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1.
Inorg Chem ; 63(26): 12370-12376, 2024 Jul 01.
Article in English | MEDLINE | ID: mdl-38897587

ABSTRACT

Rising energy needs and environmental issues have prompted the creation of effective and affordable photocatalysts for converting biomass. Utilizing abundant biomass, oxidation of 5-hydroxymethylfurfural (HMF) emerges as a method for generating high-value chemicals from biomass, offering an alternative to fossil fuels. We synthesized defect-engineered metal oxides (ZnO and WO3) by calcination with NaBH4 as a reducing agent. Atomic-level analyses identified oxygen vacancy defects induced by the reduction of metal ions within the metal oxide nanoparticles. Further analysis showed an unchanged band gap but an up to 4-fold increase in current density. This enhancement is attributed to the trapping of electrons in defect sites created during the calcination process. The formation of new electron donor states hindered photogenerated electron-hole recombination, enhancing the photocatalytic efficiency of the metal oxide. The photocatalytic degradation yield of HMF was over 95%, and the selective organic products 2,5-diformylfuran (DFF) and 2,5-furandicarboxylic acid (FDCA) were obtained without byproducts. Kinetic studies demonstrated that the photocatalytic conversion reaction rates were accelerated by up to 3.5-fold. Improved photocatalytic activity for HMF oxidation was achieved by introducing oxygen vacancy defects upon the reduction of metal ions within the metal oxides. Our results provide a promising approach for designing efficient photocatalysts.

2.
Inorg Chem ; 63(26): 12054-12062, 2024 Jul 01.
Article in English | MEDLINE | ID: mdl-38870407

ABSTRACT

The synthesis, enhancement, and maintenance of magnetite-based catalyst nanoparticles (NPs) are important for photocatalytic activity and recovery rates. We used a sodium borohydride (NaBH4) calcination method to modify MnFe2O4 nanoparticles to optimize their performance in the photocatalytic oxidation of 2,5-hydroxymethylfurfural. The results indicated a 94% increase in photocatalytic efficiency, while magnetic assessments performed using a vibrating sample magnetometer showed an 8.9% improvement in magnetic properties without degradation. These findings show the dual benefits of increased photocatalytic performance with strong magnetic properties, which are important for the application and reusability of photocatalysts. The recycling of these photocatalysts reduces secondary pollution and increases the process cost-effectiveness. These results contribute to the solution of problems with the use of photocatalytic materials.

3.
Inorg Chem ; 62(8): 3703-3711, 2023 Feb 27.
Article in English | MEDLINE | ID: mdl-36795758

ABSTRACT

Photocatalysts are useful for various applications, including the conservation and storage of energy, wastewater treatment, air purification, semiconductors, and production of high-value-added products. Herein, ZnxCd1-xS nanoparticle (NP) photocatalysts with different concentrations of Zn2+ ions (x = 0.0, 0.3, 0.5, or 0.7) were successfully synthesized. The photocatalytic activities of ZnxCd1-xS NPs varied with the irradiation wavelength. X-ray diffraction, high-resolution transmission electron microscopy, energy-dispersive X-ray spectroscopy, and ultraviolet-visible spectroscopy were used to characterize the surface morphology and electronic properties of the ZnxCd1-xS NPs. In addition, in situ X-ray photoelectron spectroscopy was performed to investigate the effect of the concentration of Zn2+ ions on the irradiation wavelength for photocatalytic activity. Furthermore, wavelength-dependent photocatalytic degradation (PCD) activity of the ZnxCd1-xS NPs was investigated using biomass-derived 2,5-hydroxymethylfurfural (HMF). We observed that the selective oxidation of HMF using ZnxCd1-xS NPs resulted in the formation of 2,5-furandicarboxylic acid via 5-hydroxymethyl-2-furancarboxylic acid or 2,5-diformylfuran. The selective oxidation of HMF was dependent on the irradiation wavelength for PCD. Moreover, the irradiation wavelength for the PCD depended on the concentration of Zn2+ ions in the ZnxCd1-xS NPs.

4.
Inorg Chem ; 62(33): 13428-13434, 2023 Aug 21.
Article in English | MEDLINE | ID: mdl-37555962

ABSTRACT

Modulating the oxygen vacancy (V0) in nanostructures has opened a new avenue for efficient catalyst design, facilitating biomass oxidation reactions and electrocatalytic properties. In this study, we have investigated the properties of NiO-based catalysts with varying degrees of V0 achieved through ion doping of the catalyst with cations of different oxidation states (TM3+) or the same valence state (TM2+) as Ni2+ in the NiO matrix. By introducing charge-mismatched dopants, we enhanced the concentration of V0 in the NiO catalyst, resulting in remarkable selectivity (∼50%) for the conversion of 2,5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA), as well as a lower overpotential in the oxygen evolution reaction (OER). We believe that charge-mismatched doping offers a novel avenue for optimizing defect engineering in oxide-based catalysts, which can enable more efficient biomass conversion and water splitting. These findings have made a significant contribution to the field of multipurpose catalysis and hold the potential to inspire new catalyst designs that would usher in a more sustainable future.

5.
Inorg Chem ; 62(32): 12913-12919, 2023 Aug 14.
Article in English | MEDLINE | ID: mdl-37530612

ABSTRACT

This study focuses on the synthesis and investigation of ZnIn2S4 nanoparticle (NP) photocatalysts treated with different sulfur sources, thioacetamide (TAA), or thiourea (TU), to explore their wavelength-dependent photocatalytic activity. The research aims to understand the impact of Zn vacancies present on the surface of ZnIn2S4 NPs. The investigation involves electron spin resonance and in situ X-ray photoelectron spectroscopy to study the photocatalytic activity of ZnIn2S4-TU and ZnIn2S4-TAA NPs, following the characterization of surface morphology and electronic properties using high-resolution transmission electron microscopy and X-ray diffraction. Additionally, the study delves into the wavelength-dependent photocatalytic degradation (PCD) activity of the ZnIn2S4 NPs using 2,5-hydroxymethylfurfural (HMF) across a wide range. Notably, the selective oxidation of HMF using ZnIn2S4-TU NPs resulted in the formation of 2,5-furandicarboxylic acid (FDCA) via 2,5-diformylfuran, with an efficiency exceeding 40% over the broad wavelength range. The research demonstrates that the irradiation wavelength for PCD is influenced by the number of defect structures introduced into the ZnIn2S4 NPs through the sulfur source.

6.
Inorg Chem ; 61(42): 16887-16894, 2022 Oct 24.
Article in English | MEDLINE | ID: mdl-36223637

ABSTRACT

A charge mismatch between transition-metal-ion dopants and metal oxide nanoparticles (MO NPs) within an engineered complex engenders a significant number of oxygen vacancies (VO) on the surface of the MO NP construct. To elucidate in-depth the mechanism of this tendency, Co ions with different charge states (Co3+ and Co2+) were doped into ZnO NPs, and their atomic structural changes were correlated with their photocatalytic efficiency. We ascertained that the increase of the Zn-O bond distances was distinctly affected by Co3+-ion doping, and, subsequently, the number of VO was noticeably increased. We further investigated the mechanistic pathways of the photocatalytic oxidation of 2,5-hydroxymethylfurfural (HMF), which have been widely investigated as biomass derivatives because of their potential use as precursors for the synthesis of sustainable alternatives to petrochemical substances. To identify the reaction products in each oxidation step, selective oxidation products obtained from HMF in the presence of pristine ZnO NPs, Co3+- and Co2+-ion-doped ZnO NPs were evaluated. We confirmed that Co3+-ion-doped ZnO NPs can efficiently and selectively oxidize HMF with a good conversion rate (∼40%) by converting HMF to 2,5-furandicarboxylic acid (FDCA). The present study demonstrates the feasibility of improving the production efficiency of FDCA (an alternative energy material) by using enhanced photocatalytic MO NPs with the help of the charge mismatch between MO and metal-ion dopants.


Subject(s)
Metal Nanoparticles , Zinc Oxide , Zinc Oxide/chemistry , Biomass , Metal Nanoparticles/chemistry , Ions , Organic Chemicals , Oxygen
7.
Platelets ; 33(4): 632-639, 2022 May 19.
Article in English | MEDLINE | ID: mdl-34904525

ABSTRACT

Platelets and their subcellular components (e.g., dense granules) are essential components in hemostasis. Understanding their chemical heterogeneities at the sub-micrometer scale, particularly their activation during hemostasis and production of platelet-derived extracellular vesicles, may provide important insights into their mechanisms; however, this has rarely been investigated, mainly owing to the lack of appropriate chemical characterization tools at nanometer scale. Here, the use of scanning transmission X-ray microscopy (STXM) combined with X-ray absorption near edge structure (XANES) to characterize human platelets and their subcellular components at the carbon K-edge and calcium L2,3-edge, is reported. STXM images can identify not only the spatial distribution of subcellular components in human platelets, such as dense granules (DGs) with sizes of ~200 nm, but also their granule-to-granule chemical heterogeneities on the sub-micrometer scale, based on their XANES spectra. The calcium distribution map as well as the principal component analysis of the STXM image stacks clearly identified the numbers and locations of the calcium-rich DGs within human platelets. Deconvolution of the carbon K-edge XANES spectra, extracted from various locations in the platelets, showed that amide carbonyl and carboxylic acid functional groups were mainly found in the cytoplasm, while ketone-phenol-nitrile-imine, aliphatic, and carbonate functional groups were dominant in the platelet DGs. These observations suggest that platelet DGs are most likely composed of calcium polyphosphate associated with adenosine triphosphate (ATP) and adenosine diphosphate (ADP), with significant granule-to-granule variations in their compositions, while the cytoplasm regions of platelets contain significant amounts of proteins.


Subject(s)
Blood Platelets , Calcium , Blood Platelets/metabolism , Calcium/metabolism , Carbon/metabolism , Carbon/pharmacology , Cytoplasmic Granules/metabolism , Humans , Microscopy , X-Rays
8.
J Viral Hepat ; 28(2): 353-363, 2021 02.
Article in English | MEDLINE | ID: mdl-33051945

ABSTRACT

It is unclear whether suboptimal adherence contributes to adverse clinical outcomes in patients with chronic hepatitis B (CHB). Moreover, there is no consensus regarding the optimal level of drug adherence. This was a population-based historical cohort study including 51 975 adult CHB patients treated with entecavir (0.5 mg/d orally). Data were obtained from the Korean national health insurance service claims database, which covers >99% of the entire population, between 2007 and 2015. Medication adherence was categorized as high (proportion of days covered [PDC], ≥90%; n = 32 089), intermediate (PDC, 80%-89%; n = 10 197) and low (PDC, <80%; n = 9689). During a median 4.5 years (maximal 9 years) of follow-up in 51 975 CHB patients treated with entecavir, multivariable analyses revealed that the risk of mortality/transplantation was significantly greater in the low-adherers (adjusted hazard ratio [HR], 1.38; P < .001) and intermediate-adherers (adjusted HR, 1.44; P < .001) than the high-adherers (P for trend < 0.001). The risk of renal failure in the low- and intermediate-adherence groups was also significantly higher than the high-adherence group (P for trend < 0.001). By contrast, the risk of hepatocellular carcinoma (HCC) was not significantly different between groups (P for trend = 0.70). The higher risk of mortality/transplantation and renal failure but similar risk of HCC for low- and intermediate-adherers compared with high-adherers was consistent in inverse probability treatment weighting analysis of the entire cohort and subcohorts with or without cirrhosis. In conclusion, high medication adherence (≥90%) is required to significantly lower risk of mortality and renal failure in patients with CHB during long-term treatment with entecavir.


Subject(s)
Carcinoma, Hepatocellular , Hepatitis B, Chronic , Liver Neoplasms , Adult , Antiviral Agents/therapeutic use , Carcinoma, Hepatocellular/drug therapy , Cohort Studies , Guanine/analogs & derivatives , Hepatitis B, Chronic/drug therapy , Humans , Incidence , Liver Neoplasms/drug therapy , Medication Adherence
9.
J Neuroeng Rehabil ; 18(1): 110, 2021 07 03.
Article in English | MEDLINE | ID: mdl-34217328

ABSTRACT

BACKGROUND: Abnormal intermuscular coordination limits the motor capability of stroke-affected upper limbs. By evaluating the intermuscular coordination in the affected limb under various biomechanical task constraints, the impact of a stroke on motor control can be analyzed and intermuscular coordination-based rehabilitation strategies can be developed. In this study, we investigated upper limb intermuscular coordination after a stroke during isokinetic movements. METHODS: Sixteen chronic stroke survivors and eight neurologically intact individuals were recruited. End-point forces and electromyographic activities of the shoulder and elbow muscles were measured while the participants performed isokinetic upper limb movements in a three-dimensional space. Intermuscular coordination of the stroke survivors and the control participants was quantified in the form of muscle synergies. Then, we compared the number, composition, and activation coefficients of muscle synergies and the end-point force between the groups. The correlation between the alteration of muscle synergies and the level of motor impairment was investigated. RESULTS: Four and five muscle synergies in the stroke and control groups were observed, respectively. The composition of muscle synergies was comparable between the groups, except that the three heads of the deltoid muscle were co-activated and formed one synergy in the stroke group, whereas those muscles formed two synergies in the control group. When the number of muscle synergies between the groups matched, the comparable composition of muscle synergies was observed in both groups. Alternatively, the modulation of synergy activation coefficients was altered after a stroke. The severity of motor impairments was negatively correlated with the similarity of the post-stroke synergies with respect to the mean control synergies. CONCLUSIONS: Stroke-affected upper limbs seemed to modularize the activation of the shoulder and elbow muscles in a fairly similar way to that of neurologically intact individuals during isokinetic movements. Compared with free (i.e., unconstrained) movement, exercise under biomechanical constraints including the isokinetic constraint might promote the activation of muscle synergies independently in stroke survivors. We postulated the effect of biomechanical constraints on the intermuscular coordination and suggested a possible intermuscular coordination-based rehabilitation protocol that provides the biomechanical constraint appropriate to a trainee throughout the progress of rehabilitation.


Subject(s)
Neurological Rehabilitation , Stroke Rehabilitation , Stroke , Biomechanical Phenomena , Electromyography , Humans , Movement , Muscle, Skeletal , Upper Extremity
10.
Int J Mol Sci ; 22(6)2021 Mar 17.
Article in English | MEDLINE | ID: mdl-33802993

ABSTRACT

Despite advances in the preparation of metal oxide (MO) nanoparticles (NPs) as catalysts for various applications, concerns about the biosafety of these particles remain. In this study, we prepared transition metal-doped cerium oxide (TM@CeO2; TM = Cr, Mn, Fe, Co, or Ni) nanoparticles and investigated the mechanism underlying dopant-dependent toxicity in HaCaT human keratinocytes. We show that doping with Cr or Co but not Fe, Mn, or Ni increased the toxicity of CeO2 NPs in dose- and time-dependent manners and led to apoptotic cell death. Interestingly, while both undoped and transition metal-doped NPs increased intracellular reactive oxygen species (ROS), toxic Cr@CeO2 and Co@CeO2 NPs failed to induce the expression of NRF2 (nuclear factor erythroid 2-related factor 2) as well as its downstream target genes involved in the antioxidant defense system. Moreover, activation of NRF2 transcription was correlated with dynamic changes in H3K4me3 and H3K27me3 at the promoter of NRF2, which was not observed in cells exposed to Cr@CeO2 NPs. Furthermore, exposure to relatively non-toxic Fe@CeO2 NPs, but not the toxic Cr@CeO2 NPs, resulted in increased binding of MLL1 complex, a major histone lysine methylase mediating trimethylation of histone H3 lysine 4, at the NRF2 promoter. Taken together, our findings strongly suggest that failure of cells to respond to oxidative stress is critical for dopant-dependent toxicity of CeO2 NPs and emphasize that careful evaluation of newly developed NPs should be preceded before industrial or biomedical applications.


Subject(s)
Cerium/toxicity , HaCaT Cells/metabolism , Histones/metabolism , NF-E2-Related Factor 2/genetics , Nanoparticles/toxicity , Transcriptional Activation/genetics , Apoptosis/drug effects , Cell Survival/drug effects , HaCaT Cells/drug effects , Humans , Methylation , NF-E2-Related Factor 2/metabolism , Nanoparticles/ultrastructure , Promoter Regions, Genetic/genetics , Reactive Oxygen Species/metabolism
11.
Phys Chem Chem Phys ; 18(21): 14172-6, 2016 05 25.
Article in English | MEDLINE | ID: mdl-27171609

ABSTRACT

We report the formation of both right- and left-handed chiral nanopores within a single domain during the self-assembly of an amino acid derivative on an inert Au(111) surface using STM. DFT calculations employed to rationalize this unusual result identified that intermolecular interactions between chiral, windmill-shaped tetramers are crucial for self-assembly.


Subject(s)
Amino Acids/chemistry , Gold/chemistry , Nanopores , Amino Acids/metabolism , Microscopy, Electron, Scanning , Stereoisomerism , Surface Properties
12.
Phys Chem Chem Phys ; 17(27): 17771-7, 2015 Jul 21.
Article in English | MEDLINE | ID: mdl-26084713

ABSTRACT

We report about the mechanistic studies of the reaction between a newly synthesized (S)-2-((R)-3H-dinaphtho[2,1-c:1',2'-e]azepin-4(5H)-yl)-2-phenylethanol based on the binaphthyl skeleton and (E)-2-methyl-5-phenylpent-2-enoic acid for the asymmetric hydrogenation of α,ß-unsaturated acids with heterogeneous palladium catalysts. The specific interactions between the chiral ligand and reactant were investigated in solution with palladium nanoparticles, as well as under ultrahigh vacuum (UHV) conditions on the palladium metal surface in the absence of hydrogen. The reactions were explored using nuclear magnetic resonance (NMR) spectroscopy, scanning tunneling microscopy (STM), and high-resolution photoemission spectroscopy (HRPES) combined with density functional theory (DFT) calculations. A NMR study identified the interaction between both molecules with palladium nanoparticles in solution. In addition, STM and HRPES studies revealed the spatial distribution and configuration of both compounds on the palladium metal surface under UHV conditions. The theoretical results support the experimental results with respect to the interaction energy value. It was found that the reaction between the ligand and reactant occurs with hydrogen bonding on palladium surface, simultaneously. The present study provides mechanistic details of the asymmetric hydrogenation reaction, which bears a correlation between the ligand, reactant, and catalyst during the reaction.


Subject(s)
Ligands , Palladium/chemistry , Catalysis , Hydrogen/chemistry , Hydrogen Bonding , Hydrogenation , Magnetic Resonance Spectroscopy , Metal Nanoparticles/chemistry , Microscopy, Scanning Tunneling , Phenylethyl Alcohol/chemistry , Stereoisomerism
13.
JACS Au ; 4(3): 1097-1106, 2024 Mar 25.
Article in English | MEDLINE | ID: mdl-38559718

ABSTRACT

Colloidal quantum dots (CQDs) have garnered significant attention in nanoscience and technology, with a particular emphasis on achieving high monodispersity in their synthesis. Recent advances in understanding the chemistry of reaction intermediates such as magic-sized nanoclusters (MSC) have paved the way for innovative synthetic strategies. Notably, monodisperse CQDs of various compositions, including indium phosphide, indium arsenide, and cadmium chalcogenide, have been successfully prepared using nanocluster intermediates as single-source precursors. Still, the early stage conversion chemistry of these nanoclusters preceding CQD formation has not been fully unveiled yet. Herein, we report the first-order conversion of amorphous nanoclusters (AMCs) to InAs MSCs prior to the formation of CQDs. We find that MSC, isolated via gel-permeation chromatography, is more stable than purified AMCs, as demonstrated in various chemical and thermolytic reactions. While the surface of InAs AMCs and MSC is similarly bound with carboxylate ligands, detailed structural analyses employing synchrotron X-ray scattering and X-ray absorption spectroscopy unveil subtle distinctions arising from the distinct surface properties and structural disorder characteristics of InAs nanoclusters. We propose that InAs AMCs undergo a surface reduction and structural ordering process, resulting in the formation of an InAs MSC in a thermodynamically local minimum state. Furthermore, we demonstrate that both types of nanoclusters serve as viable precursors, providing a similar monomer supply rate at elevated temperatures of around 300 °C. This study offers invaluable insights into the interplay of structure and chemical stability in binary nanoclusters, enhancing our ability to design these nanoclusters as precursors for highly monodisperse CQDs.

14.
ACS Appl Mater Interfaces ; 16(6): 7353-7363, 2024 Feb 14.
Article in English | MEDLINE | ID: mdl-38315818

ABSTRACT

This study entailed the synthesis of Ru nanocatalyst decorated on Nb-grafted SBA-15. A Nb-grafted SBA-15 support with varying Nb contents was utilized as a support for the Ru nanoparticles. The effect of Nb grafting on the immobilized Ru nanoparticle catalyst was systematically investigated, and its catalytic performance in the synthesis of furandicarboxylic acid using 5-hydroxymethylfurfural under base-free reaction conditions was evaluated. The results indicate the increased productivity of the Ru@Nb-grafted SBA-15 catalyst with a yield exceeding 95%, representing a significant advancement in catalysis. This study also affords insights into the complex relationship between the catalytic activity and selectivity and its unique surface attributes. Moreover, acidic sites were created, and the electron density within the active sites was modulated by monomeric Nb oxide species on the SBA-15. Additionally, the role of high-electron-density Ru atoms in facilitating the efficient adsorption and activation of the reactant, resulting in enhanced catalytic efficacy, was highlighted.

15.
Chemphyschem ; 14(11): 2491-6, 2013 Aug 05.
Article in English | MEDLINE | ID: mdl-23728842

ABSTRACT

We investigated the adsorption mechanism of homocysteine (HS-CH2-CH2-CH(NH2)-COOH) on the Ge(100) surface along with its electronic structures and adsorption geometries to determine the sequence of adsorption of this amino acid's functional groups using core-level photoemission spectroscopy (CLPES) in conjunction with density functional theory (DFT) calculations. We found that the "SH-dissociated OH-dissociated N-dative-bonded structure" and the "SH-dissociated OH-dissociation-bonded structure" were preferred at a monolayer (ML) coverage of 0.30 (lower coverage) and 0.60 (higher coverage), respectively. The "SH-dissociated OH-dissociated N-dative-bonded structure" was the most stable structure. Moreover, we systematically confirmed the sequence of adsorption of the functional groups of the homocysteine molecule on the Ge(100) surface, which is thiol group (-SH), carboxyl group (-COOH), and amine group (-NH2).


Subject(s)
Germanium/chemistry , Models, Chemical , Adsorption , Homocysteine/chemistry , Kinetics , Photoelectron Spectroscopy , Quantum Theory , Surface Properties , Thermodynamics
16.
Phys Chem Chem Phys ; 15(39): 16594-8, 2013 Oct 21.
Article in English | MEDLINE | ID: mdl-23959000

ABSTRACT

We confirmed the coverage dependent variation of tautomers of 2-mercaptothiazoline (the thiolate and thione forms) adsorbed on the Ge(100) surface under UHV conditions by using HRXPS measurements in conjunction with the DFT calculation method, which was studied before only in aqueous systems. The C 1s, S 2p, and N 1s core-level spectra obtained using HRXPS revealed the simultaneous presence of two distinct adsorption structures in different proportions at both low (0.15 ML) and high (0.65 ML) coverages. Moreover, we modelled the adsorption structures and geometric configurations of the bond states of 2-mercaptothiazoline on the Ge(100) surface by using the DFT calculation method, and found that the S dative bonded structure is the most stable adsorption structure for the thione form of 2-mercaptothiazoline and that the S-H dissociated-N dative bonded structure is the most stable adsorption structure for the thiolate form.


Subject(s)
Germanium/chemistry , Thiazolidines/chemistry , Adsorption , Models, Molecular , Stereoisomerism , Surface Properties
17.
Molecules ; 18(9): 10301-11, 2013 Aug 26.
Article in English | MEDLINE | ID: mdl-24064446

ABSTRACT

High-resolution photoemission spectroscopy (HRPES) measurements were collected and density functional theory (DFT) calculations were performed to track the exposure-dependent variation of the adsorption structure of 2-thiophenecarboxaldehyde (C4H3SCHO: TPCA) on the Ge(100) 2 × 1 reconstructed surface at room temperature. In an effort to identify the most probable adsorption structures on the Ge(100)-2 × 1 reconstructed surface, we deposited TPCA molecules at low exposure and at high exposure and compared the differences between the electronic features measured using HRPES. The HRPES data suggested three possible adsorption structures of TPCA on the Ge(100)-2 × 1 reconstructed surface, and DFT calculations were used to determine the plausibility of these structures. HRPES analysis corroborated by DFT calculations, indicated that an S-dative bonded structure is the most probable adsorption structure at relatively low exposure levels, the [4 + 2] cycloadduct structure is the second most probable structure, and the [2 + 2]-C=O cycloadduct structure is the least probable structure on the Ge(100)-2 × 1 reconstructed surface at relatively high exposure levels.


Subject(s)
Aldehydes/chemistry , Germanium/chemistry , Thiophenes/chemistry , Adsorption , Models, Chemical , Photoelectron Spectroscopy , Quantum Theory , Semiconductors , Surface Properties
18.
Brain Circ ; 9(2): 61-63, 2023.
Article in English | MEDLINE | ID: mdl-37576574

ABSTRACT

Stroke is one of the primary causes of morbidity and death worldwide. While intravenous (IV) thrombolysis with alteplase has been widely proven to be beneficial for acute ischemic stroke patients, it still has many limitations. Tenecteplase, a revised version of alteplase, is a potential alternative IV thrombolytic agent that has benefits over alteplase. The aim of this mini-review is to summarize the advancements in IV thrombolysis for severe ischemic stroke, specifically the development and transition from alteplase to tenecteplase.

19.
World Neurosurg ; 2023 Jun 27.
Article in English | MEDLINE | ID: mdl-37385438

ABSTRACT

OBJECTIVE: Explore the consequences of the coronavirus pandemic (COVID-19) on patients suffering from cerebrovascular disorders necessitating interventions. METHODS: Using the National Surgical Quality Improvement Program database, patients with cerebrovascular disease who underwent procedures before (2018-2019) and during (2020-2021) COVID-19 were identified. ICD-10 and Current Procedure Terminology codes were employed to classify diseases and elective cases, respectively. Our study analyzed variations in diagnoses, procedures, demographics, mortality and morbidity likelihood scores, and outcomes. Analysis was conducted using R 4.2.1 with tidyverse, haven, and Ime4 packages. Statistical significance was defined as P < 0.05. RESULTS: There was a significant rise in cerebrovascular accidents (CVAs) (9.96% vs. 12.28%) and a decrease in elective carotid endarterectomies (92.30% vs. 87.22%). Carotid stenting increased significantly (7.63% vs. 12.62%), and mortality probability scores rose for CVAs and carotid interventions. Ethnic (Hispanic) and racial minorities (Asians and Black/African American) were disproportionately affected (P < 0.001). Conditions from delayed care increased, and total operative times rose (117.46 vs. 124.33 minutes). Various patient outcomes worsened (P < 0.05), and multivariate analyses showed Hispanic patients had higher mortality and morbidity probability scores (P < 0.05). CONCLUSIONS: The pandemic led to more severe disease progression and reduced diagnoses due to screening delays, indicating deferred care. Prolonged operative times, extended hospital stays, and worsening outcomes, including infections and thrombotic events, hint at the repercussions of persistent staff shortages in health care facilities. Ethnic and racial minorities faced disproportionate impacts. To minimize harm to patients with cerebrovascular disease in future public health crises, it is crucial to develop policies that address these findings.

20.
Article in English | MEDLINE | ID: mdl-38082751

ABSTRACT

Abnormal intermuscular coordination in stroke-affected upper limbs contributes to motor deficits after stroke. In particular, abnormalities in the activation of upper limb muscle synergies after stroke were demonstrated for endpoint force control during isokinetic exercises. This study aimed to investigate the feasibility of isokinetic training to alter these abnormal synergy activations and improve motor control. Muscle synergies and Wolf Motor Function Test Functional Ability Scale (WMFT-FAS) score were compared before and after three weeks of electromyography-based training. The proposed training changed the synergy activation and improved the WMFT-FAS score in a chronic stroke survivor while preserving the muscle weights of the synergies.Clinical Relevance- This study presents the feasibility of neuromuscular training to modify the activation of upper limb muscle synergies against stroke-specific patterns of intermuscular coordination and improve WMFT-FAS score.


Subject(s)
Stroke Rehabilitation , Stroke , Humans , Feasibility Studies , Upper Extremity , Stroke/complications , Muscles
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