Gold and Palladium Relay Catalytic [4 + 4] Cycloadditions of Enynamides and γ-Methylene-δ-valerolactones: Diastereoselective Construction of Furan-Fused Azacyclooctanes.

We report a highly efficient and diastereoselective gold and palladium sequential relay catalysis system for the synthesis of furan-fused eight-membered heterocycles. Employing a one-pot procedure, easily accessible enynamides undergo cyclization to generate azadienes in situ, which subsequently participate in diastereoselective formal [4 + 4] cycloadditions with γ-methylene-δ-valerolactones. This strategy enables the rapid and efficient construction of a series of furan-fused azacyclooctanes with diverse substituents in good yields (63-97%) and a high level of diastereoselectivity (7:1 → 20:1 dr).

A systematic pan-cancer analysis of PXDN as a potential target for clinical diagnosis and treatment.

Peroxidasin (PXDN), also known as vascular peroxidase-1, is a newly discovered heme-containing peroxidase; it is involved in the formation of extracellular mesenchyme, and it catalyzes various substrate oxidation reactions in humans. However, the role and specific mechanism of PXDN in tumor are unclear, and no systematic pan-cancer studies on PXDN have been reported to date. This study employed data from multiple databases, including The Cancer Genome Atlas and The Genotype-Tissue Expression, to conduct a specific pan-cancer analysis of the effects of PXDN expression on cancer prognosis. Further, we evaluated the association of PXDN expression with DNA methylation status, tumor mutation burden, and microsatellite instability. Additionally, for the first time, the relationship of PXDN with the tumor microenvironment and infiltration of fibroblasts and different immune cells within different tumors was explored, and the possible molecular mechanism of the effect was also discussed. Our results provide a comprehensive understanding of the carcinogenicity of PXDN in different tumors and suggest that PXDN may be a potential target for tumor immunotherapy, providing a new candidate that could improve cancer clinical diagnosis and treatment.

Exploring potential targets of Actinidia chinensis Planch root against hepatocellular carcinoma based on network pharmacology and molecular docking and development and verification of immune-associated prognosis features for hepatocellular carcinoma.

Background: Hepatocellular carcinoma (HCC) is one of the malignant tumors with the highest morbidity and mortality worldwide, and its prognosis remains a challenge. Actinidia chinensis Planch (ACP) root has good efficacy against HCC. This study aimed to explore the link between ACP and potential targets of HCC, and to develop a novel immune-based gene signature to predict HCC patient survival. Methods: Transcriptome data and clinical information on HCC were obtained from The Cancer Genome Atlas (TCGA; HCC: 374, normal: 50) and International Cancer Genome Consortium (ICGC) database (HCC: 243, normal: 202). Combined with the 2,483 immune-related genes from the Immport database, we used the least absolute shrinkage and selection operator (LASSO) to construct a prognostic model. Patients were divided into high-risk and low-risk groups by the median of the risk scores of the TCGA cohort. Kaplan-Meier survival analysis and receiver operating characteristic (ROC) curves were used to estimate the predictability of the model in HCC prognosis, and carried out external validation based on ICGC cohort. We analyzed the correlation of this model with immune cells and immune checkpoint genes. Finally, molecular docking of these genes and the corresponding ACP components. Results: We constructed a prognostic model composed of 3 immune-related genes [epidermal growth factor (EGF), baculoviral inhibitor of apoptosis repeat-containing protein 5 (BIRC5), and secreted phosphoprotein 1 (SPP1)]. And the high-risk group had a lower overall survival (OS) rate compared to the low-risk group (TCGA cohort: P=1.761e-05, ICGC cohort: P=8.716e-04). The outcomes of the AUC of ROC of prognostic risk model to predict for 1-, 2-, and 3-year OS: TCGA cohort: 0.749, 0.710, and 0.653 and ICGC cohort: 0.698, 0.736, and 0.753. Molecular docking results showed that quercetin had good binding activities with SPP1, BIRC5, and EGF, and ursolic acid (UA) and BIRC5 also had this feature. Conclusions: Our study speculates that ACP root anti-HCC may be involved in the immune regulation of the body by targeting EGF, BIRC5 and SPP1, which possess great potential and value as early warning molecules for HCC. This model may provide a reference for individualized diagnosis and treatment for HCC patients.

Preparation and separation of pure spherical cellulose nanocrystals from microcrystalline cellulose by complex enzymatic hydrolysis.

Spherical cellulose nanocrystals (CNCs), as a new and high value cellulose derivative, shows excellent application potential in many fields due to its special structure. The accurate and effective separation of pure spherical CNCs lays foundation for its further application. In this work, spherical CNCs were prepared by enzymatic hydrolysis of microcrystalline cellulose (MCC) with complex enzymes. In order to determine the optimal separation conditions of pure spherical CNCs, turbidity and Zeta potential were used to analyze the influence of pH on system stability, and the size and morphology of samples were characterized by DLS, AFM and SEM. The results showed that spherical CNCs with particle size of 24-76 nm can be separated from large particles with the help of alkali (pH = 9) dispersion and centrifugation speed of 3000 rpm. After three acid (pH = 4) washes, pure spherical CNCs were extracted and reducing sugars and enzyme proteins were removed. Compared with MCC, spherical CNCs had lower crystallinity but stronger reactivity and higher heat transfer. DTG results showed that the maximum weight loss temperature of spherical CNCs prepared by enzymatic hydrolysis was 309 °C.

Assessment of multiple environmental factors on the adsorptive and photocatalytic removal of gaseous formaldehyde by a nano-TiO2 colloid: Experimental and simulation studies.

Environmental factors affecting the photocatalytic oxidation of volatile organic compounds (VOCs) have previously been studied experimentally, but there are few theoretical studies, especially those on surface intermolecular forces. Because of this, it is unclear how multiple coexisting factors impact photocatalytic processes. Herein, comprehensive multi-factorial impact mechanisms of the photocatalytic oxidation of formaldehyde were assessed using experiments and density functional theory simulations. The influence of humidity, concentration, and intermediate formate was investigated using a nano-TiO2 colloid, followed by adsorption and photocatalytic simulations. The maximum photocatalytic reaction rate and degradation efficiency occurred at 50% humidity due to the initially enhanced and then weakened adsorption and photocatalysis of formaldehyde. This stemmed from the increased number of water molecules and the narrower TiO2 band gap at low humidities, as well as the competitive adsorption between formaldehyde and excess water molecules at high humidities. Upon increasing the formaldehyde concentration, its photocatalytic oxidation rate increased due to enhanced adsorption, but weakened photocatalysis decreased the photocatalytic efficiency. The intermediate formate enhanced the adsorption and inhibited photocatalysis and did not significantly change the photocatalytic oxidation rate of formaldehyde upon changing the irradiation time. These findings provide guidance for the photocatalytic oxidation of VOCs produced by industrial air pollution.

Spherical vs rod-like cellulose nanocrystals from enzymolysis: A comparative study as reinforcing agents on polyvinyl alcohol.

In this paper, we have isolated cellulose nanocrystallines (CNCs) with different morphologies by enzymatic hydrolysis, and prepared flexible and transparent nanocomposite films with PVA matrix via solution casting. By means of SEM, UV-vis, XRD, DTG, FT-IR and mechanical methods, the effects of rod-shaped cellulose nanocrystallines (RCNCs) and spherical cellulose nanocrystallines (SCNCs) on PVA nanocomposite films were compared systematically. The results showed CNCs with different morphologies had little effect on the transparency of the composite films, and the crystallinity fluctuated with the change of CNCs additive amount. Compared with the RCNCs, SCNCs had a better improve ability to the thermal stability of the composite films by promoting pyrolysis temperature 60-80 °C. On the contrary, the maximum mechanical properties of the composite films of RCNCs were much higher than those of SCNCs, and the Young's modulus of the PVA/RCNCs composite film were increased by 120.97 % in comparison with the pure PVA.

Electrophysiological features: The next precise step for SCN2A developmental epileptic encephalopathy.

BACKGROUND: To investigate the relationships among phenotypes, genotypes, and funotypes of SCN2A-related developmental epileptic encephalopathy (DEE). METHODS: We enrolled five DEE patients with five de novo variants of the SCN2A. Functional analysis and pharmacological features of Nav1.2 channel protein expressed in HEK293T cells were characterized by whole-cell patch-clamp recording. RESULTS: The phenotypes of c.4712T>C(p. I1571T), c.2995G>A(p.E999K), and c.4015A>G(p. N1339D) variants showed similar characteristics, including early seizure onset with severe to profound intellectual disability. Electrophysiological recordings revealed a hyperpolarizing shift in the voltage dependence of the activation curve and smaller recovery time constants of fast-inactivation than in wild type, indicating a prominent gain of function (GOF). Moreover, pharmacological electrophysiology showed that phenytoin inhibited over a 70% peak current and was more effective than oxcarbazepine and carbamazepine. In contrast, c.4972C>T (p.P1658S) and c.5317G>A (p.A1773T) led to loss of function (LOF) changes, showing reduced current density and enhanced fast inactivation. Both showed seizure onset after 3 months of age with moderate development delay. Interestingly, we discovered that choreoathetosis was a specific phenotype feature. CONCLUSION: These findings provided the insights into the phenotype-genotype-funotype relationships of SCN2A-related DEE. The preliminary evaluation using the distinct hints of GOF and LOF helped plan the treatment, and the next precise step should be electrophysiological study.

Preparation and characterization of spherical cellulose nanocrystals with high purity by the composite enzymolysis of pulp fibers.

The spherical cellulose nanocrystals (CNCs) with high purity were prepared, the processes included composite enzymolysis of pulp fibers and the purification of product. The impurities in the crude product CNCs were analyzed with FTIR, coomassie brilliant blue-G250 and ionic chromatography. The pure CNCs were characterized with SEM, XRD, DLS and TGA. The results indicated that the crude CNCs was flocculated and washed twice with a dilute acid solution (pH = 2) to get pure spherical CNCs, the purity was approximate 99.99%. The obtained pure spherical CNCs had a narrow particle size distribution with diameter 15-40 nm. FTIR and XRD analyses proved that the crystal phase of the spherical CNCs did not change, but the crystallinity decreased slightly compared with pulp fibers. The thermal degradation showed that the spherical CNCs had better thermal stability than one from other methods, and the temperature of maximum weight loss rate (Tmax) was 329.2 °C.

Preparation and characterization of the ribbon-like cellulose nanocrystals by the cellulase enzymolysis of cotton pulp fibers.

The enzymolytic preparation of cellulose nanocrystals (CNCs) has the unique advantages due to its green chemistry process. In this work, the cotton pulp fibers were enzymolyzed with the cellulase to prepare the ribbon-like CNC, and the samples were characterized by SEM, FTIR, XRD and DLS. The results indicated the CNC with the length 250-900 nm and width 30-45 nm could be produced from cotton pulp fibers at the lower cellulase concentration, the time 5-11 h and temperature 50 ºC. When the cellulase concentration rose up to 100 /ml, the granular CNC appeared, and at 300 µ/ml all of the formed CNC were granular. FTIR and XRD analyses proved that the ribbon-like CNC had the same crystal style and chemical structure with original cotton pulp fibers, but its crystallinity was weakened slightly. Despite the fact that there are the weakened crystallinity and aggregates, the as-prepared samples were still called as CNCs for simplicity. In addition, the article has discussed the mechanism for the forming ribbon-like CNC from the enzymolysis of cotton pulp fibers.

A room temperature operated ammonia gas sensor based on Ag-decorated TiO2 quantum dot clusters.

In this research, nanometer size aggregates (clusters) of titanium dioxide (TiO2) quantum dot clusters (QDs) have been successfully prepared via a convenient hydrolysis method at a low temperature (80 °C). Then different amounts (0-5%) of Ag were further decorated on the TiO2 QDs via dipping and annealing under a nitrogen atmosphere. After Ag decoration, the TiO2 QD sensing materials were synthesized, and characterization and NH3 gas sensing performance studies were carried out. Analysis via XRD and EDS was conducted, and the results showed that Ag+ ions were successfully reduced to Ag and decorated on the surface of the anatase TiO2 QDs. Noble metal Ag acted as the sites for adsorbates, catalysts, or promoters during the surface reactions, and as the element improving the thermal stability of the nanostructure. Therefore, the Ag-decorated gas sensor possessed better gas sensing performance than an undecorated gas sensor, and 3% Ag dopant proved to be the optimal amount of addition. The fabricated 3% Ag-decorated TiO2 QDs gas sensor, compared with the undecorated TiO2 QDs sensor, displayed a 6-times-higher sensing response at room temperature and demonstrated excellent gas sensing properties toward 10-100 ppm NH3 gas, good selectivity, gas sensitivity and stability, rapid response/recovery time, and a linear relationship between the response and the target gas concentration. In particular, the excellent performance of the Ag decorated-TiO2 QDs gas sensor was achieved at room temperature, which suggests the great possibility of a prompt gas sensing response, with the use of paper as a substrate, that requires a low operation temperature.

On-line chemical oxygen demand estimation models for the photoelectrocatalytic oxidation advanced treatment of papermaking wastewater.

Chemical oxygen demand (COD), an important indicative measure of the amount of oxidizable pollutants in wastewater, is often analyzed off-line due to the expensive sensor required for on-line analysis. However, its off-line analysis is time-consuming. An on-line COD estimation method was developed with photoelectrocatalytic (PEC) technology. Based on the on-line data of the oxidation-reduction potential (ORP), dissolved oxygen (DO) and pH of wastewater, four different artificial neural network methods were applied to develop working models for COD estimation. Six different batches of sequence batch reactor (SBR) effluent from a paper mill were treated with PEC oxidation for 90 minutes, and 546 data points were collected from the on-line measurements of ORP, DO and pH, and the off-line COD analysis. After having training and validation with 75% and 25% of data, and evaluation with four statistical criteria (R2, RMSE, MAE and MAPE), the estimation results indicated that the developed radial basis neural network (RBNN) model demonstrated the highest precision. Subsequently, the application of the RBNN model to a new batch of SBR effluent from the paper mill revealed that the RBNN model was acceptable for COD estimation during the PEC advanced treatment process of papermaking wastewater, which implied its possible application in the future.

Preparation and characterization of the spherical nanosized cellulose by the enzymatic hydrolysis of pulp fibers.

In this work, the pulp fibers were enzymolyzed to prepare the nanosized cellulose (NC). The as-prepared samples were characterized by optical microscopy, electron microscopy, and Raman spectra. The experimental results indicated that enzymatic hydrolysis of pulp fibers could produce the spherical NC with a mean particle size of about 30nm, which had the excellent monodispersity and uniformity. When the concentration of complex enzymes was 20u/mL (cellulase: xylanase=9: 1), the yield of NC was 13.6%. The single cellulase was used, even if the enzyme concentration reached up to 200u/mL, only a mixture of strip and granular flocculation were obtained. The positive synergistic effect between xylanase and cellulase could be due to the enzymolysis of hemicellulose located on the cellulose microfibers to be favorable of cutting and splitting of the microfibers by the endoglucanase in cellulase.

Geodesic Video Stabilization in Transformation Space.

We present a novel formulation of video stabilization in the space of geometric transformations. With the setting of the Riemannian metric, the optimized smooth path is cast as the geodesics on the Lie group embedded in transformation space. While solving the geodesics has a closed-form expression in a certain space, path smoothing can be easily implemented by using geometric interpolation, rather than optimizing any space-time energy function. Specially, by using the geodesic solution in the space of rigid transformations, our approach even gains speedup 10× faster than state-of-the-art methods for path smoothing and motion compensation, and guarantees no extra distortion drawn into the stabilized frames. The experiments demonstrate the efficiency and effectiveness of our algorithm on stabilizing a variety of shaky videos.

[Simultaneous determination of glyphosate and glufosinate-ammonium residues in tea by ultra performance liquid chromatography-tandem mass spectrometry coupled with pre-column derivatization].

A method was developed for the determination of glyphosate (GLY) and glufosinate-ammonium (GLUF) in tea using ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The sample was extracted with ultrapure water and dichloromethane for 30 min under ultrasonication, followed by a simple cleanup with a C18 solid phase extraction (SPE) cartridge, and then GLY and GLUF were derivatized using 9-fluorenylmethoxycarbonyl (FMOC-Cl) in borate buffer for 2 h. The derivatives of GLY and GLUF were separated on a Waters C18 column (50 mm x 2.1 mm, 1.7 µm) in a gradient elution mode, and finally detected with positive electrospray ionization-mass spectrometry (ESI-MS/MS ) in multiple reaction monitoring (MRM) mode. The quantification analysis was performed by external standard method. The method showed a good linearity (r > 0. 990) in the range of 0.003 125-0.1 mg/L. The limits of detection (LODs) of GLY and GLUF were 0.03 mg/kg. At the spiked levels of 0.375, 1.5 and 4.5 mg/kg, the recoveries of GLY and GLUF were 87.37%-99.11% and 81.44% -86.17% respectively, and the relative standard deviations (RSDs) (n = 6) of GLY and GLUF were 0.68%-1.35% and 1.01%-2.33%, respectively. This method is simple, rapid and characterized with acceptable sensitivity and accuracy to meet the requirements for the analysis of GLY and GLUF simultaneously in tea.

Extracellular matrix metalloproteinase inducer (EMMPRIN) is present in smooth muscle cells of human aneurysmal aorta and is induced by angiotensin II in vitro.

The aim of the present study was to determine whether EMMPRIN (extracellular matrix metalloproteinase inducer) is present and is up-regulated in human aneurysmal aortas, and to assess a possible association with AngII (angiotensin II)-induced aneurysm formation. The presence of EMMPRIN was assessed in 41 surgical specimens from patients with a TAA (thoracic aortic aneurysm) (Type A aortic dissection, n=12; Type B aortic dissection, n=7; and TAA without dissection, n=7) or an AAA (abdominal aortic aneurysm, n=15) by immunohistochemistry. EMMPRIN expression in aortic aneurysm tissues was compared with 12 aortas obtained during autopsy (free of any vascular diseases), and scored for both staining intensity and the percentage of vascular cells stained. EMMPRIN protein levels in cultured human aortic SMCs (smooth muscle cells) following stimulation of AngII were analysed by Western blotting. Significant EMMPRIN immunoreactivity was detected in aortic aneurysm lesions from patients with TAAs and AAAs. In the aneurysmal wall, alpha-actin-positive SMCs were the main source of EMMPRIN. The frequency of EMMPRIN overexpression was significantly higher (P=0.026) in TAAs with dissection (68.4%) than TAAs without dissection (14.3%). AngII stimulation up-regulated the expression of EMMPIRN in cultured human aortic SMCs, which was suppressed by the addition of the AT1R (AngII type 1 receptor) antagonist losartan. In conclusion, the present study is the first to report the expression of EMMPRIN in aortic aneurysmal diseases, and we speculate that EMMPRIN may be important in the pathogenesis of these diseases. Whether these abnormalities are potential therapeutic targets deserve further investigation.