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Postoperative adhesions occur widely in various tissues, bringing the risk of secondary surgery and increased medical burden. Hydrogel barriers with Janus-adhesive ability can achieve physical isolation of adjacent tissues and are therefore considered an ideal solution. However, integrating endoscopic delivery convenience and viscoelastic Janus hydrogel formation remains a great challenge. Here, we present a report of the in situ formation of Janus-adhesive hydrogel barrier using a sprayable fast-Janus-gelation (FJG) powder. We first methacrylate the polysaccharide macromolecules to break the intermolecular hydrogen bonds and impart the ability of rapid hydration. FJG powder can rapidly absorb interfacial water and crosslink through borate ester bonds, forming a toughly adhesive viscoelastic hydrogel. The Janus barrier can be simply formed by further hydrating the upper powder with cationic solution. We construct rat models to demonstrate the antiadhesions efficiency of viscoelastic FJG hydrogels in organs with different motion modalities (e.g., intestine, heart, liver). We also developed a low-cost delivery device with a standardized surgical procedure and further validated the feasibility and effectiveness of FJG powder in minimally invasive surgery using a preclinical translational porcine model. Considering the advantages in terms of therapeutic efficacy, clinical convenience, and commercialization, our results reveal the great potential of Janus-gelation powder materials as a next-generation antiadhesions barrier.
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Adesivos , Hidrogéis , Ratos , Animais , Suínos , Hidrogéis/química , Pós , Aderências Teciduais/prevenção & controle , ÁguaRESUMO
OBJECTIVES: To define how dynamic changes in pre- versus post-operative serum aspartate aminotransferase (AST) and alanine aminotransaminase (ALT) levels may impact postoperative morbidity after curative-intent resection of hepatocellular carcinoma (HCC). BACKGROUND: Hepatic ischemia/reperfusion can occur at the time of liver resection and may be associated with adverse outcomes following liver resection. METHODS: Patients who underwent curative resection for HCC between 2010-2020 were identified from an international multi-institutional database. Changes in AST and ALT (CAA) on postoperative day (POD) 3 versus preoperative values () were calculated using the formula: based on a fusion index via Euclidean norm, which was examined relative to the comprehensive complication index (CCI). The impact of CAA on CCI was assessed by the restricted cubic spline regression and Random Forest analyses. RESULTS: A total of 759 patients were included in the analytic cohort. Median CAA was 1.7 (range, 0.9 to 3.25); 431 (56.8%) patients had a CAA<2, 215 (28.3%) patients with CAA 2-5, and 113 (14.9%) patients had CAA ≥5. The incidence of post-operative complications was 65.0% (n=493) with a median CCI of 20.9 (IQR, 20.9-33.5). Spline regression analysis demonstrated a non-linear incremental association between CAA and CCI. The optimal cutoff value of CAA=5 was identified by the recursive partitioning technique. After adjusting for other competing risk factors, CAA≥5 remained strongly associated with risk of post-operative complications (Ref. CAA<5, OR 1.63, 95%CI 1.05-2.55, P=0.03). In fact, the use of CAA to predict post-operative complications was very good in both the derivative (AUC 0.88) and external (ACU 0.86) cohorts (n=1137). CONCLUSIONS: CAA was an independent predictor of CCI after liver resection for HCC. Use of routine labs such as AST and ALT can help identify patients at highest risk of post-operative complications following HCC resection.
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To the deep tissue penetration and ultra-low background, developing near-infrared (NIR) chemiluminescence probes for human health and environmental safety has attracted more and more attention, but it remains a huge challenge. Herein, a novel NIR chemiluminescence (CL) system was rationally designed and developed, utilizing Cr3+-activated ZnGa2O4 (ZGC) nanoparticles as a catalytic luminophore via hypochlorite (NaClO) activation for poisonous target (hydrazine, N2H4) detection. With superior optical performance and unique catalytic structure of ZGC nanoparticles, the fabricated ZGC-NaClO-N2H4 CL system successfully demonstrated excellent NIR emission centered at 700 nm, fast response, and high sensibility (limit of detection down to 0.0126 µM). Further experimental studies and theoretical calculations found the cooperative catalytic chemiluminescence resonance energy transfer mechanism in the ZGC-NaClO-N2H4 system. Remarkably, the ZGC-based NIR CL system was further employed for N2H4 detection in a complicated matrix involving bioimaging and real water samples, thereby opening a new way as a highly reliable and accurate tool in biomedical and environmental monitoring applications.
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A simple and stable cataluminescence (CTL) sensing platform based on a single sensing material for effective and rapid detection of aldehydes is an urgent need due to growing concerns for the environment, security, and health. Here, an effective and user-friendly identification method is successfully proposed to determine six common aldehydes of homologous compounds via a heterothermic CTL sensor system. Using Gd2O3 with excellent catalytic activity as a sensing material, thermodynamic and kinetic insights into the interactions between Gd2O3 and aldehydes at different temperatures were extracted and integrated to generate a unique constellation profile for each tested aldehyde, whereby achieving their effective and prompt determination. Moreover, the sensor system allowed the quantitative analysis of aldehydes with detection limits of 0.001, 0.009, 0.011, 0.011, 0.007, and 0.003 µg mL-1. Significantly, the sensor system had an excellent stability of up to 30 days. The CTL sensing platform was constructed based on a thermal regulation strategy that can provide a new approach to chemical agent identification.
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In light of deep tissue penetration and ultralow background, near-infrared (NIR) persistent luminescence (PersL) bioprobes have become powerful tools for bioapplications. However, the inhomogeneous signal attenuation may significantly limit its application for precise biosensing owing to tissue absorption and scattering. In this work, a PersL lifetime-based nanoplatform via deep learning was proposed for high-fidelity bioimaging and biosensing in vivo. The persistent luminescence imaging network (PLI-Net), which consisted of a 3D-deep convolutional neural network (3D-CNN) and the PersL imaging system, was logically constructed to accurately extract the lifetime feature from the profile of PersL intensity-based decay images. Significantly, the NIR PersL nanomaterials represented by Zn1+xGa2-2xSnxO4: 0.4 % Cr (ZGSO) were precisely adjusted over their lifetime, enabling the PersL lifetime-based imaging with high-contrast signals. Inspired by the adjustable and reliable PersL lifetime imaging of ZGSO NPs, a proof-of-concept PersL nanoplatform was further developed and showed exceptional analytical performance for hypochlorite detection via a luminescence resonance energy transfer process. Remarkably, on the merits of the dependable and anti-interference PersL lifetimes, this PersL lifetime-based nanoprobe provided highly sensitive and accurate imaging of both endogenous and exogenous hypochlorite. This breakthrough opened up a new way for the development of high-fidelity biosensing in complex matrix systems.
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Técnicas Biossensoriais , Aprendizado Profundo , Ácido Hipocloroso , Técnicas Biossensoriais/métodos , Ácido Hipocloroso/análise , Luminescência , Raios Infravermelhos , Humanos , Animais , Nanoestruturas/química , Medições Luminescentes/métodos , CamundongosRESUMO
DNA walking machines have achieved significant breakthroughs in areas such as biosensing, bioimaging, and early cancer diagnosis, facilitated by the self-assembly of DNA or its combination with other materials, such as magnetic beads and metal nanoparticles. However, current DNA walking machine strategies are constantly challenged by inadequate analytical sensitivity, while sophisticated signal amplification procedures are often indispensable. Single-particle inductively coupled plasma mass spectrometry (SP-ICPMS) provides superior sensitivity and can effectively discriminate between background noise and detected signals due to the large number of metal atoms in a nanoparticle and the concentrating effect of single nanoparticle detection. In this study, we present a novel approach utilizing single nanoparticle counting and duplex-specific nuclease (DSN)-assisted signal amplification to construct a 3D DNA walking machine for detecting the aggressive prostate cancer (PCa) biomarker miRNA-200c. The proposed strategy showed an improvement in sensitivity with a detection limit (LOD) of 0.93 pM (28 amol) and was successfully applied in human serum samples. To the best of our knowledge, this is the first report of the DNA walking machine with single nanoparticle counting study.
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DNA , MicroRNAs , Humanos , MicroRNAs/análise , MicroRNAs/sangue , DNA/química , Limite de Detecção , Neoplasias da Próstata/diagnóstico , Masculino , Nanopartículas Metálicas/química , Espectrometria de MassasRESUMO
Labile toxic pollutants detection remains a challenge due to the problem that a single method is prone to producing false-negative/-positive signals. The construction of a multisignal sensing platform with the advantages of different strategies is an effective way to solve this problem. Herein, a novel resonant light scattering (RLS), fluorescent and rapid visual multisignals sensing strategy for p-aminophenol (p-AP) detection was designed based on the adsorption and oxidation effects of defective amino-functionalized Ag-based nano metal-organic frameworks (NH2-Ag-nMOFs). In this reaction process, NH2-Ag-nMOFs with incomplete coordination oxidize H2O2 to produce singlet oxygen (1O2) which rapidly oxidizes p-AP, leading to the reduction of Ag+ to Ag0, thereby disrupting the structure of NH2-Ag-nMOFs and resulting in fluorescence quenching of NH2-Ag-nMOFs. Synchronously, owing to Ag0 aggregation and p-AP oxidation, the color of the system changed from colorless to purplish-red and pale brown within 20 s. The assay has realized the rapid naked-eye detection of 5 µM p-AP rapidly. Additionally, thanks to the intermolecular hydrogen bonding, NH2-Ag-nMOFs-p-AP aggregates formed, which enhanced the RLS signal. With the RLS signal, the designed multisignals sensing platform can analyze p-AP at a concentration as low as 11 nM and yield a wider dynamic response range than any single signal strategy reported before, which can quickly meet the measurement requirement of different actual samples. Overall, the proposed strategy without assembling various signal indicators presented an accurate, rapid, cost-effective, and sensitive multisignals sensing platform for p-AP analysis and has great prospects in labile toxic pollutants monitoring.
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Over the years, a number of state-of-the-art data analysis tools have been developed to provide a comprehensive analysis of data collected from gas chromatography-mass spectrometry (GC-MS). Unfortunately, the time shift problem remains unsolved in these tools. Here, we developed a novel comprehensive data analysis strategy for GC-MS-based untargeted metabolomics (AntDAS-GCMS) to perform total ion chromatogram peak detection, peak resolution, time shift correction, component registration, statistical analysis, and compound identification. Time shift correction was specifically optimized in this work. The information on mass spectra and elution profiles of compounds was used to search for inherent landmarks within analyzed samples to resolve the time shift problem across samples efficiently and accurately. The performance of our AntDAS-GCMS was comprehensively investigated by using four complex GC-MS data sets with various types of time shift problems. Meanwhile, AntDAS-GCMS was compared with advanced GC-MS data analysis tools and classic time shift correction methods. Results indicated that AntDAS-GCMS could achieve the best performance compared to the other methods.
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Cromatografia Gasosa-Espectrometria de Massas , Metabolômica , Cromatografia Gasosa-Espectrometria de Massas/métodos , Metabolômica/métodos , Animais , Fatores de Tempo , Análise de DadosRESUMO
BACKGROUND: We sought to define the accuracy of preoperative imaging to detect lymph node metastasis (LNM) among patients with pancreatic neuroendocrine tumors (pNETs), as well as characterize the impact of preoperative imaging nodal status on survival. METHODS: Patients who underwent curative-intent resection for pNETs between 2000 and 2020 were identified from eight centers. Sensitivity and specificity of computed tomography (CT), magnetic resonance imaging (MRI), positron emission tomography (PET)-CT, and OctreoScan for LNM were evaluated. The impact of preoperative lymph node status on lymphadenectomy (LND), as well as overall and recurrence-free survival was defined. RESULTS: Among 852 patients, 235 (27.6%) individuals had LNM on final histologic examination (hN1). The sensitivity, specificity, positive predictive value (PPV), and negative predictive value (NPV) were 12.4%, 98.1%, 71.8%, and 74.4% for CT, 6.3%, 100%, 100%, and 80.1% for MRI, 9.5%, 100%, 100%, and 58.7% for PET, 11.3%, 97.5%, 66.7%, and 70.8% for OctreoScan, respectively. Among patients with any combination of these imaging modalities, overall sensitivity, specificity, PPV, and NPV was 14.9%, 97.9%, 72.9%, and 75.1%, respectively. Preoperative N1 on imaging (iN1) was associated with a higher number of LND (iN1 13 vs. iN0 9, p = 0.003) and a higher frequency of final hN1 versus preoperative iN0 (iN1 72.9% vs. iN0 24.9%, p < 0.001). Preoperative iN1 was associated with a higher risk of recurrence versus preoperative iN0 (median recurrence-free survival, iN1âhN1 47.5 vs. iN0âhN1 92.7 months, p = 0.05). CONCLUSIONS: Only 4% of patients with LNM on final pathologic examine had preoperative imaging that was suspicious for LNM. Traditional imaging modalities had low sensitivity to determine nodal status among patients with pNETs.
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Tumores Neuroectodérmicos Primitivos , Tumores Neuroendócrinos , Neoplasias Pancreáticas , Humanos , Prognóstico , Tumores Neuroendócrinos/diagnóstico por imagem , Tumores Neuroendócrinos/cirurgia , Tumores Neuroendócrinos/patologia , Excisão de Linfonodo , Metástase Linfática/patologia , Neoplasias Pancreáticas/diagnóstico por imagem , Neoplasias Pancreáticas/cirurgia , Neoplasias Pancreáticas/patologia , Tumores Neuroectodérmicos Primitivos/patologia , Tumores Neuroectodérmicos Primitivos/cirurgia , Linfonodos/diagnóstico por imagem , Linfonodos/cirurgia , Linfonodos/patologiaRESUMO
BACKGROUND: Intrahepatic cholangiocarcinoma (ICC) constitutes a group of heterogeneous malignancies within the liver. We sought to subtype ICC based on anatomical origin of tumors, as well as propose modifications of the current classification system. METHODS: Patients undergoing curative-intent resection for ICC, hilar cholangiocarcinoma (CCA), or hepatocellular carcinoma (HCC) were identified from three international multi-institutional consortia of databases. Clinicopathological characteristics and survival outcomes were assessed. RESULTS: Among 1264 patients with ICC, 1066 (84.3%) were classified as ICC-peripheral subtype, whereas 198 (15.7%) were categorized as ICC-perihilar subtype. Compared with ICC-peripheral subtype, ICC-perihilar subtype was more often associated with aggressive tumor characteristics, including a higher incidence of nodal metastasis, macro- and microvascular invasion, perineural invasion, as well as worse overall survival (OS) (median: ICC-perihilar 19.8 vs. ICC-peripheral 37.1 months; p < 0.001) and disease-free survival (DFS) (median: ICC-perihilar 12.8 vs. ICC-peripheral 15.2 months; p = 0.019). ICC-perihilar subtype and hilar CCA had comparable OS (19.8 vs. 21.4 months; p = 0.581) and DFS (12.8 vs. 16.8 months; p = 0.140). ICC-peripheral subtype tumors were associated with more advanced tumor features, as well as worse survival outcomes versus HCC (OS, median: ICC-peripheral 37.1 vs. HCC 74.3 months; p < 0.001; DFS, median: ICC-peripheral 15.2 vs. HCC 45.5 months; p < 0.001). CONCLUSIONS: ICC should be classified as ICC-perihilar and ICC-peripheral subtype based on distinct clinicopathological features and survival outcomes. ICC-perihilar subtype behaved more like carcinoma of the bile duct (i.e., hilar CCA), whereas ICC-peripheral subtype had features and a prognosis more akin to a primary liver malignancy.
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Neoplasias dos Ductos Biliares , Carcinoma Hepatocelular , Colangiocarcinoma , Neoplasias Hepáticas , Humanos , Carcinoma Hepatocelular/cirurgia , Neoplasias Hepáticas/patologia , Colangiocarcinoma/patologia , Prognóstico , Neoplasias dos Ductos Biliares/patologia , Ductos Biliares Intra-Hepáticos/patologiaRESUMO
Heart failure (HF) can be caused by a variety of causes characterized by abnormal myocardial systole and diastole. Ca2+ current through the L-type calcium channel (LTCC) on the membrane is the initial trigger signal for a cardiac cycle. Declined systole and diastole in HF are associated with dysfunction of myocardial Ca2+ function. This disorder can be correlated with unbalanced levels of phosphorylation / dephosphorylation of LTCC, endoplasmic reticulum (ER), and myofilament. Kinase and phosphatase activity changes along with HF progress, resulting in phased changes in the degree of phosphorylation / dephosphorylation. It is important to realize the phosphorylation / dephosphorylation differences between a normal and a failing heart. This review focuses on phosphorylation / dephosphorylation changes in the progression of HF and summarizes the effects of phosphorylation / dephosphorylation of LTCC, ER function, and myofilament function in normal conditions and HF based on previous experiments and clinical research. Also, we summarize current therapeutic methods based on abnormal phosphorylation / dephosphorylation and clarify potential therapeutic directions.
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Cálcio , Insuficiência Cardíaca , Humanos , Insuficiência Cardíaca/metabolismo , Insuficiência Cardíaca/fisiopatologia , Fosforilação , Cálcio/metabolismo , Canais de Cálcio Tipo L/metabolismo , Retículo Endoplasmático/metabolismo , Miocárdio/metabolismo , Miofibrilas/metabolismoRESUMO
INTRODUCTION: To investigate the impact of prognostic nutritional index (PNI) on short- and long-term outcomes of patients who underwent curative-intent resection for gastro-entero-pancreatic neuroendocrine tumors (GEP-NETs). METHODS: Patients with GET-NETs who underwent curative-intent resection were identified from a multi-center database. The prognostic impact of clinicopathological factors including PNI on post-operative outcomes were evaluated. A novel nomogram was developed and externally validated. RESULTS: A total of 2,099 patients with GEP-NETs were included in the training cohort; 255 patients were in the external validation cohort. Median PNI (n = 973) was 47.4 (IQR 43.1-52.4). At the time of presentation, 1,299 (61.9%) patients presented with some type of clinical symptom. Low-PNI (≤42.2) was associated with gastrointestinal symptoms, as well as nodal metastasis and distant metastasis (all p < 0.05). Patients with a low PNI had a higher incidence of severe (≥Clavien-Dindo grade IIIa: low PNI 24.9% vs. high PNI 15.4%, p = 0.001) and multiple (≥3 types of complications: low PNI 14.5% vs. high PNI 9.2%, p = 0.024) complications, as well as a worse overall survival (OS)(5-year OS, low PNI 73.7% vs. high PNI 88.5%, p < 0.001), and RFS (5-year RFS, low PNI 68.5% vs. high PNI 79.8%, p = 0.008) versus patients with high PNI (>42.2). A nomogram based on PNI, tumor grade and metastatic disease demonstrated excellent discrimination and calibration to predict OS in both the training (C-index 0.748) and two external validation (C-index 0.827, 0.745) cohorts. CONCLUSIONS: Low PNI was common and associated with worse short- and long-term outcomes among patients with GEP-NETs.
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Tumores Neuroendócrinos , Neoplasias Pancreáticas , Humanos , Avaliação Nutricional , Prognóstico , Tumores Neuroendócrinos/cirurgia , Neoplasias Pancreáticas/cirurgia , Estudos RetrospectivosRESUMO
A Gram-stain-negative, non-endospore-forming, motile, short rod-shaped strain, designated SYSU G07232T, was isolated from a hot spring microbial mat, sampled from Rehai National Park, Tengchong, Yunnan Province, south-western China. Strain SYSU G07232T grew at 25-50â°C (optimum, 37â°C), at pH 5.5-9.0 (optimum, pH 6.0) and tolerated NaCl concentrations up to 1.0â% (w/v). Phylogenetic analysis based on the 16S rRNA gene sequences revealed that strain SYSU G07232T showed closest genetic affinity with Chelatococcus daeguensis K106T. The genomic features and taxonomic status of this strain were determined through whole-genome sequencing and a polyphasic approach. The predominant quinone of this strain was Q-10. Major cellular fatty acids comprised C19â:â0 cyclo ω8c and summed feature 8. The whole-genome length of strain SYSU G07232T was 4.02 Mbp, and the DNA G+C content was 69.26âmol%. The average nucleotide identity (ANIm ≤84.85â% and ANIb ≤76.08ââ%) and digital DNA-DNA hybridization (≤ 21.9â%) values between strain SYSU G07232T and the reference species were lower than the threshold values recommended for distinguishing novel prokaryotic species. Thus, based on the provided phenotypic, phylogenetic, and genetic data, it is proposed that strain SYSU G07232T (=KCTC 8141T=GDMCC 1.4178T) be designated as representing a novel species within the genus Chelatococcus, named Chelatococcus albus sp. nov.
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Beijerinckiaceae , Fontes Termais , Filogenia , RNA Ribossômico 16S/genética , Composição de Bases , China , Ácidos Graxos/química , Análise de Sequência de DNA , DNA Bacteriano/genética , Técnicas de Tipagem Bacteriana , BactériasRESUMO
Incorporating a functional unit into the multidimensional coordination polymer skeleton is an efficient way to improve the stability of materials and expand their application. In this paper, anionic copper iodide inorganic functional modules are incorporated into one-dimensional extended chains by using a unique bidentate cationic organic ligand. Benefiting from the ionic extended structure, the resulting hybrid possesses a remarkable stability with a decomposition temperature as high as 300 °C. Meanwhile, the hybrid material exhibits intrinsic greenish white-light emission with a high photoluminescent quantum yield of 70%. The emission was investigated by temperature-dependent emission spectra, which proved to be the result of the synergistic effect of two energy states. The novel synthetic strategy provides an efficient route for the development of functional organic metal halides.
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Nonlinear optical (NLO) crystals are widely used in various fields. The introduction of lone-pair cations is regarded as an effective strategy to explore NLO crystals. In this work, two novel lead phosphite halides, centrosymmetric Pb6(HPO3)(H2PO3)Cl9 and noncentrosymmetric Pb6(HPO3)2Br8(H2O)·H2O, were obtained via a hydrothermal method. Pb6(HPO3)(H2PO3)Cl9 is the first reported lone-pair metal phosphite with two kinds of phosphite groups (HPO32- and H2PO3-) and Pb6(HPO3)2Br8(H2O)·H2O is the first inorganic NLO phosphite halide with a phase-matchable SHG effect of 1.02 × KDP. In addition, the Pb-centered polyhedral units of PbOCl4, PbOCl6, PbO2Cl5, PbO2Br5, PbOBr6, and PbO3(H2O)Br3 in these two structures have never been reported before. An in-depth study on the structure-property relationship of the two compounds with halogen substitution is also performed.
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Effective design and synthesis of second-order nonlinear optical (NLO) materials hold immense significance in driving modern science and technology advancements. In this study, we synthesized a new acentric mercury nitrate, (C5H12N2S)Hg(NO3)2, by regulating the coordination of the Hg atom through the introduction of a heteroatom. It exhibits an unprecedented [(C5H12N2S)2Hg2(NO3)4]∞ chain composed of Hg2+, NO3-, and organic molecule C5H12N2S. Notably, (C5H12N2S)Hg(NO3)2 demonstrates an unprecedented HgO3S unit and a second harmonic generation (SHG) intensity of 1.3 × KDP at 1064 nm, presenting the second-order nonlinear mercury nitrate constructed by organic molecule. Theoretical calculations suggest that the HgO3S unit and organic molecule C5H12N2S significantly contribute to the SHG effect. This study demonstrates that the incorporation of heteroatoms is an effective strategy for the development of new NLO materials.
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Tuning the surface chemical property and the local environment of nanocrystals is crucial for realizing a high catalytic performance in various reactions. Herein, we aim to elucidate the structure sensitivity of Pd facets on the surface catalytic hydrogenation reaction and to identify what role the nanoconfinement effect plays in the catalytic properties of Pd nanocrystal catalysts. By controlling the coating structures of mesoporous silica (mSiO2) on Pd nanocrystals with different exposed facets that include {100}, {111}, and {hk0}, we present a series of Pd@mSiO2 nanoreactors in core-shell and yolk-shell structures and the discovery of a partial-coated structure, which can provide different types of nanoconfinement, and we propose a seed size-dominated growth mechanism. We demonstrate that a superior activity was exhibited in Pd nanocrystals enclosed by the {hk0} facet as compared to the Pd{100} and Pd{111} facets, and substantially enhanced efficiency and stability were achieved in Pd@mSiO2 particles with yolk-shell structures, indicating a crucial superiority of optimizing the configuration of crystal facets and nanoconfinement. Our study provides an efficient strategy to rationally design and optimize nanocatalysts for promoting catalytic performance.
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Exploring ultraviolet (UV) nonlinear-optical (NLO) materials is significant for the conversion of a high-frequency laser. Two scandium phosphites, Sc(HPO3)(H2PO3)(H2O) and Sc(H2PO3)3, were successfully synthesized. Centric Sc(HPO3)(H2PO3)(H2O) exhibits a short UV cutoff edge (<200 nm) and a unique double-layer structure of [Sc2(HPO3)2(H2PO3)2(H2O)2]∞. The acentric Sc(H2PO3)3 exhibits a three-dimensional [Sc(H2PO3)3]∞ structure with a large band gap of 4.05 eV, and it demonstrates a moderately phase-matchable second-harmonic-generation response [0.60 × KDP (KH2PO4)] at 1064 nm. The crystal structures, optical properties, and theoretical calculations of the two compounds are discussed. This work will promote the exploration of new NLO phosphite materials.
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Exploring nonlinear optical (NLO) materials with short ultraviolet cutoff edges are significant for developing an all-solid-state laser. Here, a noncentrosymmetric zinc fluoride hydrate, ZnF2(H2O)4, was synthesized by a hydrothermal method. It crystallizes in the polar space group of Pca21. The compound consists of the central Zn2+ combined with F- and coordination water to form the [ZnF2(H2O)4] octahedra, and each octahedron is isolated from each other to form a 0-dimensional structure. As an acentric compound, ZnF2(H2O)4 shows a phase-matchable second-harmonic-generation (SHG) activity with an intensity about 0.5 times that of KH2PO4. More attractively, it also shows a short ultraviolet cutoff edge below 200 nm, which is rare in reported halide hydrate systems. Interestingly, from ZnF2 to ZnF2(H2O)4, the partial substitution of the coordinated F atoms by H2O molecules leads to the structural transformation from centric to acentric with SHG activity off to on. Structural analyses, NLO activity, and theoretical calculations are presented in this work.
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Low-dimensional crystalline materials have attracted much attention due to their special physical and chemical properties. Herein, two new oxalate chlorides, C(NH2)3Cd(C2O4)Cl(H2O)·H2O and BaCd(C2O4)1.5Cl(H2O)2, were synthesized. C(NH2)3Cd(C2O4)Cl(H2O)·H2O presents the unique {[Cd(C2O4)Cl(H2O)]-}∞ zigzag chain, while BaCd(C2O4)1.5Cl(H2O)2 shows a novel {[Cd(C2O4)1.5Cl]2-}∞ layer. They showed large measured band gaps, which were 3.76 and 4.53 eV, respectively, and the latter was the largest band gap in the A-M-C2O4-X (A = Monovalent cationic or alkaline earth metals, X = F, Cl, Br, I) family. They exhibit a large calculated birefringence of 0.075 and 0.096 at 1064 nm, respectively. This study promotes the exploration of synthesizing low-dimensional crystalline materials with balanced overall optical performances by a chemical scissors strategy.