lapse incubator. At the time of pronuclear breakdown (PNBD), we categorized the blastocysts into two groups based on the kinetic degree of clustering NPBs at the interface of the two pronuclei: clustered NPBs (CL) and non-clustered NPBs (NCL). We then compared morphokinetic parameters, abnormal behavioral events, and the rate of aneuploidy between the two groups.Results: Pronuclear fading and the first cleavage occurred earlier in the NCL group than in the CL group. However, the initiation of blastocyst formation and blastocyst expansion was delayed in the NCL group relative to the CL group. No differences were found in the rate of abnormal cleavage events, such as multinucleation at the 2-cell stage, direct cleavage from one to three cells, and from two to five cells between the CL and NCL groups. However, the fragmentation rate at the 8-cell stage was higher in the NCL group than in the CL group (10.3% vs. 1.9%, p<0.05). Additionally, the euploid rate in the CL group was significantly higher than in the NCL group (37.9% vs. 12.4%, p<0.05).Conclusion: These results demonstrate the effectiveness of combining NPB clustering at PNBD with morphokinetics as a parameter for selecting embryos with higher developmental potential in in vitro fertilization.

Effects of a Combined Chinese Herbal Medicine on Growth Performance, Intestinal Barrier Function, Immune Response, and Cecal Microflora in Broilers Infected with Salmonella enteritidis.

This study investigated the effects of CCHM in drinking water on broilers infected with Salmonella enteritidis. One-day-old male Cobb 500 broilers (n = 300) were randomly assigned to five groups: a control (NC) group, a Salmonella enteritidis challenge (SE) group, an antibiotic (AB) group, a low dose of CCHM (CL) group, and a high dose of CCHM (CH) group. Each group had six replicate cages with ten broilers per cage. The broilers in the NC and SE groups were given normal drinking water. From days 12 to 18, the AB group received water treated with ciprofloxacin lactate injection (1 mL/L), while the CL and CH groups received water containing CCHM at doses of 5 mL/L and 10 mL/L, respectively. Broilers in all groups except the NC group were orally given Salmonella enteritidis daily from days 9 to 11. The experimental period was 28 days. The results showed that, compared with the SE group, the CL and CH groups showed improved growth performance; increased immune organ indices, expressions of ileal occludin and ZO-1 proteins, jejunal and ileal villus heights (except at day 19), and cecal Lactobacillus counts on days 19 and 28 (p < 0.05); and decreased jejunal and ileal lesion scores, ileal interleukin 1β (IL-1β) (except at day 19), interferon-γ (IFN-γ), interleukin 6 (IL-6) (except at day 19), secretory immunoglobulin A (slgA) and tumor necrosis factor α (TNF-α) (except at day 19) levels, serum D-lactic acid and diamine oxidase (DAO) (except at day 19) contents, jejunal and ileal crypt depths (except at day 19), and cecal Salmonella and Escherichia coli counts on days 19 and 28 (p < 0.05). On day 28, except for the levels of ileal interleukin 10 (IL-10), TNF-α, slgA, and serum D-lactic acid content, there were no differences among the NC, AB, and CL groups (p > 0.05). In conclusion, drinking water supplemented with CCHM alleviated the intestinal damage caused by Salmonella enteritidis infection and improved growth performance and cecal microbiota in broilers. The optimal addition rate of CCHM was 5 mL/L.

SnSe2 Quantum Dots and Chlorhexidine Acetate Suppress Synergistically Non-radiative Recombination Loss for High Efficiency and Stability Perovskite Solar Cells.

Non-radiative recombination losses limit the property of perovskite solar cells (PSCs). Here, a synergistic strategy of SnSe2QDs doping into SnO2 and chlorhexidine acetate (CA) coating on the surface of perovskite is proposed. The introduction of 2D SnSe2QDs reduces the oxygen vacancy defects and increases the carrier mobility of SnO2. The optimized SnO2 as a buried interface obviously improves the crystallization quality of perovskite. The CA containing abundant active sites of ─NH2/─NH─, ─C═N, CO, ─Cl groups passivate the defects on the surface and grain boundary of perovskite. The alkyl chain of CA also improves the hydrophobicity of perovskite. Moreover, the synergism of SnSe2QDs and CA releases the residual stress and regulates the energy level arrangement at the top and bottom interface of perovskite. Benefiting from these advantages, the bulk and interface non-radiative recombination loss is greatly suppressed and thereby increases the carrier transport and extraction in devices. As a result, the best power conversion efficiency (PCE) of 23.41% for rigid PSCs and the best PCE of 21.84% for flexible PSCs are reached. The rigid PSC maintains 89% of initial efficiency after storing nitrogen for 3100 h. The flexible PSCs retain 87% of the initial PCE after 5000 bending cycles at a bending radius of 5 mm.

Association of prenatal Cleft Lip and Palate ultrasound abnormalities with copy number variants at a single Chinese tertiary center

BackgroudA systematic analysis was conducted to investigate the molecular etiology of fetal cleft lip and/or palate (CL/P) and the association between various types of CL/P and copy number variations (CNVs), as well as their impact on birth outcomes.MethodsIn this retrospective study conducted between January 2016 and July 2022, a cohort of pregnancies diagnosed with fetal CL/P was enrolled and comprehensive clinical data for all cases were extracted from our medical record database, including demographic data about the pregnancies, ultrasound findings, results of Chromosomal microarray (CMA), as well as relevant pregnant and perinatal outcomes.ResultsAmong the 358 cases, 32 clinically significant variants in 29 (8.1%) fetuses with CL/P were detected by CMA. In 338 singleton pregnancies, the diagnostic yield of CMA in the context of CL/P fetuses was determined to be 7.7% (26/338). CP cases exhibited a relatively higher prevalence of pathogenic/likely pathogenic CNVs at a rate of 25% (3/12), followed by CLP cases at 8.0% (23/288). Notably, the CL group did not demonstrate any pathogenic/likely pathogenic CNV findings among the examined cases (0/38). The diagnostic rate of clinically significant variants was notably higher in the non-isolated CL/P group than in the isolated CL/P group (11/33, 33.3% vs. 15/305, 4.9%, p < 0.001). Within the remaining 20 twin pregnancies, three clinically significant variants (15%) were observed.ConclusionsThis study provides powerful evidence supporting the efficacy of CMA as a valuable tool for facilitating the prenatal genetic diagnosis of fetal CL/P. The presence of CP and CLP in fetal cases demonstrated a relatively higher incidence of pathogenic/likely pathogenic CNVs. Moreover, when these cases were accompanied by additional ultrasound abnormalities, the likelihood of identifying diagnostic CNVs significantly increased. Conversely, cases of CL alone might not be associated with positive CNVs. The present data may significantly enhance prenatal diagnosis accuracy and facilitate informed genetic counseling for cases of fetal CL/P.

Synthesis and Characterization of Symmetrical N-Heterocyclic Carbene Copper(II) Complexes-An Investigation of the Influence of Pyridinyl Substituents.

Three new tridentate copper(II) N-heterocyclic carbene (NHC) complexes have been obtained and characterized with symmetrical C-4 substitutions on their pendent pyridine rings. Substitutions including methyl (Me), methoxy (OMe), and chloro (Cl) groups, which extend the library pincer Cu-NHC complexes under investigation, modify the impact of pyridinyl basicity on NCN pincer complexes. Both ligand precursors and copper(II) complexes are characterized using a range of techniques, including nuclear magnetic resonance (NMR) spectroscopy for 1H, 13C, 31P, and 19F nuclei, electrospray ionization mass spectrometry (ESI-MS), X-ray crystallography, cyclic voltammetry, and UV-Vis spectroscopy. The pyridine substitutions lead to minimal changes to bond lengths and angles in the X-ray crystal structures of these related complexes; there is a pronounced impact on the electrochemical behavior of both the ligand precursors and copper complexes in the solution. The substitution in the pyridinyl units of these complexes show an impact on the catalytic reactivity of these complexes as applied to a model C-N bond-forming reaction (CEL cross-coupling) under well-established conditions; however, this observation does not correlate to the expected change in basicity in these ligands.

FeCl3 induced sonochemical heteroarylation: Synthesis of meridianin alkaloid analogues for their in silico/in vitro evaluation against SIRT1

Meridianins A − G, the indole based marine alkaloids have displayed a diverse range of biological properties including anti-cancer / anti-tumour activities. Based on reported correlation between anticancer activities and SIRT1 inhibition, the meridianin alkaloid analogues were explored as possible inhibitors of SIRT1. The FeCl3 mediated regioselective heteroarylation under ultrasound irradiation was employed for the synthesis of this class of N-heterocycles. The methodology involved CC bond forming reaction between 2-amino-4-chloropyrimidine and indole to afford a library of desired compounds in varied yield depending on nature of substituent present on the reactant indole. Indeed the product yield was decreased when the NO2 or OH or two chloro groups were present on the indole ring. The usefulness of the current approach was demonstrated via functionalization of one of the synthesized compound i.e. Meridianin G under ultrasound. All the synthesized compounds were characterized by 1H and 13C NMR and MS spectral data. When docked into the SIRT1 in silico, promising interactions with this protein were noted for some of the meridianin analogues synthesized in addition to their probable selectivity towards SIRT1 over SIRT2. The common interacting residues of SIRT1 were found to be VAL412, PHE413, ILE347, ALA262, ILE411, HIS363, GLN345, ASN346, ILE270, PHE273 and PHE297. Indeed, the top four compounds e.g. 3b, 3c, 3d and 3f participated in H-bond interactions through their indole “NH” and the primary amino group with ASN346, HIS363 and VAL412 of SIRT1. Correlating the findings of in silico studies, these compounds showed promising inhibition of SIRT1 in vitro with IC50 ∼2.9–3.7 µM when 3f emerged as the best active molecule. The SAR (Structure-Activity-Relationship) analysis suggested high to good activities for the NO2, Cl, Br or MeO group at C-5 of indole ring (due to participation of these groups in H-bonding interaction as noted during the in silico docking studies) whereas a free NH moiety of the indole ring was essential for activity. The in silico and in vitro studies along with ADME predictions suggested that compound 3b, 3c, 3d and 3f could be of further pharmacological interest.

Dicopper Complexes of p-Cresol-2,6-bis(amide-tether-dpa4-X) (X = MeO and Cl): Selective ROS Generation and Cytotoxicity Enhancement Controlled by Electronic and Hydrophobic Effects of the MeO and Cl Groups.

Two new p-cresol-2,6-bis(amide-tether-dpa4-X) ligands (HL4-X, X = MeO and Cl) and their dicopper complexes [Cu2(μ-1,1-OAc)(μ-1,3-OAc)(L4-MeO)]Y (Y = PF6 1a, OAc 1b) and [Cu2(μ-1,3-OAc)2(L4-Cl)]Y (Y = ClO4 2a, OAc 2b) were synthesized. The electronic and hydrophobic effects of the MeO and Cl groups were examined compared with nonsubstituted complex [Cu2(μ-1,1-OAc)(μ-1,3-OAc)(L)]+ (3). The electronic effects were found in crystal structures, spectroscopic characterization, and redox potentials of these complexes. 1b and 2b were reduced to Cu(I)Cu(I) with sodium ascorbate and reductively activated O2 to produce H2O2 and HO•. The H2O2 release and HO• generation are promoted by the electronic effects. The hydrophobic effects increased the lipophilicity of 1b and 2b. Cellular ROS generation of 1b, 2b, and 3 was visualized by DCFH-DA. To examine the intracellular behavior, boron dipyrromethene (Bodipy)-modified complexes 4B and 5B corresponding to 1b and 2b were synthesized. These support that 1b and 2b are localized at the ER and Golgi apparatus. The cytotoxicity of 1b and 2b against various cell lines was examined by MTT assay. 1b and 2b were 7- and 41-fold more cytotoxic than 3. 1b generated ROS selectively in cancer cell but 2b nonselectively in cancer and normal cells, causing cancer- and normal-cell-selective cytotoxicity, respectively.

Benzylidene-isophorone hybrids with strong anticancer activity

Isophorone is a cyclic ketone that has gained significant attention in the field of organic chemistry due to its versatile reactivity and structural attributes. Derivatives of isophorone offer a broad spectrum of applications ranging from pharmaceuticals to polymer chemistry. With the aim of developing novel hybrid structures based on benzylidene by combining with isophorone scaffold, we report 3 derivatives of the benzylidene-isophorone hybrids and its potent anticancer activity. In order to optimize the anticancer activity of hybrids di-substitution of –Cl group in C2 and C6 position of phenyl ring (compound1), –OCH3 group in C2 and C5 position of phenyl ring (compound2), and –OCH3 group in C2 and C3 position of phenyl ring (compound3) of benzylidene (PhCH=) moiety were made. The structure of Compounds1,2 and 3 were elucidated using spectral and XRD methods. Compounds1,2 and 3 exhibit space group P c a 21, P-1, and P 1 21/n 1 respectively. Compounds1,2 and 3 were tested for the potent anticancer activity on MDA MB-231 cell line. All the three compounds exhibit good anticancer activity on the breast cancer cells. The parent hybrid with ortho, ortho directing –Cl (1) exhibits strong antiproliferation effect (IC50 = 0.028 µM) on MDA-MB 231 cell line. However, hybrid structures with ortho, meta directing –OCH3 (2) group showed moderate effect (IC50 = 0.061 µM) and hybrid with ortho, meta directing –OCH3 (3) substitution showed the least potent anticancer activity (IC50 = 0.074 µM). The benzylidene-isophorone hybrids exhibit anticancer effects in the following order: 1 > 2 > 3.

Cenicriviroc Suppresses and Reverses Steatohepatitis by Regulating Macrophage Infiltration and M2 Polarization in Mice.

The inhibition of hepatic macrophage and Kupfer cell recruitment and activation is a potential strategy for treating insulin resistance and nonalcoholic steatohepatitis (NASH). Cenicriviroc (CVC), a dual C-C chemokine receptor 2 (CCR2) and CCR5 antagonist, has shown antifibrotic activity in murine models of NASH and has been evaluated in clinical trials on patients with NASH. This study investigated the effects of CVC on macrophage infiltration and polarization in a lipotoxic model of NASH. C57BL/6 mice were fed a high-cholesterol, high-fat (CL) diet or a CL diet containing 0.015% CVC (CL + CVC) for 12 weeks. Macrophage recruitment and activation were assayed by immunohistochemistry and flow cytometry. CVC supplementation attenuated excessive hepatic lipid accumulation and peroxidation and alleviated glucose intolerance and hyperinsulinemia in the mice that were fed the CL diet. Flow cytometry analysis revealed that compared with the CL group, mice fed the CL + CVC diet had fewer M1-like macrophages, more M2-like macrophages, and fewer T cell counts, indicating that CVC caused an M2-dominant shift of macrophages in the liver. Similarly, CVC decreased lipopolysaccharide-stimulated M1-like macrophage activation, whereas it increased interleukin-4-induced M2-type macrophage polarization in vitro. In addition, CVC attenuated hepatic fibrosis by repressing hepatic stellate cell activation. Lastly, CVC reversed insulin resistance as well as steatosis, inflammation, and fibrosis of the liver in mice with pre-existing NASH. In conclusion, CVC prevented and reversed hepatic steatosis, insulin resistance, inflammation, and fibrogenesis in the liver of NASH mice via M2 macrophage polarization.

Evaluation of Deficient Nutrients in Infants and Toddlers Mainly Taking Amino Acid-Based Elemental Formulas: An Exploratory Study

Introduction: This study evaluated nutrient deficiencies in infants and toddlers with inflammatory bowel disease (IBD) and eosinophilic gastrointestinal disorders (EGIDs), whose primary nutritional source is elemental formulas (EFs). Methods: The nutrient status of children with IBD and EGID aged 6 months to 6 years was evaluated. Results: Twenty-one children fed with EFs (EF group) and 25 controls (CL group) were enrolled. The selenium level in the EF group was lower than that in the CL group (2.2 μg/dL vs. 9.3 μg/dL; p < 0.01). Although fat-soluble vitamins were deficient in some EF group participants, no significant differences were observed in their concentration and insufficiency proportion. However, ascorbic acid deficiency was more frequent in the EF group, with significantly lower levels (8.6 μg/mL vs. 12.0 μg/mL; p < 0.01). The triene:tetraene ratio was significantly higher in the EF group (0.046 vs. 0.010; p < 0.01). Asparagine and taurine levels were significantly lower in the EF group (asparagine: p < 0.01; taurine: p < 0.01) and tyrosine and phenylalanine levels were higher in the EF group, resulting in a lower Fisher’s ratio (p < 0.01). Conclusion: Long-term feeding with EFs can cause deficiencies in essential fatty acids, selenium, and ascorbic acid and also carries a risk of amino acid imbalance in infants and toddlers.

Enhanced solubility and oral bioavailability of niclosamide- sulfobutylether-β-cyclodextrin sodium inclusion complexes: An approach to improve its repurposing potential

Niclosamide monohydrate (NCL) displays promising efficacy across diverse medical conditions, but its limited solubility (1.6 µg/mL at 20°C) and oral bioavailability (10%) hinder its translational potential. In this study, we investigate the complexation of NCL with sulfobutylether-β-cyclodextrin sodium (SBECD) as a strategy to enhance its solubility, dissolution rate and oral bioavailability. Molecular docking studies revealed weak binding (∆Gbind < 2.0 kcal/mole) between NCl and SBECD. The nitrophenyl ring inserted into the SBECD cavity, while the phenyl ring, housing Cl and OH groups, prominently extended outside. Phase solubility studies confirmed a 1:1 inclusion complex formation with a stability constant of 186 M−1. Inclusion complexes, prepared via co-grinding, kneading, solvent evaporation, and spray drying, significantly improved NCL dissolution. Specifically, the spray dried and kneaded complexes achieved complete drug release within 60 min, unlike pure NCL exhibiting only 16% dissolution at 90 min. Microscopic analysis showcased reduced particle surface area in the spray dried complex. Oral bioavailability assessments demonstrated an approximately1.6-fold increase for the spray dried and kneaded complexes compared to pure NCL. Our findings support the scalability and efficacy of NCL-SBECD complexation as a strategic approach for enhancing the repurposing potential of NCL in therapeutic applications.

Focal brain cooling suppresses spreading depolarization and reduces endothelial nitric oxide synthase expression in rats

This study aimed to investigate the effects of focal brain cooling (FBC) on spreading depolarization (SD), which is associated with several neurological disorders. Although it has been studied from various aspects, no medication has been developed that can effectively control SD. As FBC can reduce neuronal damage and promote functional recovery in pathological conditions such as epilepsy, cerebral ischemia, and traumatic brain injury, it may also potentially suppress the onset and progression of SD. We created an experimental rat model of SD by administering 1 M potassium chloride (KCl) to the cortical surface. Changes in neuronal and vascular modalities were evaluated using multimodal recording, which simultaneously recorded brain temperature (BrT), wide range electrocorticogram, and two-dimensional cerebral blood flow. The rats were divided into two groups (cooling [CL] and non-cooling [NC]). Warm or cold saline was perfused on the surface of one hemisphere to maintain BrT at 37°C or 15°C in the NC and CL groups, respectively. Western blot analysis was performed to determine the effects of FBC on endothelial nitric oxide synthase (eNOS) expression. In the NC group, KCl administration triggered repetitive SDs (mean frequency = 11.57/h). In the CL group, FBC increased the duration of all KCl-induced events and gradually reduced their frequency. Additionally, eNOS expression decreased in the cooled brain regions compared to the non-cooled contralateral hemisphere. The results obtained by multimodal recording suggest that FBC suppresses SD and decreases eNOS expression. This study may contribute to developing new treatments for SD and related neurological disorders.

Tuning structural and electronic properties of metal-organic framework 5 by metal substitution and linker functionalization.

The chemical flexibility of metal-organic frameworks (MOFs) offers an ideal platform to tune structure and composition for specific applications, from gas sensing to catalysis and from photoelectric conversion to energy storage. This variability gives rise to a large configurational space that can be efficiently explored using high-throughput computational methods. In this work, we investigate from first principles the structural and electronic properties of MOF-5 variants obtained by replacing Zn with Be, Mg, Cd, Ca, Sr, and Ba and by functionalizing the originally H-passivated linkers with CH3, NO2, Cl, Br, NH2, OH, and COOH groups. To build and analyze the resulting 56 structures, we employ density-functional theory calculations embedded in an in-house developed library for automatized calculations. Our findings reveal that structural properties are mainly defined by metal atoms and large functional groups, which distort the lattice and modify coordination. The formation energy is largely influenced by functionalization and enhanced by COOH and OH groups, which promote the formation of hydrogen bonds. The charge distribution within the linker is especially influenced by functional groups with electron-withdrawing properties, while the metal nodes play a minor role. Likewise, the bandgap size is crucially determined by ligand functionalization. The smallest gaps are found with NH2 and OH groups, which introduce localized orbitals at the top of the valence band. This characteristic makes these functionalizations particularly promising for the design of MOF-5 variants with enhanced gas uptake and sensing properties.

A Self-Transformed N-Chlorinated ε-Polylysine Coating Endows Titanium Implants with Programmed Integration of Robust Antibacterial and Pro-Osteogenic Abilities

Implant-associated infection and poor osseointegration are the main causes of orthopedic implantation failure. For a long-term successful implantation, simultaneously introducing prevention of infection and promotion of osteogenesis into implants is highly desired but remains a grand challenge. Inspired by the human immune mechanism of tissue repair under bacterial infection, we propose a self-transformed strategy for the modification of titanium with porous N-chlorinated ε-polylysine coating (Ti-PL-NCl) through pore-making, surface grafting and chlorination. The as-prepared Ti-PL-NCl exhibits an excellent antibacterial activity against S. aureus and E. coli in the presence of N-chloramine in the early stage, with an antibacterial rate as high as 95.8% and 99.4%, respectively. With the consumption of oxidative chlorine, the N─Cl groups of Ti-PL-NCl are transformed into N─H groups with moderate antibacterial yet strong pro-osteogenic abilities. The self-transformed N-chlorinated ε-polylysine coating enables Ti-PL-NCl to achieve long-lasting antibacterial activity as well as enhanced pro-osteogenesis, thus providing adaptive bioactivities for bone-implant integration. Rat implant-associated osteomyelitis model confirms that Ti-PL-NCl has excellent efficacy of infection prevention and osseointegration promotion. This work may provide a new paradigm of designing multifunctional implants to achieve long-term successful implantation.

Wheat germ supplementation has modest effects on gut health markers but improves glucose homeostasis markers in adults classified as overweight: A randomized controlled pilot study

Wheat germ (WG), a by-product of flour milling, is rich in bioactive substances that may help improve health complications associated with increased adiposity. This study investigated the effects of WG on gut health, metabolic, and inflammatory markers in adults classified as overweight. We hypothesized that WG, because of its many bioactive components, would improve gut health and metabolic, and inflammatory markers in overweight adults. Forty adults (18-45 years old) and with a body mass index between 25 and 30 kg/m2 participated in this single-blinded randomized controlled pilot study. Participants consumed the study supplements containing 30 g of either cornmeal (control, CL) or WG daily for 4 weeks. Primary outcome variables were gut health markers including gut microbiota, gut integrity markers, and fecal short-chain fatty acids, whereas secondary outcome variables included metabolic and inflammatory parameters assessed at baseline and at the end of supplementation. Thirty-nine participants (n = 19 and 20 for CL and WG group, respectively) completed the study. The genus Faecalibacterium was significantly higher in the WG group compared to CL post-supplementation but no significant changes in other gut health markers, short-chain fatty acids, inflammatory markers, and lipid profiles were observed. Compared with baseline, WG improved markers of glucose homeostasis including insulin (P = .02), homeostatic model assessment of insulin resistance (P = .03), glycated hemoglobin (P = .07), and the pro-inflammatory adipokine, resistin (P = .04). However, these parameters after intervention were not different with control. Our findings suggest that WG supplementation have modest effects on gut health but may provide an economical option for individuals to improve glycemic control.

Theoretical investigation of the conformational preference and spectroscopic analysis of cinnamoyl chloride and cinnamide

The rotational isomers of cinnamoyl chloride and cinnamide have been computed using the B3LYP method and the 6-311++G (d, p) basis set to calculate their molecular structure, conformational stability, and spectroscopic properties. Computations revealed that the s-cis rotamers of both compounds are the most stable rotamers in both the gas phase and in the solution. The s-trans rotational barrier is 8.76 kcal/mol and 5.63 kcal/mol for cinnamoyl chloride and cinnamide, respectively. Replacing the Cl group of the cinnamoyl chloride with the NH2 group in the cinnamide has reduced the highest occupied molecular orbital – lowest unoccupied molecular orbital (HOMO-LUMO) gap. The solvation effects on the conformational stability of rotamers have been studied in nine solvents (heptane, chloroform, tetrahydrofuran, dichloroethane, acetone, ethanol, methanol, dimethyl sulfoxide, and water) using the integral equation formalism of the polarizable continuum model. The chemical shifts of 13C and 1H NMR spectra have been simulated in the gas phase, dimethyl sulfoxide (DMSO), and chloroform using the gauge-independent atomic orbital (GIAO) method. The UV absorption spectral analysis has been computed in different solvents (chloroform, methanol, and water), and atomic charges calculated. The examination of vibrational wave numbers and their corresponding assignments revealed excellent agreement between simulated and experimental infrared spectra for the studied molecules.

Effect of immunization against OPN5 on the reproductive performance in Shan Partridge ducks under different photoperiods

Photoperiod is an important environmental factor that influences seasonal reproduction behavior in birds. Birds translate photoperiodic information into neuroendocrine signals through deep brain photoreceptors (DBPs). OPN5 has been considered candidate DBPs involved in regulating seasonal reproduction in birds. We found that OPN5 could mediate light to regulate the follicle development in ducks. In this study, we further verified the effect of OPN5 on follicular development in Shan Partridge ducks by immunizing against the extracellular domain (ECD) of OPN5. We investigated the specific regulatory mechanism of photoperiod mediated by OPN5 on the reproductive activity of ducks. The trial randomly divided 120 Shan Partridge ducks into 3 groups with different treatments: the immunization of OPN5 group was done at d0, d15, d30, and d40 with 1 mL of vaccine containing OPN5 protein (thus containing 1, 1, 0.5, and 0.5 mg of OPN5-KLH protein), and the control group (CS and CL groups) was injected at the same time with the same dose of OPN5-uncontained blank vaccine. The group of CS (900 lux), OPN5 (600 lux), and CL (600 lux) lasted for 40 d in 12 L:12 D photoperiods, respectively. Then, the groups of CS, OPN5, and CL subsequently received 12 L:12 D, 12 L:12 D, and 17 L:7 D light treatments for 33 d, respectively. The ducks were caged in 3 constant rooms with the same feeding conditions for each group, free water, and limited feeding (150 g per duck each day). Duck serum and tissue samples were collected at d 40, d 62, and d 73 (n = 12). It was found that before prolonged light, the group of immunization (group OPN5) and the group of strong light intensity (group CS) were higher than the group of CL in egg production. Subsequent to prolonged light, the group CL in egg production rose about the same as the group immunization, while the strong light group (group CS) was lower. Group OPN5 increased the ovarian index of ducks, and both the immunization of group OPN5 and group CL (extended light) increased the thickness of the granular layer and promoted the secretion of E2, P4, LH, and PRL hormones. Compared with group CS, group CL and OPN5 increased the mRNA level and protein expression of OPN5 in the hypothalamus on d 62 and d 73 (P < 0.05). The gene or protein expression patterns of GnRH, TRH, TSHβ, DIO2, THRβ, VIP, and PRL were positively correlated with OPN5, whereas the gene expression patterns of GnIH and DIO3 were negatively correlated with OPN5. The results showed that immunization against OPN5 could activate the corresponding transmembrane receptors to promote the expression of OPN5, up-regulate the expression of TSHβ and DIO2, and then regulate the HPG axis-related genes to facilitate the follicular development of Shan Partridge ducks. In addition, in this experiment, prolonging the photoperiod or enhancing the light intensity could also enhance follicle development, but the effect was not as significant as immunizing against OPN5. Our results will offer beneficial data and more supportive shreds of evidence in favor of elucidating the role of OPN5 in relation to photoperiods and reproduction.