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The rapid recombination of carriers on plasmon metal nanoparticles leads to relatively low efficiency of traditional photocatalysts. The combination of a metal and a semiconductor allows to the separation of hot electrons and holes to improve photocatalytic efficiency. In this study, Au nanoparticles were integrated with semiconductor TiO2 nanoparticles of different sizes to improve the photocatalytic activity. Various techniques have been developed to study the mechanism of catalytic activity, the significance of band bending in the space-charge region within metal–semiconductor nanocomposites, and the built-in electric field. The results provide theoretical and experimental evidence for the design of a high-performance surface plasmon resonance (SPR) photocatalyst. To reveal the interface band structure, surface-enhanced Raman spectroscopy (SERS) was employed to analyze the band structure of the TiO2–metal composites. This approach was based on the electrochemical Stark effect and a molecular probe strategy, combined with X-ray photoelectron spectroscopy (XPS), Electrochemical impedance spectroscopy (EIS), and other techniques at the molecular level. The results demonstrated that charge transfer occurred spontaneously between the Au nanoparticles and TiO2, and that the TiO2–metal interface constitutes a Schottky barrier. Moreover, the size of the TiO2 nanoparticles affects the degree of band bending. Optimal state matching was achieved with TiO2 (60 nm)–Au, improving the photocatalytic activity of the nanocomposite. The photocatalytic coupling reaction of p-aminothiophenol (PATP) acted as a probe to study the catalytic performance of TiO2–metal nanocomposites. The results revealed that the introduction of TiO2 improves the SPR catalytic activity of Au, mainly through the efficient separation of electrons and holes at the TiO2–metal interface.

Background Recent studies have confirmed that combined surgery and anti-TNF therapy could improve outcomes in patients with perianal fistulising Crohn’s disease (PFCD). However, the optimal timing for infliximab infusion after surgical intervention is uncertain. We aimed to determine the long-term efficacy of early initiation of infliximab following surgery among PFCD patients. Methods We performed a retrospective cohort study of PFCD patients who received combined infliximab and surgical treatment between 2010 and 2018 at a tertiary referral hospital. Patients were grouped according to the time interval between surgery and infliximab infusion, with 6 weeks into delayed infliximab induction group. The primary outcome was to compare surgical re-intervention between early and delayed infliximab induction groups. The secondary outcomes were fistula healing and predictors associated with these outcomes of early infliximab induction approach. Results One hundred and seventeen patients were included (73 in early infliximab induction, 44 in delayed infliximab induction). The median interval between surgery and infliximab initiation was 9.0 (IQR 5.5–17.0) days in early infliximab induction group and 188.0 (IQR 102.25–455.75) days in delayed infliximab induction group. After followed-up for a median of 36 months, 61.6% of patients in early infliximab induction group and 65.9% in delayed infliximab induction group attained fistula healing (p = 0.643). The cumulative re-intervention rate was 23%, 32%, 34% in early infliximab induction group and 16%, 25%, 25% in delayed infliximab induction group, at 1, 2, and 3 years respectively (p = 0.235). Presence of abscess at baseline (HR = 5.283; 95% CI, 1.61–17.335; p = 0.006) and infliximab maintenance therapy > 3 infusions (HR = 3.691; 95% CI, 1.233–11.051; p = 0.02) were associated with re-intervention in early infliximab induction group. Presence of abscess at baseline also negatively influenced fistula healing (HR = 3.429, 95% CI, 1.216–9.668; p = 0.02). Conclusion Although no clear benefit was shown compared with delayed infliximab induction group, early initiation of infliximab after surgery could achieve promising results for PFCD patients. Before infliximab infusion, durable drainage is required for patients with concomitant abscess or prolonged infliximab maintenance therapy.

Wheat is the main food crop in China while at the same time, heavy metals pose a significant threat to crop growth and food security. Many studies indicate that rhizospheric microorganism play an important role in regulating crop development and stress resistance. In this study, the variation in wheat root-associated microbial communities under copper pollution was studied using high-throughput sequencing. The microbial community structure and diversity among different wheat rhizocompartments were compared after sequencing of microbial communities in the bulk soil, rhizosphere, and endosphere of wheat under copper pollution in combination with pot-based experiments. The results showed that the microbial diversity of the endosphere was significantly lower than in the rhizosphere and bulk soil(

Zuojin capsule (ZJC), a classical prescription, is outstanding in improving the conditions of patients with gastrointestinal diseases and colorectal cancer (CRC). Although ZJC has multi-ingredient and multi-target characteristics, its pharmacological effect on colorectal cancer and the underlying mechanism remain unclear.Here, the activity of ZJC against CRC was evaluated by the experiments with CRC cells and HCT-116 xenografted mice. The key genes of CRC were obtained from the cancer genome atlas (TCGA). The genes potentially targeted by ZJC were collected from traditional Chinese medicine systems pharmacology (TCMSP) database. The underlying pathways related to selected targets were analyzed through gene ontology (GO) and pathway enrichment analyses. Western blot (WB), cellular thermal shift assay (CETSA), molecular docking and quantitative real-time PCR (QRT-PCR) were carried out to confirm the validity of the targets.In vitro and in vivo results indicated that ZJC may inhibit CRC cells and tumor growth. The network pharmacological analysis indicated that 22 compounds, 51 targets and 20 pathways were involved in the compound-target-pathway network. Our results confirmed that ZJC inhibited cycle progression, migration and induced apoptosis by targeting candidate genes (CDKN1A, Bcl2, E2F1, PRKCB, MYC, CDK2, and MMP9). We found that ZJC could directly change the protein level by regulating the protein stability and transcriptional activity of the target.In summary, combined network pharmacology and biological experiments proved that the main ingredients of ZJC such as quercetin, (R)-Canadine, palmatine, rutaecarpine, evodiamine, beta-sitosterol and berberine can target CDKN1A, Bcl2, E2F1, PRKCB, MYC, CDK2 and MMP9 to combat colorectal cancer. The results of this study provide a basic theory for the clinical trials of Zuojin Capsules against colorectal cancer.

Background: Clinical characteristics are keys to improve identification and treatment of Crohn´s disease (CD) so that large sample analysis is of great value. Aim: To explore the clinical characteristics of perianal fistulising CD. Methods: Analysis of 139 cases focused on their clinical data. Results: The proportion of males and females is 3.3:1; the mean age is 28.2 years; 47.5% of patients had anal fistula before CD diagnosis. Patients with prior perianal surgery and medication accounted for 64.7% and 74.1% respectively. The L3 type of lesion was present in 49.6% and the B1 and B2 types for 51.8% and 48.2% respectively; complex anal fistula was diagnosed in 90.6%. Symptoms of diarrhea were found in 46% and perianal lesions alone in 29.5% of patients. Abnormal BMI values was present in 44.6%; active CD activity index in 64.7%; and 94.2% had active perianal disease activity index. A proportion of patients manifest abnormal C-reactive protein, erythrocyte sedimentation rate, platelet, hemoglobin and albumin. Conclusion: We suggest that patients with anal fistula associated to these clinical features should alert the medical team to the possibility of CD, which should be further investigated through endoscopy and imaging examination of alimentary tract to avoid the damage of anal function by routine anal fistula surgery. RESUMO Racional: As características clínicas são fundamentais para melhorar a identificação e o tratamento da doença de Crohn (DC), de modo que a análise da amostra seja de grande valor. Objetivo: Explorar as características clínicas da DC fistulizante perianal. Métodos: Análise de 139 casos focados em seus dados clínicos. Resultados: A proporção de homens e mulheres foi de 3,3: 1; a média de idade de 28,2 anos; 47,5% dos pacientes tiveram fístula anal antes do diagnóstico de DC. Pacientes com cirurgia perianal prévia e medicação representaram 64,7% e 74,1%, respectivamente. O tipo de lesão L3 estava presente em 49,6% e os tipos B1 e B2, em 51,8% e 48,2%, respectivamente; fístula anal complexa foi diagnosticada em 90,6%. Sintomas de diarréia foram encontrados em 46% e lesões perianais isoladas em 29,5% dos pacientes. Valores anormais de IMC estavam presentes em 44,6%; índice de atividade DC ativa em 64,7%; e 94,2% tinham índice de atividade de doença perianal ativo. Proporção significativa de pacientes tinha proteína-C reativa, taxa de sedimenta do eritrócito, plaquetas hemoglobina e albumina anormais. Conclusão: Sugere-se que pacientes com fístula anal associada às essas características clínicas alertem a equipe médica para a possibilidade de DC, que deve ser investigada por endoscopia e exame de imagem do trato digestivo para evitar dano na função anal pela operação que rotineiramente é realizada no tratamento da fístula anal.

A simple 1,2-squaraine based chemosensor material (SQ) has been reported to show dual sensing performance for colorimetric detection of Fe3+ and Hg2+ ions. Compared to common instrumental analysis, this method could provide fast and direct detection though colorimetric changes by the naked eye. The sensor has shown excellent selectivity over the other metal ions by tuning different solvent environments. The detection limit for Fe3+ could reach to 0.538 &mu, M, which was lower than that in the environmental agency guideline (U.S. Environmental Protection Agency, U.S. EPA) in drinking water. And for Hg2+ detection, the limit was calculated as 1.689 &mu, M in our case. A 1:1 binding mode between SQ&ndash, Fe3+ and SQ&ndash, Hg2+ ion were evidenced by Job&rsquo, s plot measurement and IR analysis. The proposed different binding mechanisms were also supported by Density Function Theory (DFT) calculation. All these findings provide a unique material and a simple, facile, and low cost colorimetric method for dual metal ions analysis and have shown preliminary analytical applications in industrial water sample analysis.

The water and sediments of urban rivers are spatially heterogeneous because of the influence of environmental and anthropogenic factors. However, the spatial and functional diversity of bacterial communities in urban river sediments are unclear. We investigated the spatial distribution of microbial compositions in sediments in Qingdao section of the Dagu River, and the effects of sediment physiochemical properties on the variation were explored. Among the seven heavy metals analyzed, only the average concentration of Cd significantly exceeded the safety limit for sediments. The detailed composition and spatial distribution of bacterial communities fluctuated substantially between sites along the river. Bacterial datasets were separated into three clusters according to the environmental characteristics of sampling areas (the urbanized, scenic, and intertidal zones). For the urbanized zone, Acidobacteria, Firmicutes, Gemmatimonadetes, Bacteroidetes, and Gammaproteobacteria were significantly enriched, implying the effects of human activity. In the intertidal zone, Alphaproteobacteria and Deltaproteobacteria were significantly enriched, which are associated with S redox processes, as in the marine environment. Variation partitioning analysis showed that the amount of variation independently explained by variables of Na, Al, total S and Zn was largest, followed by sediment nutrients, while heavy metals and pH explained independently 13% and 9% of the variance, respectively. Overall, microbial structures in the Dagu River exhibited spatial variation and functional diversity as a result of natural and anthropogenic factors. The results will enable the prediction of the changes in urban river ecosystems that maintain their ecological balance and health.

A new squaraine based chemosensor TSQ was developed for colorimetric detection of Fe

A thymine moiety as ion binding accepter was introduced into asymmetric squaraine fluorophore by amide coupling reaction to develop a new thymine-squaraine based fluorescent chemosensor (SQ). Its detection ability towards heavy metal ions was investigated by UV-vis and fluorescent spectrometry. The results showed that the sensor had high selectivity towards Cd

Traditional "sandwich" structure immunoassay is mainly based on the self-assembly of "antibody on solid substrate-antigen-antibody with nanotags" architectures, and the sensitivity of this strategy is critically depended on the surface enhanced Raman scattering (SERS) activities and stability of nanotags. Therefore, the rational design and fabrication on the SERS nanotags attracts the common interests to the bio-related detecting and imaging. Herein, silica encapsulated Au with mercaptobenzoic acid (MBA) core-shell nanoparticles (Au-MBA@SiO

The SiO2 shell with the thickness of 4 nm was attached onto high surface enhanced Raman spectroscopy (SERS) active Au core nanoparticles to obtain Au@SiO2 core shell nanoparticles by the hydrolysis of sodium silicate solution with the boiling water bath. The inert shell of SiO2 isolated the direct interaction of Au nanoparticles and probe molecules. The stable, compact and uniform monolayer nanoparticles film was self assembled at water/oil interface, and one to six monolayers film was transferred to Si wafer as SERS substrates through layer by layer technique. The relationship between the SERS activities and layers of the monolayer nanoparticles film on Si surface was investigated. The SERS mapping was developed to determine the layers of the Au@SiO2 film. The coupling effect among the Au@SiO2 films was explored by changing the adsorption location of the probe on the multilayer films. The result revealed that the monolayer film was a favourable candidate with high-quality performances for the SERS application. The SERS signal was distributed on the surface with high uniformity at the same monolayer film, and it was enhanced in the intensity with the increase in film layers. It reached the maximun intensity as the film was over five layers. It indicated that the SERS signal was contributed mainly by the first five monolayers. The probe molecules were immobilized onto the first monolayer nanoparticles film, and the SERS signal from the probe approached to the maximum as the second monolayer covered the probe modified first nanoparticles film. It was dominated by the coupling effect ("hot spots") of the adjacent layers. The SERS signal decreased in intensity when the third layer was transferred onto the second layer, and it disappeared after the fouth layer was covered, mainly duo to the shield of the nanoparticles film to the incident laser and Raman signal. The preliminary results provided guidance for fabricating optimal SERS substrates.

Th concentrations of Cu, As, Pb, Zn, Cr, Cd, Ni in interstitial water were analyzed by ICP-MS from the heavily polluted area of Xiaoqing River. A modified BCR's sequential extraction procedure was used to investigate the fraction of the heavy metals in the surface sediments. The aquatic toxicity of heavy metals in interstitial water was assessed by US Water Quality Criteria (CCC, CMC). Based on the speciation of the metals in the surface sediments, the ecological risk of heavy metals was assessed with methods of risk assessment code (RAC) and potential ecological risk index. The results showed that: The tested heavy metals would not pose chronic toxicity for aquatic ecosystem. The contents of heavy metals (Cu, Pb, Zn, Cr, Cd, Ni) in the surface sediments were higher than the background values of the local soils, indicating enrichment of heavy metals. Cu, As and Ni were mainly composed with residual fractions, Pb and Cr were mainly constituted of residual and oxidizable fractions, and mass fractions of Zn and Cd existed mainly in acid soluble and reducible factions. The contents of bio-available fractions of Cd, Zn, Cr and Pb in the sediments were higher those of residual fractions, indicating high potential for secondary release. Based on calculation of RAC method, Cu, Pb, Cr and As posed extremely low to low risk to the environment. Accordingly, Ni was of low to medium risk, Cd was of medium to high risk, and Zn was of medium to extremely high risk to the environment. The potential ecological risk of heavy metals in the sediments was in the descending order of CdZnNiAsCuCrPb. Cd had high to very high potential ecological risk comparing with the other heavy metals. The potential ecological risk indexes (RI) of the heavy metals in the sediments were in the range of 136.83-264.83, and posed medium to high potential ecological risks for Xiaoqing River.

A new approach was developed for the magnetic separation of copper(II) ions with easy operation and high efficiency. p-Mercaptobenzoic acid served as the modified tag of Fe2O3@Au nanoparticles both for the chelation ligand and Raman reporter. Through the chelation between the copper(II) ions and carboxyl groups on the gold shell, the Fe2O3@Au nanoparticles aggregated to form networks that were enriched and separated from the solution by a magnet. A significant decrease in the concentration of copper(II) ions in the supernatant solution was observed. An extremely sensitive method based on surface-enhanced Raman spectroscopy was employed to detect free copper(II) ions that remained after the magnetic separation, and thus to evaluate the separation efficiency. The results indicated the intensities of the surface-enhanced Raman spectroscopy bands from p-mercaptobenzoic acid were dependent on the concentration of copper(II) ions, and the concentration was decreased by several orders of magnitude after the magnetic separation. The present protocol effectively decreased the total amount of heavy metal ions in the solution. This approach opens a potential application in the magnetic separation and highly sensitive detection of heavy metal ions.

The surface-enhanced Raman scattering (SERS) effect was critically dependent on the shape of the plasmonic nanostructures. It still remains a significant challenge in exploring the correlation between the SERS effect and the shape of nanostructures. Here, the polarized SERS combined with finite difference time domain (FDTD) calculation was developed to elucidate the origination of the SERS effect on an anisotropic spindle-shaped Fe2O3@Au nanoparticle. The surface enhancement factor for spindle-shaped Fe2O3@Au nanoparticles was estimated to be about six-orders by using pyridine as model molecules. A dramatic variation in SERS effect was observed by changing the excitation polarization direction. The maximum SERS intensity was detected when the excitation polarization was parallel to the long axes of Fe2O3@Au nanoparticles, while the minimum intensity was observed at the perpendicular orientation. The remarkable polarization-dependent SERS effects can be attributed to the local enhanced electric field that strongly depends on the polarization direction. The theoretical simulation based on the FDTD method was performed to evaluate the distribution of a local electromagnetic field on Fe2O3@Au single nanoparticles. It was in good agreement with the experimental results. This strategy provided deeper insight into the distribution of the SERS effect on a single anisotropic nanoparticle.

In the present paper, the authors reported the assembly and SERS studies of a simple device unit of a metal nanowire-molecule-metal nanoparticles junction in an anodic aluminum oxide (AAO) template. The AAO template was fabricated by two-step electrochemical oxidation. Metals were filled into the pores by AC deposition. Then the AAO template with metal nafiowires was immersed into the solution of 1,4-benzenedithiol (1,4-BDT), which was followed by the immersion into silver nanoparticles with appropriate diameter. 1,4-BDT served as the probe molecule for SERS detection as well as the molecule for linking the metal nanowires and metal nanoparticles. The simple junction of metal-molecule-metal embedded in AAO template was built successfully. The SERS effect of the junction was investigated through the dissolution of AAO template to expose the junctions in the same orientation (standing on the substrate vertically). The giant enhancement from the former junction might be attributed to the coupling effect in the junction. The authors' preliminary results revealed that SERS might be a characteristic tool for the junction and the construction on the junction will be beneficial to the investigation of the complex SERS mechanism.