Dual-Hyperspectral Optical Pump-Probe Microscopy with Single-Nanosecond Time Resolution.

In recent years, optical pump-probe microscopy (PPM) has become a vital technique for spatiotemporally imaging electronic excitations and charge-carrier transport in metals and semiconductors. However, existing methods are limited by mechanical delay lines with a probe time window up to several nanoseconds (ns) or monochromatic pump and probe sources with restricted spectral coverage and temporal resolution, hindering their amenability in studying relatively slow processes. To bridge these gaps, we introduce a dual-hyperspectral PPM setup with a time window spanning from nanoseconds to milliseconds and single-nanosecond resolution. Our method features a wide-field probe tunable from 370 to 1000 nm and a pump spanning from 330 nm to 16 µm. We apply this PPM technique to study various two-dimensional metal-halide perovskites (2D-MHPs) as representative semiconductors by imaging their transient responses near the exciton resonances under both above-band gap electronic pump excitation and below-band gap vibrational pump excitation. The resulting spatially and temporally resolved images reveal insights into heat dissipation, film uniformity, distribution of impurity phases, and film-substrate interfaces. In addition, the single-nanosecond temporal resolution enables the imaging of in-plane strain wave propagation in 2D-MHP single crystals. Our method, which offers extensive spectral tunability and significantly improved time resolution, opens new possibilities for the imaging of charge carriers, heat, and transient phase transformation processes, particularly in materials with spatially varying composition, strain, crystalline structure, and interfaces.

Spatially Confined Radical Addition Reaction for Electrochemical Synthesis of Carboxylated Graphene and its Applications in Water Desalination and Splitting.

Due to the chemical stability of graphene, synthesis of carboxylated graphene still remains challenging during the electrochemical exfoliation of graphite. In this work, a spatially confined radical addition reaction which occurs in the sub-nanometer scaled interlayers of the expanded graphene sheets for the electrochemical synthesis of highly stable carboxylated graphene is reported. Here, formate anions act as both intercalation ions and co-reactant acid for the confinement of electro-generated carboxylic radical (●COOH) in the sub-nanometer scaled interlayers, which facilitates the radical addition reaction on graphene sheets. The controllable carboxylation of graphene is realized by tuning the concentration of formate anions in the electrolyte solution. The high crystallinity of the obtained product indicates the occurrence of spatially confined ●COOH addition reaction between the sub-nanometer interlayers of expanded graphite. In addition, the carboxylated graphene have been used for water desalination and hydrogen/oxygen reduction reaction. Therefore, this work provides a new method for the in situ preparation of functionalized graphene through the electrolysis and its applications in water desalination and hydrogen/oxygen reduction reactions.

Sheet-Isolated MoS2 Used for Dispersing Pt Nanoparticles and its Application in Methanol Fuel Cells.

It is highly challenging to activate the basal plane and minimize the π-π stacking of MoS2 sheets, thus enhancing its catalytic performance. Here, we display an approach for making well-dispersed MoS2 . By using the N-doped multi-walled carbon nanotubes (NMWCNTs) as an isolation unit, the aggregation of MoS2 sheets was effectively reduced, favoring the dispersion of Pt nanoparticles (noted as Pt/NMWCNTs-isolated-MoS2 ). Excellent bifunctional catalytic performance for methanol oxidation and oxygen reduction reaction (MOR/ORR) were demonstrated by the produced Pt/NMWCNTs-isolated-MoS2 . In comparison to Pt nanoparticles supported on MoS2 (Pt/MoS2 ), the MOR activity (2314.14 mA mgpt -1 ) and stability (317.69 mA mgpt -1 after 2 h of operation) on Pt/NMWCNTs-isolatedMoS2 were 24 and 232 times higher, respectively. As for ORR, Pt/NMWCNTs-isolated-MoS2 holds large half-wave potential (0.88 V) and high stability (92.71 % after 22 h of operation). This work presents a tactic for activating the basal planes and reducing the π-π stacking of 2D materials to satisfy their applications in electrocatalysis. In addition, the proposed sheet-isolation method can be used for fabricating other 2D materials to promote the dispersion of nanoparticles, which assist its application in other fields of energy as well as the environment.

Impacts of Perfluoroalkyl Substances on Aqueous and Nonaqueous Phase Liquid Dechlorination by Sulfidized Nanoscale Zerovalent Iron.

Per- and poly fluoroalkyl substances (PFASs) are often encountered with nonaqueous phase liquid (NAPL) in the groundwater at fire-fighting and military training sites. However, it is unclear how PFASs affect the dechlorination performance of sulfidized nanoscale zerovalent iron (S-nFe0), which is an emerging promising NAPL remediation agent. Here, S-nFe0 synthesized with controllable S speciation (FeS or FeS2) were characterized to assess their interactions with PFASs and their dechlorination performance for trichloroethylene NAPL (TCE-NAPL). Surface-adsorbed PFASs blocked materials' reactive sites and inhibited aqueous TCE dechlorination. In contrast, PFASs-adsorbed particles with improved hydrophobicity tended to enrich at the NAPL-water interface, and the reactive sites were re-exposed after the PFASs accumulation into the NAPL phase to accelerate dechlorination. This PFASs-induced phenomenon allowed the materials to present a higher reactivity (up to 1.8-fold) with a high electron efficiency (up to 99%) for TCE-NAPL dechlorination. Moreover, nFe0-FeS2 with a higher hydrophobicity was more readily enriched at the NAPL-water interface and more reactive and selective than nFe0-FeS, regardless of coexisting PFASs. These results unveil that a small amount of yet previously overlooked coexisting PFASs can favor selective reductions of TCE-NAPL by S-nFe0, highlighting the importance of materials hydrophobicity and transportation induced by S and PFASs for NAPL remediation.

Stellate ganglion block ameliorated central post-stroke pain with comorbid anxiety and depression through inhibiting HIF-1α/NLRP3 signaling following thalamic hemorrhagic stroke.

BACKGROUND: Central post-stroke pain (CPSP) is an intractable and disabling central neuropathic pain that severely affects patients' lives, well-being, and socialization abilities. However, CPSP has been poorly studied mechanistically and its treatment remains challenging. Here, we used a rat model of CPSP induced by thalamic hemorrhage to investigate its underlying mechanisms and the effect of stellate ganglion block (SGB) on CPSP and emotional comorbidities. METHODS: Thalamic hemorrhage was produced by injecting collagenase IV into the ventral-posterolateral nucleus (VPL) of the right thalamus. The up-and-down method with von Frey hairs was used to measure the mechanical allodynia. Behavioral tests were carried out to examine depressive and anxiety-like behaviors including the open field test (OFT), elevated plus maze test (EPMT), novelty-suppressed feeding test (NSFT), and forced swim test (FST). The peri-thalamic lesion tissues were collected for immunofluorescence, western blotting, and enzyme-linked immunosorbent assay (ELISA). Genetic knockdown of thalamic hypoxia-inducible factor-1α (HIF-1α) and NOD-like receptor thermal protein domain associated protein 3 (NLRP3) with microinjection of HIF-1α siRNA and NLRP3 siRNA into the VPL of thalamus were performed 3 days before collagenase injection into the same regions. Microinjection of lificiguat (YC-1) and MCC950 into the VPL of thalamus were administrated 30 min before the collagenase injection in order to inhibited HIF-1α and NLRP3 pharmacologically. Repetitive right SGB was performed daily for 5 days and laser speckle contrast imaging (LSCI) was conducted to examine cerebral blood flow. RESULTS: Thalamic hemorrhage caused persistent mechanical allodynia and anxiety- and depression-like behaviors. Accompanying the persistent mechanical allodynia, the expression of HIF-1α and NLRP3, as well as the activities of microglia and astrocytes in the peri-thalamic lesion sites, were significantly increased. Genetic knockdown of thalamic HIF-1α and NLRP3 significantly attenuated mechanical allodynia and anxiety- and depression-like behaviors following thalamic hemorrhage. Further studies revealed that intra-thalamic injection of YC-1, or MCC950 significantly suppressed the activation of microglia and astrocytes, the release of pro-inflammatory cytokines, the upregulation of malondialdehyde (MDA), and the downregulation of superoxide dismutase (SOD), as well as mechanical allodynia and anxiety- and depression-like behaviors following thalamic hemorrhage. In addition, repetitive ipsilateral SGB significantly restored the upregulated HIF-1α/NLRP3 signaling and the hyperactivated microglia and astrocytes following thalamic hemorrhage. The enhanced expression of pro-inflammatory cytokines and the oxidative stress in the peri-thalamic lesion sites were also reversed by SGB. Moreover, LSCI showed that repetitive SGB significantly increased cerebral blood flow following thalamic hemorrhage. Most strikingly, SGB not only prevented, but also reversed the development of mechanical allodynia and anxiety- and depression-like behaviors induced by thalamic hemorrhage. However, pharmacological activation of thalamic HIF-1α and NLRP3 with specific agonists significantly eliminated the therapeutic effects of SGB on mechanical allodynia and anxiety- and depression-like behaviors following thalamic hemorrhage. CONCLUSION: This study demonstrated for the first time that SGB could improve CPSP with comorbid anxiety and depression by increasing cerebral blood flow and inhibiting HIF-1α/NLRP3 inflammatory signaling.

Engineered Fenofibrate as Oxidation-Sensitive Nanoparticles with ROS Scavenging and PPARα-Activating Bioactivity to Ameliorate Nonalcoholic Fatty Liver Disease.

Nonalcoholic fatty liver disease (NAFLD) is the most common chronic liver disease in western countries and China. Fenofibrate (FNB) can activate peroxisome proliferator-activated receptor α (PPARα) to increase fatty acid oxidation and ameliorate NAFLD. However, the application of FNB is limited in clinic due to its poor water solubility and low oral bioavailability. In this study, FNB-loaded nanoparticles (FNB-NP) based on a reactive oxygen species (ROS)-responsive peroxalate ester derived from vitamin E (OVE) and an amphiphilic conjugate 1,2-distearoyl-sn-glycerol-3-phosphoethanolamine-N-[methoxy(poly(ethylene glycol))-2000] (DSPE-PEG) were developed to enhance the preventive effects of FNB against NAFLD. In in vitro studies, FNB-NP displayed a high encapsulation efficiency of 97.25 ± 0.6% and a drug loading efficiency of 29.67 ± 0.1%, with a size of 197.0 ± 0.2 nm. FNB released from FNB-NP was dramatically accelerated in the medium with high H2O2 concentrations. Moreover, FNB-NP exhibited well storage stability and plasma stability. In pharmacokinetic (PK) studies, FNB-NP, compared with FNB crude drug, significantly increased the AUC0→t and AUC0→∞ of the plasma FNB acid by 3.3- and 3.4-fold, respectively. In pharmacodynamics (PD) studies, compared with an equal dose of FNB crude drug, FNB-NP more significantly reduced hepatic lipid deposition via facilitating FNB release in the liver and further upregulating PPARα expression in NAFLD mice. Meanwhile, oxidative stress in NAFLD was significantly suppressed after FNB-NP administration, suggesting that OVE plays a synergistic effect on antioxidation. Therefore, ROS-sensitive FNB delivery formulations FNB-NP enhance the preventive effects of FNB against NAFLD and could be further studied as a promising drug for the treatment of NAFLD in clinic.

Tailoring Fe0 Nanoparticles via Lattice Engineering for Environmental Remediation.

Lattice engineering of nanomaterials holds promise in simultaneously regulating their geometric and electronic effects to promote their performance. However, local microenvironment engineering of Fe0 nanoparticles (nFe0) for efficient and selective environmental remediation is still in its infancy and lacks deep understanding. Here, we present the design principles and characterization techniques of lattice-doped nFe0 from the point of view of microenvironment chemistry at both atomic and elemental levels, revealing their crystalline structure, electronic effects, and physicochemical properties. We summarize the current knowledge about the impacts of doping nonmetal p-block elements, transition-metal d-block elements, and hybrid elements into nFe0 crystals on their local coordination environment, which largely determines their structure-property-activity relationships. The materials' reactivity-selectivity trade-off can be altered via facile and feasible approaches, e.g., controlling doping elements' amounts, types, and speciation. We also discuss the remaining challenges and future outlooks of using lattice-doped nFe0 materials in real applications. This perspective provides an intuitive interpretation for the rational design of lattice-doped nFe0, which is conducive to real practice for efficient and selective environmental remediation.

Particle-Scale Understanding of Arsenic Interactions with Sulfidized Nanoscale Zerovalent Iron and Their Impacts on Dehalogenation Reactivity.

Co-occurrence of organic contaminants and arsenic oxoanions occurs often at polluted groundwater sites, but the effect of arsenite on the reactivity of sulfidized nanoscale zerovalent iron (SNZVI) used to remediate groundwater has not been evaluated. Here, we study the interaction of arsenite [As(III)] with SNZVI at the individual-particle scale to better understand the impacts on the SNZVI properties and reactivity. Surface and intraparticle accumulation of As was observed on hydrophilic FeS-Fe0 and hydrophobic FeS2-Fe0 particles, respectively. X-ray absorption spectroscopy indicated the presence of realgar-like As-S and elemental As0 species at low and high As/Fe concentration ratios, respectively. Single-particle inductively coupled plasma time-of-flight mass spectrometry analysis identified As-containing particles both with and without Fe. The probability of finding As-containing particles without Fe increased with the S-induced hydrophobicity of SNZVI. The interactions of SNZVI materials with coexisting arsenite inhibited their reactivity with water (∼5.8-230.7-fold), trichloroethylene (∼3.6-67.5-fold), and florfenicol (∼1.1-5.9-fold). However, the overall selectivity toward trichloroethylene and florfenicol relative to water was improved (up to 9.0-fold) because the surface-associated As increased the SNZVI hydrophobicity. These results indicate that reactions of SNZVI with arsenite can remove As from groundwater and improve the properties of SNZVI for dehalogenation selectivity.

Triflylpyridinium Enables Rapid and Scalable Controlled Reduction of Carboxylic Acids to Aldehydes using Pinacolborane.

Building up new and efficient methods for the controlled conversion of carboxylic acids to aldehydes is important. Herein, we report a rapid, modular and scalable method for the conversion of carboxylic acids to aldehydes using pinacolborane at ambient temperature, in which a triflylpyridinium reagent is used. The conversion of carboxylic acid to intermediate acylpyridinium by triflylpyridinium is new. A binary pyridine-coordinated boronium complex is generated after reduction. The unprecedented reduction of the acylpyridinium by HBpin opens up a practically direct synthesis of aldehydes from carboxylic acids. Theoretical studies indicate that the reduction of acylpyridinium requires a lower activation free energy than that of the product aldehyde. The synthetic advantage of this protocol is further highlighted by the scalable synthesis of aldehyde via continuous flow process. Configuration retention for chiral acids are presented in those syntheses.

Identification and quantification of immune infiltration landscape on therapy and prognosis in left- and right-sided colon cancer.

BACKGROUND: The left-sided and right-sided colon cancer (LCCs and RCCs, respectively) have unique molecular features and clinical heterogeneity. This study aimed to identify the characteristics of immune cell infiltration (ICI) subtypes for evaluating prognosis and therapeutic benefits. METHODS: The independent gene datasets, corresponding somatic mutation and clinical information were collected from The Cancer Genome Atlas and Gene Expression Omnibus. The ICI contents were evaluated by "ESTIMATE" and "CIBERSORT." We performed two computational algorithms to identify the ICI landscape related to prognosis and found the unique infiltration characteristics. Next, principal component analysis was conducted to construct ICI score based on three ICI patterns. We analyzed the correlation between ICI score and tumor mutation burden (TMB), and stratified patients into prognostic-related high- and low- ICI score groups (HSG and LSG, respectively). The role of ICI scores in the prediction of therapeutic benefits was investigated by "pRRophetic" and verified by Immunophenoscores (IPS) (TCIA database) and an independent immunotherapy cohort (IMvigor210). The key genes were preliminary screened by weighted gene co-expression network analysis based on ICI scores. And they were further identified at various levels, including single cell, protein and immunotherapy response. The predictive ability of ICI score for prognosis was also verified in IMvigor210 cohort. RESULTS: The ICI features with a better prognosis were marked by high plasma cells, dendritic cells and mast cells, low memory CD4+ T cells, M0 macrophages, M1 macrophages, as well as M2 macrophages. A high ICI score was characterized by an increased TMB and genomic instability related signaling pathways. The prognosis, sensitivities of targeted inhibitors and immunotherapy, IPS and expression of immune checkpoints were significantly different in HSG and LSG. The genes identified by ICI scores and various levels included CA2 and TSPAN1. CONCLUSION: The identification of ICI subtypes and ICI scores will help gain insights into the heterogeneity in LCC and RCC, and identify patients probably benefiting from treatments. ICI scores and the key genes could serve as an effective biomarker to predict prognosis and the sensitivity of immunotherapy.

Recent advances of aminoazanium salts as amination reagents in organic synthesis.

Nitrogen-containing organic compounds are widely distributed in natural products, pharmaceuticals, and functional materials. Several methods have been reported for the construction of the C-N bond including the Curtius rearrangement, the Schmidt rearrangement, the Ullmann reaction, etc. Various sources of amines have been developed, among which the aminoazanium salt is a unique amine precursor because of its high operability, diversity of structures and diverse reaction modes. This review describes the synthesis of aminoazanium salts and discusses the relationship between their structure and reaction mode, in addition to highlighting the amination reactions using aminoazanium salts.

Fatigue behavior of endodontically treated maxillary premolars with MOD defects under different minimally invasive restorations.

OBJECTIVES: To analyze the stress distribution and subsequent fracture resistance of human maxillary premolars with mesial-occlusal-distal (MOD) defects restored with different minimally invasive restorations. MATERIALS AND METHODS: Seventy non-carious human maxillary premolars were selected and divided into seven groups (n = 10). Ten teeth without further preparation served as control. The remaining teeth were endodontically treated and received three restorative patterns: inlays without cusp coverage (I), onlays with palatal coverage (O), overlays with both buccal and palatal coverage (Ov). Lithium disilicate glass ceramics (EM) and machinable composite resin (LU) were used for restoration. Specimens were tested under cycling loading with tongue direction of 45° for 1.2 × 106 cycles at a 50-N load and 2.0-Hz frequency. The survival time and two fracture mode classifications were assessed. Three-dimensional models of each group were designed. The magnitude and pattern of stresses were analyzed under the same condition of the in vitro test using finite element stress analysis. RESULTS: Although the overlay model pattern produced more favorable stress distribution, three restorative patterns restored with the same material had no difference in survival curves (P > 0.05). Only the survival curve of the EM-Ov group had no statistical difference with that of the control group (P > 0.05). EM groups presented mainly interface adhesive failure, while LU groups were mainly material cohesive failure. CONCLUSION: For the endodontically treated maxillary premolars with MOD defect, the lithium disilicate glass ceramic overlay pattern can reach the best restorative effect. CLINICAL RELEVANCE: Comparing with restorative pattern, restorative material had a greater influence on the minimally invasive restoration of posterior teeth.

Effect of COVID-19 on epidemiological characteristics of road traffic injuries in Suzhou: a retrospective study.

BACKGROUND: To present the new trends in epidemiology of road traffic injuries (RTIs) during the Coronavirus disease 2019 (COVID-19) pandemic in Suzhou. METHODS: Pre-hospital records of RTIs from January to May in 2020 and the same period in 2019 were obtained from the database of Suzhou pre-hospital emergency center, Jiangsu, China. Data were extracted for analysis, including demographic characteristics, pre-hospital vital signs, transport, shock index, consciousness, pre-hospital death. A retrospective study comparing epidemiological characteristics of RTIs in Suzhou during the 5-month period in 2020 to the parallel period in 2019 was performed. RESULTS: A total of 7288 RTIs in 2020 and 8869 in 2019 met inclusion criteria. The overall volume of RTIs has statistical difference between the 2 years (p < 0.001), with fewer RTIs in 2020 compared with 2019. Electric bicycle related RTIs increased during the pandemic (2641, 36.24% vs 2380, 26.84%, p < 0.001), with a higher incidence of RTIs with disorder of consciousness (DOC) (7.22% vs 6.13%, p = 0.006). CONCLUSIONS: Under the impact of COVID-19, the total number of RTIs in Suzhou from January to May 2020 decreased. This observation was coupled with a rise in electric bicycle related injuries and an increase in the incidence of RTIs with DOC.

Comparison of base excess, lactate and pH predicting 72-h mortality of multiple trauma.

OBJECTIVE: To compare the predictive values of base excess (BE), lactate and pH of admission arterial blood gas for 72-h mortality in patients with multiple trauma. METHODS: This was a secondary analysis based on a publicly shared trauma dataset from the Dryad database, which provided the clinical data of 3669 multiple trauma patients with ISS > = 16. The records of BE, lactate, pH and 72-h prognosis data without missing values were selected from this dataset and 2441 individuals were enrolled in the study. Logistic regression model was performed to calculate the odds ratios (ORs) of variables. Area under the curve (AUC) of receiver operating curve (ROC) was utilized to evaluate the predictive value of predictors for 72 h in-hospital mortality. Pairwise comparison of AUCs was performed using the Delong's test. RESULTS: The statistically significant correlations were observed between BE and lactate (r = - 0.5861, p < 0.05), lactate and pH (r = - 0.5039, p < 0.05), and BE and pH (r = - 0.7433, p < 0.05). The adjusted ORs of BE, lactate and pH for 72-h mortality with the adjustment for factors including gender, age, ISS category were 0.872 (95%CI: 0.854-0.890), 1.353 (95%CI: 1.296-1.413) and 0.007 (95%CI: 0.003-0.016), respectively. The AUCs of BE, lactate and pH were 0.693 (95%CI: 0.675-0.712), 0.715 (95%CI: 0.697-0.733), 0.670 (95%CI: 0.651-0.689), respectively. CONCLUSIONS: There are significant correlations between BE, lactate and pH of the admission blood gas, all of them are independent predictors of 72-h mortality for multiple trauma. Lactate may have the best predictive value, followed by BE, and finally pH.

Predictive value of qSOFA score for death in emergency department resuscitation room among adult trauma patients:a retrospective study.

BACKGROUND: To explore the predictive value of the quick Sequential Organ Failure Assessment (qSOFA) score for death in the emergency department (ED) resuscitation room among adult trauma patients. METHODS: During the period November 1, 2016 to November 30, 2019, data was retrospectively collected of adult trauma patients triaged to the ED resuscitation room in the First Affiliated Hospital of Soochow University. Death occurring in the ED resuscitation room was the study endpoint. Univariate and multivariate analyses were performed to explore the association between qSOFA score and death. Receiver operating characteristic (ROC) curve analysis was also performed for death. RESULTS: A total of 1739 trauma victims were admitted, including 1695 survivors and 44 non-survivors. The death proportion raised with qSOFA score: 0.60% for qSOFA = 0, 3.28% for qSOFA = 1, 12.06% for qSOFA = 2, and 15.38% for qSOFA = 3, p < 0.001. Subgroup of qSOFA = 0 was used as a reference. In univariate analysis, crude OR for death with qSOFA = 1 was 5.65 [95% CI 2.25 to 14.24, p < 0.001], qSOFA = 2 was 22.85 [95% CI 8.84 to 59.04, p < 0.001], and qSOFA = 3 was 30.30 [95% CI 5.50 to 167.05, p < 0.001]. In multivariate analysis, with an adjusted OR (aOR) of 2.87 (95% CI 0.84 to 9.87, p = 0.094) for qSOFA = 1, aOR 6.80 (95% CI 1.79 to 25.90, p = 0.005) for qSOFA = 2, and aOR 24.42 (95% CI 3.67 to 162.27, p = 0.001) for qSOFA = 3. The Area Under the Curve (AUC) for predicting death in the ED resuscitation room among trauma patients was 0.78 [95% CI, 0.72-0.85]. CONCLUSIONS: The qSOFA score can assess the severity of emergency trauma patients and has good predictive value for death in the ED resuscitation room.

Aminoazanium of DABCO: An Amination Reagent for Alkyl and Aryl Pinacol Boronates.

The aminoazanium of DABCO (H2 N-DABCO) has been developed as a general and practical amination reagent for the direct amination of alkyl and aryl pinacol boronates. This compound is stable and practical for use as a reagent. Various primary, secondary. and tertiary alkyl-Bpin and aryl-Bpin substrates were aminated to give the corresponding amine derivatives. The amination is stereospecific. The anti-Markovnikov hydroamination of olefins was easily achieved by catalytic hydroboration with HBpin and in subsequent situ amination using H2 N-DABCO. Moreover, the combination of 1,2-diboration of olefins, using B2 pin2 , with this amination process achieved the unprecedented 1,2-diamination of olefins. The amination protocol was also successfully extended to aryl pinacol boronates.

Conformational turn triggers regio-selectivity in the bioactivation of thiophene-contained compounds mediated by cytochrome P450.

In the present work, we performed Density Functional Theory calculations to explore the bioactivation mechanism of thiophene-containing molecules mediated by P450s. For this purpose, relatively large size compounds, 2,5-diaminothiophene derivatives were selected particularly for this investigation. Here we found the successive regio-selectivity triggered by conformational turn played a significant role in the occurrence of bioactivation. 2,5-Diaminothiophene was oxidized to a 2,5-diimine thiophene-reactive intermediate by Compound I (Cpd I) through successive activations of two N-H bonds (H3-N11 and H1-N6). This reaction exhibited three special characteristics: (1) self-controlled regio-selectivity during the oxidation process. There was a large scale of conformational turn in the abstraction of the first H atom which triggers the selection of the second H for abstraction. (2) Proton-shuttle mechanism. In high spin (HS) state, proton-shuttle mechanism was observed for the abstraction of the second H atom. (3) Spin-selective manner. In protein environment, the energy barrier in HS state was much lower than that in low spin state. The novel proposed bioactivation mechanism of 2,5-diaminothiophene compounds can help us in rational design of thiophene-contained drugs avoiding the occurrence of bioactivation.

Correction to: CBFA2T2 is associated with a cancer stem cell state in renal cell carcinoma.

[This corrects the article DOI: 10.1186/s12935-017-0473-z.].

CBFA2T2 is associated with a cancer stem cell state in renal cell carcinoma.

BACKGROUND: Renal cell carcinoma (RCC) is the most common kidney cancer, accounting for approximately 80-90% of all primary kidney cancer. Treatment for patients with advanced RCC remains unsatisfactory. Rare cancer stem cells (CSCs) are proposed to be responsible for failure of current treatment. METHODS: OncoLnc was used as a tool for interactively exploring survival correlations. Gene manipulation and expression analysis were carried out using siRNA, RT-PCR and Western blotting. Wound healing and invasion assays were used for phenotypical characterization. Aldefluor assay and FACS sorting Sphere culture were used to determine the "stemness" of CSCs. Co-Immunoprecipitation (Co-IP) was used to examine the interaction between OCT4 and CBFA2T2. Student's t-test and Chi square test was used to analyze statistical significance. RESULTS: CBFA2T2 expression can significantly predict the survival of RCC patients. Knocking-down of CBFA2T2 can inhibit cell migration and invasion in RCC cells in vitro, and reduce ALDHhigh CSCs populations. CBFA2T2 expression is necessary for sphere-forming ability and cancer stem cells marker expression in RCC cell lines. CONCLUSIONS: Our data suggest that CBFA2T2 expression correlates with aggressive characteristics of RCC and CBFA2T2 is required for maintenance of "stemness" through regulation of stem cells factors, thereby highlighting CBFA2T2 as a potential therapeutic target for RCC treatment.

Effects of Different Substrates on Lignocellulosic Enzyme Expression, Enzyme Activity, Substrate Utilization and Biological Efficiency of Pleurotus Eryngii.

BACKGROUND/AIMS: Pleurotus eryngii is one of the most valued and delicious mushrooms which are commercially cultivated on various agro-wastes. How different substrates affect lignocellulosic biomass degradation, lignocellulosic enzyme production and biological efficiency in Pleurotus eryngii was unclear. METHODS AND RESULTS: In this report, Pleurotus eryngii was cultivated in substrates including ramie stalks, kenaf stalks, cottonseed hulls and bulrush stalks. The results showed that ramie stalks and kenaf stalks were found to best suitable to cultivate Pleurotus eryngii with the biological efficiency achieved at 55% and 57%, respectively. In order to establish correlations between different substrates and lignocellulosic enzymes expression, the extracellular proteins from four substrates were profiled with high throughput TMT-based quantitative proteomic approach. 241 non-redundant proteins were identified and 74 high confidence lignocellulosic enzymes were quantified. Most of the cellulases, hemicellulases and lignin depolymerization enzymes were highly up-regulated when ramie stalks and kenaf stalks were used as carbon sources. The enzyme activities results suggested cellulases, hemicellulases and lignin depolymerization enzymes were significantly induced by ramie stalks and kenaf stalks. CONCLUSION: The lignocelluloses degradation, most of the lignocellulosic enzymes expressions and activities of Pleurotus eryngii had positive correlation with the biological efficiency, which depend on the nature of lignocellulosic substrates. In addition, the lignocellulosic enzymes expression profiles during Pleurotus eryngii growth in different substrates were obtained. The present study suggested that most of the lignocellulosic enzymes expressions and activities can be used as tools for selecting better performing substrates for commercial mushroom cultivation.