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1.
Helicobacter ; 29(3): e13063, 2024.
Article in English | MEDLINE | ID: mdl-38874128

ABSTRACT

BACKGROUND: The overall benefits of the newly introduced family-based Helicobacter pylori (H. pylori) infection control and management (FBCM) and screen-and-treat strategies in preventing multiple upper gastrointestinal diseases at national level in China have not been explored. We investigate the cost-effectiveness of these strategies in the whole Chinese population. MATERIALS AND METHODS: Decision trees and Markov models of H. pylori infection-related non-ulcer dyspepsia (NUD), peptic ulcer disease (PUD), and gastric cancer (GC) were developed to simulate the cost-effectiveness of these strategies in the whole 494 million households in China. The main outcomes include cost-effectiveness, life years (LY), quality-adjusted life year (QALY), and incremental cost-effectiveness ratio (ICER). RESULTS: When compared with no-screen strategy, both FBCM and screen-and-treat strategies reduced the number of new cases of NUD, PUD, PUD-related deaths, and the prevalence of GC, and cancer-related deaths. The costs saved by these two strategies were $1467 million and $879 million, quality-adjusted life years gained were 227 million and 267 million, and life years gained were 59 million and 69 million, respectively. Cost-effectiveness analysis showed that FBCM strategy costs -$6.46/QALY and -$24.75/LY, and screen-and-treat strategy costs -$3.3/QALY and -$12.71/LY when compared with no-screen strategy. Compared to the FBCM strategy, the screen-and-treat strategy reduced the incidence of H. pylori-related diseases, added 40 million QALYs, and saved 10 million LYs, but at the increased cost of $588 million. Cost-effectiveness analysis showed that screen-and-treat strategy costs $14.88/QALY and $59.5/LY when compared with FBCM strategy. The robustness of the results was also verified. CONCLUSIONS: Both FBCM and screen-and-treat strategies are highly cost-effective in preventing NUD, PUD, and GC than the no-screen strategy in Chinese families at national level. As FBCM strategy is more practical and efficient, it is expected to play a more important role in preventing familial H. pylori infection and also serves as an excellent reference for other highly infected societies.


Subject(s)
Cost-Benefit Analysis , Helicobacter Infections , Humans , Helicobacter Infections/economics , Helicobacter Infections/prevention & control , Helicobacter Infections/diagnosis , China/epidemiology , Helicobacter pylori , Quality-Adjusted Life Years , Male , Middle Aged , Stomach Neoplasms/prevention & control , Stomach Neoplasms/economics , Female , Mass Screening/economics , Adult , Gastrointestinal Diseases/microbiology , Gastrointestinal Diseases/prevention & control , Gastrointestinal Diseases/economics , Aged , Infection Control/economics , Infection Control/methods , Peptic Ulcer/prevention & control , Peptic Ulcer/economics , East Asian People
2.
Nano Lett ; 23(18): 8445-8453, 2023 Sep 27.
Article in English | MEDLINE | ID: mdl-37677143

ABSTRACT

Tellurium (Te) is an elemental semiconductor with a simple chiral crystal structure. Te in a two-dimensional (2D) form synthesized by a solution-based method shows excellent electrical, optical, and thermal properties. In this work, the chirality of hydrothermally grown 2D Te is identified and analyzed by hot sulfuric acid etching and high-angle tilted high-resolution scanning transmission electron microscopy. The gate-tunable nonlinear electrical responses, including the nonreciprocal electrical transport in the longitudinal direction and the nonlinear planar Hall effect in the transverse direction, are observed in 2D Te under a magnetic field. Moreover, the nonlinear electrical responses have opposite signs in left- and right-handed 2D Te due to the opposite spin polarizations ensured by the chiral symmetry. The fundamental relationship between the spin-orbit coupling and the crystal symmetry in two enantiomers provides a viable platform for realizing chirality-based electronic devices by introducing the degree of freedom of chirality into electron transport.

3.
Neuroimage ; 270: 119989, 2023 04 15.
Article in English | MEDLINE | ID: mdl-36858331

ABSTRACT

Additional neural substance for reading in a second language has been reported by prior studies. However, to date, there has been little investigation into whether and how the brain's adaptation to a second language is induced by specific linguistic tasks or is a general effect during reading in a new language. To address this issue, our study investigated Chinese children learning English as a second language by combining cross-sectional and longitudinal Functional Magnetic Resonance Imaging (fMRI) studies. We compared brain activation across four reading tasks, orthographic tasks and phonological tasks in Chinese (the first language, L1) and English (the second language, L2). By comparing the activation pattern across languages, we observed greater activation in the left inferior parietal lobule (LIPL) in English compared to Chinese, suggesting a functional preference of the LIPL to L2. In addition, greater correlation between LIPL-related FC and L2 was mainly observed in the phonological task, indicating that LIPL could be associated with phonological processing. Moreover, a proportion of the children were enrolled in an 8-week phonological-based reading-training program. We observed significant functional plasticity of the LIPL elicited by this training program only in the English phonological task and not in the orthographic task, further substantiating that the additional requirements of the LIPL in L2 are mainly associated with phonological processing. The findings provide new insights into understanding the functional contribution of the LIPL to reading in a second language.


Subject(s)
Multilingualism , Reading , Child , Humans , Brain Mapping , Cross-Sectional Studies , Brain/physiology , Language , Parietal Lobe/diagnostic imaging , Magnetic Resonance Imaging
4.
Pharmacogenet Genomics ; 33(5): 101-110, 2023 07 01.
Article in English | MEDLINE | ID: mdl-37261937

ABSTRACT

BACKGROUND: Autism spectrum disorder (ASD) is a group of neurodevelopmental disorders characterized by deficits in social communication and restrictive behaviors. Mouse nerve growth factor (mNGF), a neurotrophic factor, is critical for neuronal growth and survival, and the mNGF treatment is considered a promising therapy for neurodegeneration. In light of this, we aimed to evaluate the effect of mNGF on neurological function in ASD. METHODS: An ASD rat model was established by intraperitoneal injection of valproic acid (VPA). Social behavior, learning, and memory of the rats were measured. TdT-mediated dUTP Nick-end labeling and Nissl assays were performed to detect neuronal apoptosis and survival in the hippocampus and prefrontal cortex. Apoptosis-related proteins and oxidative stress markers were detected. RESULTS: mNGF improved locomotor activity, exploratory behavior, social interaction, and spatial learning and memory in VPA-induced ASD rats. In the hippocampus and prefrontal cortex, mNGF suppressed neuronal apoptosis, increased the number of neurons, superoxide dismutase, and glutathione levels, and decreased reactive oxygen species, nitric oxide, TNF-α, and IL-1ß levels compared with the VPA group. In addition, mNGF increased the levels of Bcl-2, p-phosphoinositide-3-kinase (PI3K), and p-serine/threonine kinase (Akt), and decreased the levels of Bax and cleaved caspase-3, while the PI3K inhibitor LY294002 reversed these effects. CONCLUSION: These data suggest that mNGF suppressed neuronal apoptosis and ameliorated the abnormal behaviors in VPA-induced ASD rats, in part, by activating the PI3K/Akt signaling pathway.


Subject(s)
Autism Spectrum Disorder , Valproic Acid , Rats , Animals , Mice , Humans , Valproic Acid/adverse effects , Autism Spectrum Disorder/chemically induced , Autism Spectrum Disorder/drug therapy , Protein Serine-Threonine Kinases/adverse effects , Protein Serine-Threonine Kinases/metabolism , Phosphatidylinositol 3-Kinase/metabolism , Phosphatidylinositol 3-Kinase/pharmacology , Proto-Oncogene Proteins c-akt/metabolism , Proto-Oncogene Proteins c-akt/pharmacology , Phosphatidylinositol 3-Kinases/genetics , Phosphatidylinositol 3-Kinases/metabolism , Phosphatidylinositol 3-Kinases/pharmacology , Signal Transduction , Apoptosis , Phosphatidylinositols/adverse effects , Serine/adverse effects , Disease Models, Animal
5.
J Neurosci Res ; 101(8): 1205-1223, 2023 08.
Article in English | MEDLINE | ID: mdl-37001980

ABSTRACT

Many resting-state functional magnetic resonance imaging (rs-fMRI) studies have explored abnormal regional spontaneous brain activity in migraine. However, these results are inconsistent. To identify the consistent regions with abnormal neural activity, we meta-analyzed these studies. We gathered whole-brain rs-fMRI studies measuring differences in the amplitude of low-frequency fluctuations (ALFF), fractional ALFF (fALFF), or regional homogeneity (ReHo) methods. Then, we performed a voxel-wise meta-analysis to identify consistent abnormal neural activity in migraine by anisotropic effect size seed-based d mapping (AES-SDM). To confirm the AES-SDM meta-analysis results, we conducted two meta-analyses: activation likelihood estimation (ALE) and multi-level kernel density analysis (MKDA). We found that migraine showed increased regional neural activities in the bilateral postcentral gyrus (PoCG), left hippocampus (HIP.L), right pons, left superior frontal gyrus (SFG.L), triangular part of right inferior frontal gyrus (IFGtriang.R), right middle frontal gyrus (MFG.R), and left precentral gyrus (PreCG.L) and decreased regional intrinsic brain activities were exhibited in the right angular gyrus (ANG.R), left superior occipital gyrus (SOG.L), right lingual gyrus (LING.R). Moreover, the meta-analysis of ALE further validated the abnormal neural activities in the PoCG, right pons, ANG.R, and HIP. Meta-regression demonstrated that headache intensity was positively associated with the abnormal activities in the HIP.L, ANG.R, and LING.R. These findings suggest that migraine is associated with abnormal spontaneous brain activities of some pain-related regions, which may contribute to a deeper understanding of the neural mechanism of migraine.


Subject(s)
Migraine Disorders , Motor Cortex , Humans , Brain Mapping/methods , Brain/diagnostic imaging , Migraine Disorders/diagnostic imaging , Parietal Lobe , Magnetic Resonance Imaging/methods
6.
Plant Biotechnol J ; 21(3): 560-573, 2023 03.
Article in English | MEDLINE | ID: mdl-36448454

ABSTRACT

Currently, feed enzymes are primarily obtained through fermentation of fungi, bacteria, and other microorganisms. Although the manufacturing technology for feed enzymes has evolved rapidly, the activities of these enzymes decline during the granulating process and the cost of application has increased over time. An alternative approach is the use of genetically modified plants containing complex feed enzymes for direct utilization in animal feedstuff. We co-expressed three commonly used feed enzymes (phytase, ß-glucanase, and xylanase) in barley seeds using the Agrobacterium-mediated transformation method and generated a new barley germplasm. The results showed that these enzymes were stable and had no effect on the development of the seeds. Supplementation of the basal diet of laying hens with only 8% of enzyme-containing seeds decreased the quantities of indigestible carbohydrates, improved the availability of phosphorus, and reduced the impact of animal production on the environment to an extent similar to directly adding exogenous enzymes to the feed. Feeding enzyme-containing seeds to layers significantly increased the strength of the eggshell and the weight of the eggs by 10.0%-11.3% and 5.6%-7.7% respectively. The intestinal microbiota obtained from layers fed with enzyme-containing seeds was altered compared to controls and was dominated by Alispes and Rikenella. Therefore, the transgenic barley seeds produced in this study can be used as an ideal feedstuff for use in animal feed.


Subject(s)
6-Phytase , Hordeum , Animals , Female , Chickens , Diet , Seeds , Genetic Engineering , Animal Feed/analysis , Dietary Supplements , Animal Nutritional Physiological Phenomena
7.
Acta Neuropathol ; 145(6): 717-731, 2023 06.
Article in English | MEDLINE | ID: mdl-36964213

ABSTRACT

Cerebral amyloid-ß (Aß) accumulation due to impaired Aß clearance is a pivotal event in the pathogenesis of Alzheimer's disease (AD). Considerable brain-derived Aß is cleared via transporting to the periphery. The liver is the largest organ responsible for the clearance of metabolites in the periphery. Whether the liver physiologically clears circulating Aß and its therapeutic potential for AD remains unclear. Here, we found that about 13.9% of Aß42 and 8.9% of Aß40 were removed from the blood when flowing through the liver, and this capacity was decreased with Aß receptor LRP-1 expression down-regulated in hepatocytes in the aged animals. Partial blockage of hepatic blood flow increased Aß levels in both blood and brain interstitial fluid. The chronic decline in hepatic Aß clearance via LRP-1 knockdown specific in hepatocytes aggravated cerebral Aß burden and cognitive deficits, while enhancing hepatic Aß clearance via LRP-1 overexpression attenuated cerebral Aß deposition and cognitive impairments in APP/PS1 mice. Our findings demonstrate that the liver physiologically clears blood Aß and regulates brain Aß levels, suggesting that a decline of hepatic Aß clearance during aging could be involved in AD development, and hepatic Aß clearance is a novel therapeutic approach for AD.


Subject(s)
Alzheimer Disease , Mice , Animals , Alzheimer Disease/pathology , Amyloid beta-Protein Precursor/metabolism , Amyloid beta-Peptides/metabolism , Brain/pathology , Liver/metabolism , Liver/pathology , Mice, Transgenic , Disease Models, Animal
8.
Virol J ; 20(1): 277, 2023 Nov 28.
Article in English | MEDLINE | ID: mdl-38017515

ABSTRACT

BACKGROUND: In a randomized trial, Lianhuaqingwen (LHQW) capsule was effective for accelerating symptom recovery among patients with coronavirus disease 2019 (COVID-19). However, the lack of blinding and limited sample sizes decreased the level of clinical evidence. OBJECTIVES: To evaluate the efficacy and safety of LHQW capsule in adults with mild-to-moderate COVID-19. METHODS: We conducted a double-blind randomized controlled trial in adults with mild-to-moderate COVID-19 (17 sites from China, Thailand, Philippine and Vietnam). Patients received standard-of-care alone or plus LHQW capsules (4 capsules, thrice daily) for 14 days. The primary endpoint was the median time to sustained clinical improvement or resolution of nine major symptoms. RESULTS: The full-analysis set consisted of 410 patients in LHQW capsules and 405 in placebo group. LHQW significantly shortened the primary endpoint in the full-analysis set (4.0 vs. 6.7 days, hazards ratio: 1.63, 95% confidence interval: 1.39-1.90). LHQW capsules shortened the median time to sustained clinical improvement or resolution of stuffy or runny nose (2.8 vs. 3.7 days), sore throat (2.0 vs. 2.6 days), cough (3.2 vs. 4.9 days), feeling hot or feverish (1.0 vs. 1.3 days), low energy or tiredness (1.3 vs. 1.9 days), and myalgia (1.5 vs. 2.0 days). The duration to sustained clinical improvement or resolution of shortness of breath, headache, and chills or shivering did not differ significantly between the two groups. Safety was comparable between the two groups. No serious adverse events were reported. INTERPRETATION: LHQW capsules promote recovery of mild-to-moderate COVID-19 via accelerating symptom resolution and were well tolerated. Trial registration ChiCTR2200056727 .


Subject(s)
COVID-19 , Drugs, Chinese Herbal , Adult , Humans , Double-Blind Method , Drugs, Chinese Herbal/therapeutic use , Treatment Outcome
9.
Inorg Chem ; 62(37): 14896-14901, 2023 Sep 18.
Article in English | MEDLINE | ID: mdl-37678159

ABSTRACT

Volatile organic compounds (VOCs) have harmful effects on human health and the environment but detecting low levels of VOCs is challenging due to a lack of reliable biomarkers. However, incorporating gold nanoparticles (Au NPs) into metal-organic frameworks (MOFs) shows promise for VOC detection. In this study, we developed nanoscale Au@UiO-66 that exhibited surface-enhanced Raman scattering (SERS) activity even at very low levels of toluene vapors (down to 1.0 ppm) due to the thickness of the shell and strong π-π interactions between benzenyl-type linkers and toluene. The UiO-66 shell also increased the thermal stability of the Au NPs, preventing aggregation up to 550 °C. This development may be useful for sensitive detection of VOCs for environmental protection purposes.

10.
Nutr Metab Cardiovasc Dis ; 33(10): 1878-1887, 2023 10.
Article in English | MEDLINE | ID: mdl-37500347

ABSTRACT

BACKGROUND AND AIM: Heart failure (HF) imposes significant global health costs due to its high incidence, readmission, and mortality rate. Accurate assessment of readmission risk and precise interventions have become important measures to improve health for patients with HF. Therefore, this study aimed to develop a machine learning (ML) model to predict 30-day unplanned readmissions in older patients with HF. METHODS AND RESULTS: This study collected data on hospitalized older patients with HF from the medical data platform of Chongqing Medical University from January 1, 2012, to December 31, 2021. A total of 5 candidate algorithms were selected from 15 ML algorithms with excellent performance, which was evaluated by area under the operating characteristic curve (AUC) and accuracy. Then, the 5 candidate algorithms were hyperparameter tuned by 5-fold cross-validation grid search, and performance was evaluated by AUC, accuracy, sensitivity, specificity, and recall. Finally, an optimal ML model was constructed, and the predictive results were explained using the SHapley Additive exPlanations (SHAP) framework. A total of 14,843 older patients with HF were consecutively enrolled. CatBoost model was selected as the best prediction model, and AUC was 0.732, with 0.712 accuracy, 0.619 sensitivity, and 0.722 specificity. NT.proBNP, length of stay (LOS), triglycerides, blood phosphorus, blood potassium, and lactate dehydrogenase had the greatest effect on 30-day unplanned readmission in older patients with HF, according to SHAP results. CONCLUSIONS: The study developed a CatBoost model to predict the risk of unplanned 30-day special-cause readmission in older patients with HF, which showed more significant performance compared with the traditional logistic regression model.


Subject(s)
Heart Failure , Patient Readmission , Humans , Aged , Retrospective Studies , Heart Failure/diagnosis , Heart Failure/epidemiology , Heart Failure/therapy , Length of Stay , Logistic Models
11.
Mol Ther ; 30(1): 54-74, 2022 01 05.
Article in English | MEDLINE | ID: mdl-34678511

ABSTRACT

Fibroblasts can be reprogrammed into cardiovascular progenitor cells (CPCs) using transgenic approaches, although the underlying mechanism remains unclear. We determined whether activation of endogenous genes such as Gata4, Nkx2.5, and Tbx5 can rapidly establish autoregulatory loops and initiate CPC generation in adult extracardiac fibroblasts using a CRISPR activation system. The induced fibroblasts (>80%) showed phenotypic changes as indicated by an Nkx2.5 cardiac enhancer reporter. The progenitor characteristics were confirmed by colony formation and expression of cardiovascular genes. Cardiac sphere induction segregated the early and late reprogrammed cells that can generate functional cardiomyocytes and vascular cells in vitro. Therefore, they were termed CRISPR-induced CPCs (ciCPCs). Transcriptomic analysis showed that cell cycle and heart development pathways were important to accelerate CPC formation during the early reprogramming stage. The CRISPR system opened the silenced chromatin locus, thereby allowing transcriptional factors to access their own promoters and eventually forming a positive feedback loop. The regenerative potential of ciCPCs was assessed after implantation in mouse myocardial infarction models. The engrafted ciCPCs differentiated into cardiovascular cells in vivo but also significantly improved contractile function and scar formation. In conclusion, multiplex gene activation was sufficient to drive CPC reprogramming, providing a new cell source for regenerative therapeutics.


Subject(s)
Clustered Regularly Interspaced Short Palindromic Repeats , Myocardial Infarction , Animals , Cell Differentiation/genetics , Cellular Reprogramming/genetics , Fibroblasts/metabolism , Mice , Myocardial Infarction/genetics , Myocardial Infarction/metabolism , Myocardial Infarction/therapy , Myocytes, Cardiac/metabolism , Stem Cells/metabolism
12.
Ecotoxicol Environ Saf ; 262: 115287, 2023 Aug 09.
Article in English | MEDLINE | ID: mdl-37567105

ABSTRACT

2,4-Dinitrotoluene (2,4-DNT) as a common industrial waste has been massively discharged into the environment with industrial wastewater. Due to its refractory degradation, high toxicity, and bioaccumulation, 2,4-DNT pollution has become increasingly serious. Compared with the currently available physical and chemical methods, in situ bioremediation is considered as an economical and environmentally friendly approach to remove toxic compounds from contaminated environment. In this study, we relocated a complete degradation pathway of 2,4-DNT into Escherichia coli to degrade 2,4-DNT completely. Eight genes from Burkholderia sp. strain were re-synthesized by PCR-based two-step DNA synthesis method and introduced into E. coli. Degradation experiments revealed that the transformant was able to degrade 2,4-DNT completely in 12 h when the 2,4-DNT concentration reached 3 mM. The organic acids in the tricarboxylic acid cycle were detected to prove the degradation of 2,4-DNT through the artificial degradation pathway. The results proved that 2,4-DNT could be completely degraded by the engineered bacteria. In this study, the complete degradation pathway of 2,4-DNT was constructed in E. coli for the first time using synthetic biology techniques. This research provides theoretical and experimental bases for the actual treatment of 2,4-DNT, and lays a technical foundation for the bioremediation of organic pollutants.

13.
BMC Med Inform Decis Mak ; 23(1): 148, 2023 08 03.
Article in English | MEDLINE | ID: mdl-37537590

ABSTRACT

BACKGROUND: High-dose methotrexate (HD-MTX) is a potent chemotherapeutic agent used to treat pediatric acute lymphoblastic leukemia (ALL). HD-MTX is known for cause delayed elimination and drug-related adverse events. Therefore, close monitoring of delayed MTX elimination in ALL patients is essential. OBJECTIVE: This study aimed to identify the risk factors associated with delayed MTX elimination and to develop a predictive tool for its occurrence. METHODS: Patients who received MTX chemotherapy during hospitalization were selected for inclusion in our study. Univariate and least absolute shrinkage and selection operator (LASSO) methods were used to screen for relevant features. Then four machine learning (ML) algorithms were used to construct prediction model in different sampling method. Furthermore, the performance of the model was evaluated using several indicators. Finally, the optimal model was deployed on a web page to create a visual prediction tool. RESULTS: The study included 329 patients with delayed MTX elimination and 1400 patients without delayed MTX elimination who met the inclusion criteria. Univariate and LASSO regression analysis identified eleven predictors, including age, weight, creatinine, uric acid, total bilirubin, albumin, white blood cell count, hemoglobin, prothrombin time, immunological classification, and co-medication with omeprazole. The XGBoost algorithm with SMOTE exhibited AUROC of 0.897, AUPR of 0.729, sensitivity of 0.808, specificity of 0.847, outperforming the other models. And had AUROC of 0.788 in external validation. CONCLUSION: The XGBoost algorithm provides superior performance in predicting the delayed elimination of MTX. We have created a prediction tool to assist medical professionals in predicting MTX metabolic delay.


Subject(s)
Methotrexate , Precursor Cell Lymphoblastic Leukemia-Lymphoma , Child , Humans , Methotrexate/adverse effects , Retrospective Studies , Precursor Cell Lymphoblastic Leukemia-Lymphoma/drug therapy , Creatinine , Internet
14.
Physiol Genomics ; 54(9): 325-336, 2022 09 01.
Article in English | MEDLINE | ID: mdl-35723222

ABSTRACT

Troxerutin is known for its anti-inflammatory and antioxidative effects in nerve impairment. The purpose of this study is to investigate the effect of troxerutin and cerebroprotein hydrolysate injections (TCHis) on prenatal valproic acid (VPA)-exposed rats. The VPA was administered to pregnant rats on gestational day 12.5 to induce a model of autism. The offspring were given the treatment of TCHis on postnatal day (PND) 21-50. On PND 43-50, the behavioral analysis of offspring was performed after the treatment of TCHis for 1 h. On PND 50, the offspring were harvested and the brains were collected. The hippocampus and prefrontal cortex were isolated for relevant biochemical detections. The administration of TCHis increased pain sensitivity and improved abnormal social behaviors in prenatal VPA-exposed rats. Prenatal exposure of VPA induced neuronal loss and apoptosis, enhanced reactive oxygen species (ROS) production, and promoted oxidative stress in hippocampus and prefrontal cortex, whereas these effects were reversed by the postnatal treatment of TCHis. In addition, postnatal administration of TCHis ameliorated mitochondrial function in hippocampus and prefrontal cortex of prenatal VPA-exposed rats. This study concluded that postnatal treatment of TCHis reduced oxidative stress and ameliorated abnormal behavior in a prenatal VPA-induced rat model of autism.


Subject(s)
Autistic Disorder , Prenatal Exposure Delayed Effects , Animals , Autistic Disorder/chemically induced , Autistic Disorder/drug therapy , Behavior, Animal , Disease Models, Animal , Female , Humans , Hydroxyethylrutoside/analogs & derivatives , Oxidative Stress , Pregnancy , Prenatal Exposure Delayed Effects/chemically induced , Rats , Rats, Wistar , Social Behavior , Valproic Acid/pharmacology
15.
Chemistry ; 28(9): e202104044, 2022 Feb 16.
Article in English | MEDLINE | ID: mdl-34958482

ABSTRACT

Boronic acids are Lewis acids that exist in equilibrium with boronate forms in aqueous solution. Here we experimentally and computationally investigated the Lewis acidity of 2,6-diarylphenylboronic acids; specially designed phenylboronic acids that possess two flanking aromatic rings with tunable aromatic character. Hammett analysis of 2,6-diarylphenylboronic acids reveals that their Lewis acidity remains unchanged upon the introduction of EWG/EDG at the distant para position of the flanking aromatic rings. Structural and computational studies demonstrate that polar-π interactions and solvation effects contribute to the stabilization of boronic acids and boronate forms by aromatic rings. Our physical-organic chemistry work highlights that boronic acids and boronates can be stabilized by aromatic systems, leading to an important molecular knowledge for rational design and development of boronic acid-based catalysts and inhibitors of biomedically important proteins.


Subject(s)
Boronic Acids , Lewis Acids , Boronic Acids/chemistry , Proteins/chemistry
16.
J Org Chem ; 87(12): 7875-7883, 2022 06 17.
Article in English | MEDLINE | ID: mdl-35653132

ABSTRACT

Imidazole-based compounds are widely found in natural products, synthetic molecules, and biomolecules. Noncovalent interactions between the imidazole ring and other functional groups play an important role in determining the function of diverse molecules. However, there is a limited understanding of the underlying noncovalent interactions between imidazoles and aromatic systems. In this work, we report physical-organic chemistry studies on 2-(2,6-diarylphenyl)-1H-imidazoles and their protonated forms to investigate the noncovalent interactions between the central imidazole ring and two flanking aromatic rings possessing substituents at the para/meta position. Hammett analysis revealed that pKa values and proton affinities correlate well with Hammett σ values of para-substituents at the flanking rings. Additional quantitative Kohn-Sham molecular orbital and energy decomposition analyses reveal that through-space π-π interactions and NH-π interactions contribute to the intramolecular stabilization of the imidazolium cation. The results are important because they clearly demonstrate that the imidazolium cation forms energetically favorable noncovalent interactions with aromatic rings via the through-space effect, a knowledge that can be used in rational drug and catalyst design.


Subject(s)
Imidazoles , Cations/chemistry , Imidazoles/chemistry , Models, Molecular
17.
J Org Chem ; 87(9): 6087-6096, 2022 05 06.
Article in English | MEDLINE | ID: mdl-35471006

ABSTRACT

Arene-arene interactions are fundamentally important in molecular recognition. To precisely probe arene-arene interactions in cyclophanes, we designed and synthesized (2,6-phenol)paracyclophanes and (2,6-aniline)paracyclophanes that possess two aromatic rings in close proximity. Fine-tuning the aromatic character of one aromatic ring by fluorine substituents enables investigations on the intramolecular interactions between the electron-rich phenol and aniline with tetra-H- and tetra-F-substituted benzene. pKa measurements revealed that the tetra-F-template increases the acidity of the phenol (ΔpKa = 0.55). X-ray crystallography and computational analyses demonstrated that all [3,3]metaparacyclophanes adopt cofacial parallel conformations, implying the presence of π-π stacking interactions. Advanced quantum chemical analyses furthermore revealed that both electrostatic interactions and orbital interactions provide the key contribution to the structure and stability of [3,3]metaparacyclophanes.


Subject(s)
Aniline Compounds , Phenols , Crystallography, X-Ray , Molecular Conformation , Static Electricity
18.
Ecotoxicol Environ Saf ; 243: 114016, 2022 Sep 15.
Article in English | MEDLINE | ID: mdl-36027713

ABSTRACT

Nitrobenzene is widely present in industrial wastewater and soil. Biodegradation has become an ideal method to remediate organic pollutants due to its low cost, high efficiency, and absence of secondary pollution. In the present study, 10 exogenous genes that can completely degrade nitrobenzene were introduced into Escherichia coli, and their successful expression in the strain was verified by fluorescence quantitative polymerase chain reaction and proteomic analysis. The results of the degradation experiment showed that the engineered strain could completely degrade 4 mM nitrobenzene within 8 h. The formation of intermediate metabolites was detected, and the final metabolites entered the E. coli tricarboxylic acid cycle smoothly. This process was discovered by isotope tracing method. Results indicated the integrality of the degradation pathway and the complete degradation of nitrobenzene. Finally, further experiments were conducted in soil to verify its degradation ability and showed that the engineered strain could also degrade 1 mM nitrobenzene within 10 h. In this study, engineered bacteria that can completely degrade nitrobenzene have been constructed successfully. The construction of remediation-engineered bacteria by synthetic biology laid the foundation for the industrial application of biological degradation of organic pollutants.


Subject(s)
Environmental Pollutants , Escherichia coli , Bacteria/metabolism , Biodegradation, Environmental , Environmental Pollutants/metabolism , Escherichia coli/genetics , Escherichia coli/metabolism , Nitrobenzenes/metabolism , Proteomics , Soil
19.
Entropy (Basel) ; 24(2)2022 Feb 12.
Article in English | MEDLINE | ID: mdl-35205561

ABSTRACT

The Shannon entropy in an LS-coupled configuration space has been calculated through a transformation from that in a jj-coupled configuration space for a Ni-like isoelectronic sequence. The sudden change of Shannon entropy, information exchange, eigenlevel anticrossing, and strong configuration interaction have been presented for adjacent levels. It is shown that eigenlevel anticrossing is a sufficient and necessary condition for the sudden change of Shannon entropy, and both of them are a sufficient condition for information exchange, which is the same as the case of the jj-coupled configuration space. It is found that the structure of sudden change from jj-coupled into LS-coupled configuration spaces through the LS-jj transformation is invariant for Shannon entropy along the isoelectronic sequence. What is more, in an LS-coupled configuration space, there are a large number of information exchanges between energy levels whether with or without strong configuration interaction, and most of the ground and single excited states of Ni-like ions are more suitable to be described by a jj-coupled or other configuration basis set instead of an LS-coupled configuration basis set according to the configuration mixing coefficients and their Shannon entropy. In this sense, Shannon entropy can also be used to measure the applicability of a configuration basis set or the purity of atomic state functions in different coupling schemes.

20.
Small ; 17(5): e2007222, 2021 Feb.
Article in English | MEDLINE | ID: mdl-33448118

ABSTRACT

Magneto-optical (MO) coupling incorporates photon-induced change of magnetic polarization that can be adopted in ultrafast switching, optical isolators, mode convertors, and optical data storage components for advanced optical integrated circuits. However, integrating plasmonic, magnetic, and dielectric properties in one single material system poses challenges since one natural material can hardly possess all these functionalities. Here, co-deposition of a three-phase heterostructure composed of a durable conductive nitride matrix with embedded core-shell vertically aligned nanopillars, is demonstrated. The unique coupling between ferromagnetic NiO core and atomically sharp plasmonic Au shell enables strong MO activity out-of-plane at room temperature. Further, a template growth process is applied, which significantly enhances the ordering of the nanopillar array. The ordered nanostructure offers two schemes of spin polarization which result in stronger antisymmetry of Kerr rotation. The presented complex hybrid metamaterial platform with strong magnetic and optical anisotropies is promising for tunable and modulated all-optical-based nanodevices.

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