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Antibiotics rank as the most powerful weapons against bacterial infection, but their use is often limited by antibiotic-associated diarrhoea (AAD). Here, we reported that glutamine deficiency might act as a new link between clindamycin-induced dysbiosis and intestinal barrier dysfunction during AAD progression. Using a mouse model, we demonstrated that glutamine became a conditionally essential amino acid upon persistent therapeutic-dose clindamycin exposure, evidenced by a dramatic decrease in intestinal glutamine level and glutaminase expression. Mechanistically, clindamycin substantially confounded the abundance of butyrate-producing strains, leading to the deficiency of faecal butyrate which is normally a fundamental fuel for enterocytes, and in turn increased the compensatory use of glutamine. In addition to its pivotal roles in colonic epithelial cell turnover, glutamine was required for nitric oxide production in classic macrophage-driven host defence facilitating pathogen removal. Importantly, oral administration of glutamine effectively attenuated clindamycin-induced dysbiosis and restored intestinal barrier dysfunction in mice. Collectively, the present study highlighted the importance of gut microbiota in host energy homoeostasis and provided a rationale for introducing glutamine supplementation to patients receiving long-term antibiotic treatment.

Long noncoding RNAs (lncRNAs) have been implicated in a range of developmental processes and diseases, but the roles and mechanisms by which they act in adipogenic differentiation and adipose tissue biology are still unknown. By comparing the different expression patterns of lncRNAs before and after the adipocyte differentiation of human adipose-derived mesenchymal stem cells (hADSCs), we characterized a novel lncRNA, AC092834.1, which is significantly increased in preadipocytes. By gain- and loss-of-function experiments, we demonstrated that lncRNA AC092834.1 potentiated adipogenic differentiation through directly increasing the level of expression of DKK1, which competitively binds with LRP5 to inhibit the Wnt-β-catenin pathway and reduce the inhibition of adipogenesis by Wnt signaling. This finding provides novel mechanistic insights into a critical role for lncRNA AC092834.1 as a regulator of adipogenic differentiation, which expands our knowledge about the molecular mechanisms of obesity and other adipogenic differentiation-related disorders.

Transcription factors have already been proposed to work on some human diseases. Yet the role of translationally controlled tumor protein (TCTP) in cerebral palsy (CP) remains elusive. This study intends to examine the mechanism of TCTP on CP by regulating microRNA-200a (miR-200a).CP models of rats were established referring to the internationally recognized improved hypoxic ischemic encephalopathy modeling method. The neuroethology of rats, ultrastructure and pathological condition in brain tissues of rats were observed through several assays. The expression of TCTP, miR-200a, myelin transcription factor 1-like (Myt1L), tyrosine hydroxylase (TH) and inducible nitric oxide synthase (iNOS) along with apoptosis in brain tissues of rats was detected. The levels of reactive oxygen species (ROS), malondialdehyde (MDA), glutathione (GSH), glutathione peroxidase (GSH-Px), superoxide dismutase (SOD), tumor necrosis factor-α (TNF-α) and interleukin-6 (IL-6) in brain tissues of rats were determined. The binding site between miR-200a and Myt1L was analyzed.TCTP and Myt1L were overexpressed and miR-200a was under-expressed in CP rats. Elevated miR-200a ameliorated neurobehavior of CP rats and pathological injury in brain tissues. Elevated miR-200a up-regulated TH, GSH, GSH-Px, and SOD levels, down-regulated iNOS, ROS, MDA, TNF-α, and IL-6 levels, and attenuated neuronal apoptosis in brain tissues of CP rats. Myt1L was a target gene of miR-200a.Altogether, our study suggested that diminution of transcription factor TCTP up-regulates miR-200a to limit Myt1L expression, thereby improving neurobehavior and oxidative stress injury in CP rats.

An ultra-sensitive electrochemical immunosensor for detecting carcinoembryonic antigen was prepared. Graphene oxide-gold was used as the substrate modifier of the sandwich immunosensor. The high conductivity of graphene oxide effectively enhanced the electron transfer rate. The large specific surface area of graphene and the biocompatibility of gold nanoparticles increased the number of primary antibodies. The bovine serum albumin coated silver ��� platinum composite was used as a secondary antibody tag to prepare signal probes. The excellent biocompatibility of bovine serum albumin increased the number of secondary antibody connections. Silver nanoparticles increased the speed of electron transfer, and platinum further enhanced electrochemical sensing capabilities by catalyzing hydrogen peroxide. The immunosensor showed good performance for detecting carcinoembryonic antigen. Under the optimal conditions, the dynamic response range for carcinoembryonic antigen was from 0.005 ng��mL���1 to 100 ng��mL���1 with a detection limit of 0.76 pg��mL���1. The immunosensor also shown high selectivity, suitable stability, and good reproducibility, which provides new capabilities for clinical carcinoembryonic antigen detection.

In this study, we used inexpensive and synthetically simple electrocatalysts as replacements for conventional precious metal materials to reduce hydrogen peroxide (H2O2). We for the first time developed N-doped graphene-coated CuFe@MoC using one-step calcination of binary Prussian blue analogues (PBAs) with Mo6+ cationic grafting precursors. The synergistic interaction of CuFe PBA and MoC increased the catalytically active sites for H2O2 reduction. The catalyst was optimized in terms of the ratio of CuFe PBA to Mo6+, PVP content, and calcination temperature to improve its catalytic activity. When it was used to construct an electrochemical immunosensor for carcinoembryonic antigen (CEA) detection, polydopamine (CuFe-MoC@NG@PDA) was coated on its outer surface to increase the antibody loading and MoS2–Au NPs were used as substrates to improve Ab1 immobilization and accelerate electron transfer at the electrode interface, thereby improving the response signal of the immunosensor. Its concentration was linearly related to the response signal from 10 fg mL−1 to 80 ng mL−1, and the lowest limit of detection was 3 fg mL−1. In addition, the immunosensor has acceptable selectivity and high stability. All data indicate that nanocomposites have electrocatalytic applications.

Breast cancer is one of the most commonly diagnosed malignancies in women and is an important cause of cancer death. In this paper, the anti - breast cancer components of ginsenoside derivatives were studied by computer simulation. In this paper, effective components of ginseng were retrieved from TCSMP database, and target genes of active components were obtained from UniPort database. Through molecular docking technology, the key genes differentially expressed in the active components of ginseng and breast cancer were scored by molecular docking to obtain the active components of ginseng with the highest binding degree, and the next cell experiment was conducted for verification. The results of this study show that G_Rh2, a key active component of Chinese herbal medicine ginseng, can inhibit the proliferation, ha migration and invasion of human breast cancer cell lines MDA-MB-231 and MDA-MB-468. This result can provide a molecular basis for the further study of ginseng in the treatment of breast cancer, and also indicates the feasibility of using network pharmacology to connect large-scale target data to discover the mechanism of TCM components interfering with the disease.

Occupational trichloroethylene (TCE) exposure can cause hypersensitivity syndrome (TCE-HS). The human leukocyte antigen (HLA)-B*13:01 is reportedly an important allele involved in TCE-HS onset. However, the threshold exposure level causing TCE-HS in relation to HLA-B*13:01 remains unknown. We conducted a case-control study comprising 37 TCE-HS patients and 97 age- and sex-matched TCE-tolerant controls from the Han Chinese population. Urine and blood of patients were collected on the first day of hospitalization, and those of controls were collected at the end of their shifts. Urinary trichloroacetic acid (TCA) was measured as an exposure marker, and end-of-shift levels in the patients were estimated using the biological half-life of 83.7 h. HLA-B genotype was identified using DNA from blood. Crude odds ratios (ORs) for TCE-HS in the groups with urinary TCA concentration >15 mg/L to ≤50 mg/L and of >50 mg/L were 21.9 [95% confidence interval (CI) 4.2–114.1] and 27.6 (6.1–125.8), respectively, when the group with urinary TCA ≤15 mg/L was used as a reference. The frequency of HLA-B*13:01, the most common allele in the patients, was 62.2% (23/37), which was significantly higher than 17.5% (17/97) in the TCE-tolerant controls, with a crude OR of 8.4 (3.1–22.6). The mutually-adjusted ORs for urinary TCA >15 to ≤50 mg/L, >50 mg/L, and for HLA-B*13:01 were 33.4 (4.1–270.8), 34.0 (5.3–217.1), and 11.0 (2.4–50.7), respectively. In conclusion, reduction of TCE exposure to ≤15 mg/L is required for TCE-HS prevention because urinary TCA concentration >15 mg/L showed increased risk of TCE-HS, regardless of whether the patients had the HLA-B*13:01 allele.

A molybdenum disulfide based graphite phase carbon nitride (MoS2/g-C3N4) which is supported by a platinum-copper nanoparticle (PtCu) Z-type catalyst was created in this study. The catalyst exploits optoelectronic synergistic effect with large surface area, good catalysis, and biocompatibility to amplify the signal. The electrode impedance of the synthesized MoS2/g-C3N4-PtCu was reduced five times in visible light compared with dark conditions, thereby improving the detection of carcinoembryonic antigen (CEA). At a voltage of − 0.4 V, the immunoprobe constructed with this material is used for CEA detection. A linear relationship between 100 fg mL−1 and 80 ng mL−1 concentrations was achieved with a minimum detection limit of 33 fg mL−1 (S/N = 3). The recovery rate was 103–104%, and the relative standard deviation was 2.9–3.8%. This implies that the sandwich immunosensors have good reproducibility, selectivity, and stability and can be used in various applications.

Non-alcoholic fatty liver disease (NAFLD) is now a public health issue worldwide, but no drug has yet received approval. Genistein, an isoflavonoid derived from soybean, ameliorates high-fat-diet-induced NAFLD in mice, but the molecular underpinnings remain largely elusive. Arachidonic acid (AA) is a major ingredient of animal fats, and the AA cascade has been implicated in chronic inflammation. In this study, we investigated whether genistein was against NAFLD by targeting the AA cascade. Using a mouse model, we showed that genistein supplementation improved high-fat-diet-induced NAFLD by normalizing hepatomegaly, liver steatosis, aminotransferase abnormalities, and glucose tolerance. The thromboxane A2 (TXA2) pathway was aberrantly active in NAFLD, evidenced by an elevation of circulating TXA2 and hepatic thromboxane A2 receptor expression. Mechanistically, we found that genistein directly targeted cyclooxygenase-1 activity as well as its downstream TXA2 biosynthesis, while the TXA2 pathway might mediat...

Occupational trichloroethylene (TCE) exposure can induce life-threatening generalized dermatitis accompanied by hepatitis: TCE hypersensitivity syndrome (HS). Since the patients’ exposure levels have not been fully clarified, this study estimated end-of-shift urinary concentrations of trichloroacetic acid (TCA) and their lower limit below which the disease occurrence was rare. TCA concentration was measured in 78 TCE HS patients whose urine was collected at admission between 2nd and 14th d after their last shift. Then a linear regression model was used to calculate the mean TCA concentration with 95% confidence interval (95% CI) and 95% prediction interval (95% PI) in the end-of-shift urine. The estimated mean concentration was 83 (95% CI, 49–140) mg/l with 95% PI 9.6–720 mg/l. TCA concentrations were also measured in the end-of-shift urine of 38 healthy workers involved in the same job as were the patients. The geometric mean and its 95% CI were 127 mg/l and 16–984 mg/l, respectively. The exposure levels in HS patients might have thus overlapped with those in workers without HS. Accordingly, it was suggested that HS occurred in the environment where the workers were exposed to the TCE concentration corresponding to the urinary TCA concentration as low as 10 mg/l.

Development of metal-free carbon-based electrocatalysts with high-efficiency and excellent durability towards both oxygen and hydrogen evolution reactions (OER and HER) in a single electrolyte system is crucial yet challenging for sustainable energy generation. In this work, we report a facile and scalable strategy for fabricating self-supporting boron carbon oxynitride nanofibrous (BCNONF) mats with controllable boron contents via electrospinning and subsequent thermal treatment. Notably, the optimal BCNONF mat affords outstanding OER performance in alkaline electrolyte with low overpotential of 403 mV at 10 mA·cm−2, small Tafel slop of 72.9 mV·dec−1, and high stability (88.1% current density retention after 10 h), outperforming the commercial Ir/C benchmark. Moreover, it can serve as a remarkable HER catalyst with better stability than that of the commercial Pt/C counterpart in the same electrolyte, indicating its bifunctional characteristics. When employed as both anode and cathode of an electrolyzer, the self-supporting BCNONF mats exhibit superior activities with a potential of only 1.79 V at 10 mA·cm−2 and high long-term durability (90.6% current density retention after 50 h) for overall water splitting. Furthermore, density functional theory (DFT) calculations reveal that the remarkable OER and HER bifunctional performance of the BCNONF catalyst are originated from the reduced adsorption strength of O atom and the stronger H* adsorption on the BCNO surface as compared to those on CNO surface, which in turn facilitate efficient interfacial charge transfer between the electrocatalytic intermediates and the BCNONF catalyst.

A series of dual modified g-C3N4 (CN) composites were synthesized by integrating oxidation and doping quantum dots. Oxidation made the valance band and conduction band of the modified CN shifted to the opposite direction, resulting in higher redox activity. Meanwhile, the oxidized CN (O-CN) is more conducive to the deposition of SCNQDs due to electrostatic interaction. The introduction of sulfur-containing carbon nitride quantum dots (SCNQDs) can improve the light trapping ability and the separation efficiency of photogenerated charge-carriers. Moreover, quantum confinement effect of SCNQDs contributes to the upshift of valance band to enhance the reduction ability of composite (CN/SCNQDs), even though the band gap was not changed. The synergistic effect of dual modification made the composite (10:1-O-CN/SCNQDs) own the highest photodegradation rate of 1.43 mg/ (h·100 mg catalyst), which was 4.5, 2.0 and 1.9 times of CN, CN/SCNQDs and O-CN, respectively. Photodegradation mechanism of the composite was inferred that holes and superoxide radical played primary roles, whereas hydroxyl radical showed neglect effect. This work may provide some beneficial ideas for constructing high-performance co-modified organic photocatalysts.

In this work, we report for the first time a simple approach to fabricate 3D reduced graphene oxide/boron nitride (rGO/BN) sponges with no additional chemical cross-linkers. Encouragingly, such sponge possesses higher compressibility and better recoverability in both air and organic solvents as compared to the bare rGO sponge. The as-prepared rGO/BN sponge also exhibits excellent water resistance and high oil absorption capability, achieving up to 170 times its own weight toward a wide range of environmental contaminants. Especially, the absorbed oil can be easily removed by the absorption–squeezing process which is cost effective and environmental friendly for oil collection. Most importantly, the underlying reasons for the remarkable mechanical properties, excellent oil absorption capabilities have been analysed and revealed in depth. These exceptional characteristics together with the ease of scalable synthesis make the as-prepared 3D rGO/BN sponge show many promising applications ranging from tissue engineering, sensors, catalysis, energy storage and conversion to environmental remediation. MOE (Min. of Education, S’pore)

As one of the most exciting building blocks, DNA has gained increasing attention in the construction of promising nanostructures for various biological and medical purposes. In this contribution, we have developed an easily constructed DNA nanoassembly-based biosensing system that consists of one signal hairpin probe (SHP) and one label-free hairpin probe (LHP) for target p53 gene analysis. The probes of SHP and LHP were designed to be incapable of interacting with each other in the absence of the p53 gene. When the target gene is introduced, the 3' end of SHP (or LHP) hybridizes with the middle region of LHP (or SHP), leading to polymerase-sustained DNA nanoassembly. Because one target species can exhaust many building scaffolds to execute the programmable nanoassembly in one-pot approach, the fluorescence intensity of SHP is greatly enhanced in the presence of target gene in a simple and robust manner. The practical applicability was successfully demonstrated by screening target gene extracted from cancer cells. We believe this intriguing sensing strategy and desirable assay ability would provide new opportunities to develop versatile biochemical analysis methods.

An increasingly branched rolling circle amplification (IB-RCA) which contains a padlock probe (PP) and a structurally tailored molecular beacon (MB) was innovatively developed for highly sensitive detection of cancer gene, Kras gene codon 12. In this system, the PP can be circularized after hybridization with the precisely-matched target DNA, while the stem of MB can be also opened by target DNA, resulting in hybridization with the circularized PP to generate a long tandem single-stranded DNA (ssDNA) product. Since the MB is also designed to hybridize with ssDNA product, the newly-opened MBs are able to trigger the next RCA reactions, therapy producing branched rolling circle amplification (RCA) products and in turn leading to the increasingly branched RCA (IB-RCA). This alternately and continuously operates hybridization-based MB opening and opened MBs-triggered RCA. As a result, a great number of MBs are opened that is associated with a dramatically amplified fluorescent signal, enabling to quantify target DNA down to 100 fM. This sensing method demonstrates a new concept of IB-RCA amplification even in a simple way to efficiently transduce the fluorescence signal, accomplishing the highly sensitive and selective detection of cancer gene.

In the present study, we proposed a novel dual-cyclical nucleic acid strand-displacement polymerization (dual-CNDP) based signal amplification system for highly sensitive determination of tumor suppressor genes. The system primarily consisted of a signaling hairpin probe (SHP), a label-free hairpin probe (LHP) and an initiating primer (IP). The presence of target DNA was able to induce one CNDP through continuous process of ligation, polymerization and nicking, leading to extensively accumulation of two nicked triggers (NT1 and NT2). Intriguingly, the NT1 could directly hybridize SHP, while the NT2 could act as the target analog to induce another CNDP. The resulting dual-CNDP contributed the striking signal amplification, and only a very weak blank noise existed since the ligation template of target was not involved. In this case, the target could be detected in a wide linear range (5 orders of magnitude), and a low detection limit (78 fM) was obtained, which is superior to most of the existing fluorescent methods. Moreover, the dual-CNDP sensing system provided a high selectivity towards target DNA against mismatched target and was successfully applied to analysis of target gene extracted from cancer cells or in human serum-contained samples, indicating its great potential for practical applications.

Inspired by the significant bioactivity of ergosterol peroxide, we designed and synthesized four fluorescent coumarin and ergosterol peroxide conjugates 8a&ndash, d through the combination of ergosterol peroxide with 7-N,N-diethylamino coumarins fluorophore. The cytotoxicity of synthesized conjugates against three human cancer cells (HepG2, SK-Hep1, and MCF-7) was evaluated. The results of fluorescent imaging showed that the synthesized conjugates 8a&ndash, d localized and enriched mainly in mitochondria, leading to significantly enhanced cytotoxicity over ergosterol peroxide. Furthermore, the results of biological functions of 8d showed that it could suppress cell colony formation, invasion, and migration, induce G2/M phase arrest of HepG2 cells, and increase the intracellular ROS level.

Curcumin, a natural phenolic biphenyl compound derived from the plant Curcuma longa, modulates multiple steps of carcinogenesis partly by affecting the expression of miRNAs. Interestingly, cancer development shares many of the same signalling pathways with bone formation. Reduced bone mass creates favourable conditions for tumor metastasis. However, the effects and mechanism of curcumin on bone formation and osteogenesis are relatively unknown and controversial. We demonstrated that curcumin inhibited osteogenesis of human adipose-derived mesenchymal stem cells (hADSCs) in a concentration-dependent manner. In hADSCs, curcumin modulates the expression of a series of miRNAs, including miR-126a-3p, during osteogenesis. Overexpression or inhibition of miR-126a-3p is required for the effect of curcumin on osteogenesis. Further investigation indicated that miR-126a-3p directly targets and inhibits LRP6 through binding to its 3'-UTR, and then blocks WNT activation. Our findings suggest that the use of curcumin as an anti-tumor agent may lead to decreased bone mass through the suppression of osteogenesis. Knowing whether the long-term or high doses use of curcumin will cause decreased bone mass and bone density, which might increase the potential threat of tumor metastasis, also requires a neutral assessment of the role of curcumin in both regulating bone formation and bone absorption.

Objective Although adipocytes are the most abundant stromal cell component in breast cancer tissues, their interaction with breast cancer cells has been less investigated compared to cancer-associated fibroblasts or macrophages. Exosomes are a novel way of cell-cell communication and have been demonstrated to play an important role in various biological processes. However, to our knowledge, only a few studies have reported the effects of adipocyte exosomes on tumor development. Here, utilizing exosomes isolated from in vitro mesenchymal stromal/stem cell (MSC)-differentiated adipocytes, we systematically investigated this issue in a breast cancer model. Material and methods Exosomes were isolated from MSC-differentiated adipocytes and added to breast cancer cells MCF7. Cell proliferation was detected by MTS, and migration was analyzed by wound healing and transwell assay. An in vivo mouse xenograft model was used to evaluate MSC-differentiated adipocyte exosomes’ contribution to tumor growth. Signaling pathway activation was evaluated by western blot and immunofluorescence staining. Results We found MSC-differentiated adipocyte-derived exosomes are actively incorporated by breast cancer cell MCF7 and subsequently promote MCF7 proliferation and migration as well as protect MCF7 from serum derivation or chemotherapeutic drug-induced apoptosis in vitro. In the in vivo mouse xenograft model, depletion of exosomes reduces tumor-promoting effects of adipocytes. Transcriptomic analysis of MSC-differentiated adipocyte exosome-treated MCF7 identified several activated signaling pathways, among which we confirm the Hippo signaling pathway and found a blockade of this pathway leads to a reduced growth-promoting effect of adipocyte exosomes. Conclusion Taken together, our findings provide new insights into the role of adipocyte exosomes in the tumor microenvironment.

In this work, sulfur doped carbon nitride quantum dots (S-CNQDs) were prepared by one-pot copolymerization using melamine and thiourea as starting materials. The composite (g-C3N4/S-CNQDs), showing enlarged surface area, was fabricated by one-step in situ polymerization. The composites displayed much better photocatalytic activity than pristine g-C3N4 in degradation of methyl orange (MO) under UV–visible light irradiation. The removal efficiency of MO reached by 94.3% under visible light (λ ​> ​420 ​nm) illumination within 80 ​min, whereas it was nearly 100% under UV–visible light (λ ​> ​350 ​nm) irradiation within 40 ​min. The enhanced photocatalytic activity of composites is attributed to the doping of S-CNQDs, which leads to higher separation of photo-generated electron-holes, extended visible light response and more active sites. Additionally, the potential mechanism of photocatalytic degradation on MO by g-C3N4/S-CNQDs was proposed. This work presented a simple way for constructing S-CNQDs-based g-C3N4 catalyst.

As a maternal and developmental toxicant, cadmium (Cd) possesses weak penetrability through the placental barrier. However, the underlying mechanism remains unclear. To gain insight into the protein molecules associated with Cd toxicity in placenta and explore their roles in Cd transportation, a reproductive animal experiment was carried out using Sprague-Dawley rats. We performed proteomic analysis of the placenta by Difference Gel Electrophoresis (DIGE) combined with Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Tandem Mass Spectroscopy (MALDI-TOF/TOF MS). The DIGE assay identified 15 protein spots that were differentially expressed with a greater than 1.5-fold change in placenta of Cd-treated rats compared to the control rats. Based on the expression patterns and biological functions of the proteins, we selected the ABCG2 and ABCB4 transporter proteins for further analysis. Western blot analysis showed that Cd exposure could down-regulate the expression of ABCG2 and ABCB4 in the placenta. There was a negative dose-response relationship between Cd exposure and the expression of ABCG2 or ABCB4 protein. These results indicated that down-regulation of ABCG2 and ABCB4 transporters may regulate Cd across through placenta and thus affect the in vivo toxic effect of Cd to fetus.

Low-density polyethylene (LDPE) was modified with 2-hydroxyethyl acrylate (HEA) by a swollen phase grafting method with azobisiso-butyronitrile (AIBN) as initiator and xylene as a swelling agent. Fourier transform infrared spectroscopy (FTIR) and 1H-nuclear magnetic resonance (1H-NMR) showed that the HEA was grafted onto the PE molecular chains and the copolymer (LDPE-g-PHEA) was formed. The rheological data illustrated that the content of long chain branches (LCB) in LDPE-g-PHEA was higher than in LDPE. Melt flow index (MFI) measurements indicated that the LDPE backbone was degraded slightly when the HEA content was small in the process of grafting. X-ray diffraction (XRD) and water contact angle measurements demo-nstrated that the grafting degree had an influence on the crystallinity and polarity of the graft polymer. A staining analysis indicated that the dyeing of the product was improved continuously with increasing of the grafting degree. Polyvinylpyrrolidone (PVP), NaCl, and ultrasound were...

As DNA is employed to serve as a smart building block, an increasing interest has been devoted to the development of different DNA-based machines for the specific purpose, for example, the exploration of inter- or intramolecular interaction. In the current contribution, we developed an intelligent DNA machine and its operation can be designed to execute the ultrasensitive colorimetric detection of target nucleic acids. The DNA machine consists of a hairpin probe (HP) and an assistant template (AT). Using p53 gene as the target model to trigger the molecular machine operation, cyclic nucleic acid strand displacement polymerization (CNDP) was specifically induced, leading to the DNAzyme mediated catalytic reaction for signal readout. Specifically, with the help of polymerase and nickase, one target molecule was able to drive DNA nano-mechanical devices one-by-one through the hybridization/polymerization displacement cycles, and every initiated machine continued to operate, causing the dramatic accumulation of G-quadruplex-contained products. The G-quadruplex structure after binding to hemin could act as a horseradish peroxidase (HRP)-mimicking DNAzyme and catalyzed the oxidation of 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) by H2O2. As a result, an enhanced color change could be detected because of the generation of oxidation product ABTS•(+). In this way, the DNA machine has no any signal loss and enables the quantitative measurement of p53 DNA with a detection limit of 10fM, indicating great promise for unique application in biomedical research and early clinical diagnosis.

The development of a versatile biosensing platform to screen specific DNA sequences is still an essential issue of molecular biology research and clinic diagnosis of genetic disease. In this work, we for the first time reported a double-stem hairpin probe (DHP) that was simultaneously engineered to incorporate a DNAzyme, DNAzyme's complementary fragment and nicking enzyme recognition site. The important aspect of this hairpin probe is that, although it is designed to have a long ds DNA fragment, no intermolecular interaction occurs, circumventing the sticky-end pairing-determined disadvantages encountered by classic molecular beacon. For the DHP-based colorimetric sensing system, as a model analyte, cancer-related DNA sequence can trigger a cascade polymerization/nicking cycle on only one oligonucleotide probe. This led to the dramatic accumulation of G-quadruplexes directly responsible for colorimetric signal conversion without any loss. As a result, the target DNA is capable of being detected to 1 fM (six to eight orders of magnitude lower than that of catalytic molecular beacons) and point mutations are distinguished by the naked eye. The described DHP as a-proof-of-concept would not only promote the design of colorimetric biosensors but also open a good way to promote the diagnosis and treatment of genetic diseases.

Two novel poly(triphenylamines) (PTPAs) were prepared from 1,4-dibromobenzene, 4,4′-dibromodiphenyl ether and 4-phenoxyaniline, by a Buchwald–Hartwig coupling reaction. The structures of the resulting polymers were fully characterized by FTIR and 1H NMR. These PTPAs are thermally stable with 5% weight loss over 450 °C and the glass transition temperature (Tg) was found to be 140–149 °C. The resistive switching devices with the configuration Al/PTPA-TsOH/ITO were constructed using the conventional solution coating process. The devices demonstrated bi-directionally switchable WORM memory behavior. The ON/OFF current ratio of these devices was about 106 and the retention times can be as long as 104 s. The mechanism of the resistance switching effects of the devices can be understood on the basis of the electric field-induced doping effect, which would provide a guideline for designing new materials with high-performance memories.

We designed a novel water soluble topological structure polymer-ferrocene- terminated hyperbranched polyurethane (HPU-Fc) with good water solubility. The redox behaviors and the electrochemical kinetics parameters of HPU-Fcs were explored by cyclic voltammetry (CV) according to electrochemical principle. The topological structure polymer was applied for the design and engineering of non-enzymatic glucose sensor. The designed sensor showed good response to glucose concentration with good stability, favorable accuracy and high selectivity. The electrode was also used to detect glucose in blood samples, and the glucose contents detected by the electrode were in good agreement with those from the hospital where a common automatic biochemical analyzer (HF240–300) was used. This finding makes HPU-Fc a promising biosensor for directly sensing glucose.

Reducing the background signal and interference is an effective method for improving the sensitivity of an electrochemical immunosensor, which is greatly important for detecting tumour markers. In this study, a novel hybrid, nanoflower-like immunosensor probe was synthesised using graded copper silicate hollow spheres (CSH). A ‘close and open’ strategy was used in the immunosensor to magnify response signal. When the reaction conditions were 0.1 M PBS (pH = 7), the silicate and molybdate reaction produced a smaller signal, at which point the signal was off. When the reaction conditions were changed to 0.1 M PBS solution (containing 0.2 M HCl), MoS2 dissolved to form molybdate, while CSH-generated silicates reacted to form molybdate silicates to produce strong oxidation currents and the signal was turned on. This was the first enzyme-free electrochemical reading experiment conducted using inorganic silicate ion transduction. It had the following advantages: (1) CSH spheres with a three-dimensional hierarchical structure had a high specific surface area that allowed them to connect with more antibodies, which improved sensitivity; (2) the method was simple, the detection was fast and the background signal and interference were reduced. The immunosensor had a wide linear range from 0.1 pg mL−1 to 80 ng mL−1 and a minimum detection limit of 0.03 pg·mL−1 (S/N = 3) when detecting carcinoembryonic antigen.

A three-dimensional array of reduced graphene oxide/MoS2 @ polyaniline-layered nanosheets (denoted as rGO/MoS2 @ PANI) has a novel structure of intercalated MoS2/PANI nanosheets arrays arranged on rGO that can be used as carcinoembryonic antigen (CEA) electrochemical immunosensors (detectors). In this graded nanosheet, the PANI was embedded in the MoS2 interlayer. The MoS2/PANI nanosheets themselves limit volumetric changes when arranged as MoS2/PANI nanosheet arrays on rGO nanosheets to provide tight and sufficient heterogeneity. PANI locates on the interface itself and contains a large amount of –NH2 that can bind many antibodies. Simultaneously, we investigated the optimal amount of aniline to add. We found that these arrays had excellent film thickness and conductivity for improving CEA detection sensitivity. The tested immunosensor achieved sensitive and specific detection of CEA, with a detection limit of 0.3 pg mL−1. Under the optimal conditions, the prepared immunosensor exhibited acceptable reproducibility and selectivity and excellent stability. Satisfactory results of human serum samples indicated the potential application of the immunosensor for clinical monitoring of tumor markers.

(Liquid + liquid) equilibrium (LLE) data were determined for two ternary systems of (water + 2-propanol + ethyl butyrate) and (water + 2-propanol + n-pentyl acetate) at T = (293.15, 303.15 and 313.15) K under atmospheric pressure. The experimental data were correlated by the thermodynamic modified UNIQUAC and extended UNIQUAC models. The consistency of the experimental LLE data was further ascertained by applying Hand and Bachman equations. The extraction capability of ethyl butyrate and n-pentyl acetate was estimated by distribution coefficients and separation factors. The extraction efficiencies of ethyl butyrate and n-pentyl acetate were compared with those of other extraction agents such as isobutyl acetate, butyl acetate, butyl propionate and sec-butyl acetate. And extraction performance of ethyl butyrate and n-pentyl acetate in the extraction of 2-propanol from 2-propanol-water solutions was confirmed.

A series of novel 5α, 8α-endoperoxide steroidal hybrid derivatives containing isatin or indole substituents on the C-17 side chain were synthesized and characterized. The preliminary anti-proliferative activity of the compounds against HepG2, MCF-7, HT-29 and HeLa cell lines were investigated. Compounds 7g and 7l displayed significant anti-proliferative activity in vitro against HepG2 and Hela cells, with IC50 values lower than 8 μM. Furthermore, the biological functions of 7g were examined by flow cytometry and colony analysis. The results showed that 7g could induce HepG2 cell apoptosis, inhibited cell cycle progression, and colony growth. The studies indicated that structural modification at C-17 position could be a promising launch point for design steroidal anticancer agents.

Three-dimensional (3D) graphene architectures with well-controlled structure and excellent physiochemical properties have attracted considerable interest due to their potential applications in flexible electronic devices. However, the majority of the existing 3D graphene still encounters several drawbacks such as brittleness, non-uniform building units, and limited scale (millimeter or even micrometer), which severely limits its practical applications. Herein, we demonstrate a new scalable technique for the preparation of thin-layer graphite foam (GF) with controllable densities (27.2-69.2 mg cm-3) by carbonization of polyacrylonitrile using a template-directed thermal annealing approach. By integrating the GF with poly(dimethylsiloxane) (PDMS), macroscopic porous GF@PDMS with variable thin-layer GF contents ranging from 15.9 to 31.7% was further fabricated. Owing to the robust interconnected porous network of the GF and the synergistic effect between GF and PDMS, GF@PDMS with a 15.9% thin-layer GF content exhibited an impressive 254% increase in compressive strength over the bare GF. In addition, such 15.9% GF@PDMS can totally recover after the first compression cycle at a 95% strain and maintain ∼88% recovery even after 1000 compression cycles at an 80% strain, demonstrating its superior compressibility. Moreover, all of the as-prepared GF@PDMS samples possessed high electrical conductivity (up to 34.3 S m-1), relatively low thermal conductivity (0.062-0.076 W m-1 K-1), and excellent electromagnetic interference shielding effectiveness (up to 36.1 dB) over a broad frequency range of 8.2-18 GHz, indicating their great potential as promising candidates for high-performance electromagnetic wave absorption in flexible electronic devices. Accepted version

Reduced graphene oxide (rGO)/boron nitride (BN) composite films were successfully fabricated by facile vacuum filtration and subsequent thermal treatment. Their morphology, structure and electrochemical performance were systematically characterized by field emission scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, cyclic voltammetry, galvanostatic charge/discharge and electrochemical impedance spectroscopy. Importantly, the as-prepared rGO/BN composite film with a 2 wt.% BN content as binder-free anode material for lithium ion batteries (LIBs) exhibited a high reversible capacity of 278 mAh·g−1 at a high current density of 100 mA·g−1, high rate capability, and high capacity retention over the first 200 cycles. The enhanced electrochemical performances of rGO/BN composite film are attributed to the unique structure and the synergistic effects between layered BN and graphene, which favored electrolyte penetration and buffered the volume expansion during the lithiation and delithiation process. In addition, this work not only provides a versatile strategy for fabrication of other graphene-based films, but also shows the potential promise of rGO/BN composite film for other energy storage devices. Accepted version

Poly(vinyl alcohol) (PVA) hydrogels with tissue-like viscoelasticity, excellent biocompatibility, and high hydrophilicity have been considered as promising cartilage replacement materials. However, lack of sufficient mechanical properties is a critical barrier to their use as load-bearing cartilage substitutes. Herein, we report hydroxylated boron nitride nanosheets (OH-BNNS)/PVA interpenetrating hydrogels by cyclically freezing/thawing the aqueous mixture of PVA and highly hydrophilic OH-BNNS (up to 0.6 mg/mL, two times the highest reported so far). Encouragingly, the resulting OH-BNNS/PVA hydrogels exhibit controllable reinforcements in both mechanical and thermal responses by simply varying the OH-BNNS contents. Impressive 45, 43, and 63% increases in compressive, tensile strengths and Young’s modulus, respectively, can be obtained even with only 0.12 wt% (OH-BNNS:PVA) OH-BNNS addition. Meanwhile, exciting improvements in the thermal diffusivity (15%) and conductivity (5%) can also be successfully achieved. These enhancements are attributed to the synergistic effect of intrinsic superior properties of the as-prepared OH-BNNS and strong hydrogen bonding interactions between the OH-BNNS and PVA chains. In addition, excellent cytocompatibility of the composite hydrogels was verified by cell proliferation and live/dead viability assays. These biocompatible OH-BNNS/PVA hydrogels are promising in addressing the mechanical failure and locally overheating issues as cartilage substitutes and may also have broad utility for biomedical applications, such as drug delivery, tissue engineering, biosensors, and actuators. MOE (Min. of Education, S’pore)

Trimercaptotriazine-functionalized polystyrene chelating resin was prepared and employed for the adsorption of Ag(I) from aqueous solution. The adsorbent was characterized according to the following techniques: Fourier transform infrared spectroscopy, elemental analysis, scanning electron microscopy and the Brunauer-Emmet-Teller method. The effects of initial Ag(I) concentration, contact time, solution pH and coexisting ions on the adsorption capacity of Ag(I) were systematically investigated. The maximum adsorption capacity of Ag(I) was up to 187.1 mg/g resin at pH 0.0 and room temperature. The kinetic experiments indicated that the adsorption rate of Ag(I) onto the chelating resin was quite fast in the first 60 min and reached adsorption equilibrium after 360 min. The adsorption process can be well described by the pseudo second-order kinetic model and the equilibrium adsorption isotherm was closely fitted by the Langmuir model. Moreover, the chelating resin could selectively adsorb more Ag(I) ions than other heavy metal ions including: Cu(II), Zn(II), Ni(II), Pb(II) and Cr(III) during competitive adsorption in the binary metal species systems, which indicated that it was a highly selective adsorbent of Ag(I) from aqueous solution.

The major challenges associated with skin regeneration can include hindered vascularization and an insufficient degree of epithelization. In view of the complexity of these processes and the control signals on which they depend, one possible solution to these limitations could be simulating normal skin development and wound repair via the exogenous delivery of multiple cytokines. Here, we report the use of keratinocyte growth factor (KGF or FGF-7) and basic fibroblast growth factor (bFGF or FGF-2) released chemically modified collagen membranes to facilitate skin wound healing. The results from in vitro studies confirmed that this system resulted in higher cellular proliferation and faster cell migration. After transplanting the biomaterial onto an excisional wound healing model, the dual growth factor group, compared with the single growth factor groups and empty control group, showed more highly developed vascular networks and organized epidermal regeneration in the wounds. As a consequence, this experimental group showed mature epidermal coverage. Overall, this novel approach of releasing growth factors from a collagen membrane opens new avenues for fulfilling unmet clinical needs for wound care.

With the biological significance and important advances of nano-scale DNA devices, scientific activities have been directed toward developing molecular machinery. In this work, we present a novel two-wheel drive-based DNA nanomachine composed of one signaling recognition probe (SRP), one label-free recognition probe (LRP), and one driving primer (DP). Target DNA hybridization can activate LRP-based wheel driving by resorting to DP-mediated polymerization/nicking/displacement cycles. This in turn results in the accumulation of nicked strand 1 (NS1) that can initiate extended SRP-based wheel driving. As a result, the hairpin structure of SRP is stretched and pre-quenched fluorescence is restored. Meanwhile, lots of nicked strand 2 (NS2) are produced, which could hybridize perfectly with SRP and lead to further fluorescence amplification. It is worth noting that, because the nanomachine operation relies strongly on inputted target trigger, the unwanted background is completely eliminated. The detection limit of 1 pM and an excellent capability to recognize the single-base mutation were achieved. Significantly, the interrogating of target trigger extracted from cancer cells is already available, reflecting the potential for practical applications. As a proof-of-concept building, the unique analytical properties would significantly benefit the DNA nanomachines and reveal great promise in biochemical and biomedical studies.

Due to their exceptional chemical and thermal stabilities as well as electrically insulating property, atomically thin hexagonal boron nitride (h-BN) films have been identified as a promising class of dielectric substrate and encapsulation material for high-performance two-dimensional (2D) heterostructure devices. Herein, we report a facile chemical vapor deposition synthesis of large-area atomically thin h-BN including monolayer single crystals and C-doped h-BN (h-BCN) films utilizing a relatively low-cost, commercially available trimethylamine borane (TMAB) as a single-source precursor. Importantly, pristine 2D h-BN films with a wide band gap of ∼6.1 eV can be achieved by limiting the sublimation temperature of TMAB at 40 °C, while C dopants are introduced to the h-BN films when the sublimation temperature is further increased. The h-BCN thin films displayed band gap narrowing effects as identified by an additional shoulder at 205 nm observed in their absorbance spectra. Presence of N–C bonds in the h-BCN structures with a doping concentration of ∼2 to 5% is confirmed by X-ray photoelectron spectroscopy. The inclusion of low C doping in the h-BN films is expected to result in constructive enhancement to its mechanical properties without significant alteration to its electrically insulating nature. This study provides new insights into the design and fabrication of large-area atomically thin h-BN/h-BCN films toward practical applications and suggests that the range of precursors can be potentially extended to other anime borane complexes as well. ASTAR (Agency for Sci., Tech. and Research, S’pore) MOE (Min. of Education, S’pore)

A practical open channel microfluidic reactor with immobilized palladium complex was built on a cyclic olefin copolymer (COC) chip that was fabricated with a very simple hot-embossing technique. Palladium complex was immobilized on a photochemically grafted layer of polymerized N-[3-(dimethylamino)propyl]methacrylamide. Surface modification and catalyst immobilization onto COC were systematically characterized with streaming potential, surface contact angle, attenuated total reflection Fourier transform infrared spectrometry, scanning electron microscopy, atomic force microscopy and X-ray photoelectron spectroscopy. The reactor was comprised of a single 15 cm long serpentine channel of 120 μm (i.d.) and exhibited high efficiency for the Suzuki cross-coupling reaction of aryl iodides and bromides with arylboronic acids, affording good to excellent yields of the corresponding products. The reactions could be carried out smoothly with reduced reaction time and lower reactant consumption in the microreactor thermostated at 50°C. The proposed system may have great potential for high-throughput screening of catalysts and reaction conditions.

A mesoporous silica SBA-15-supported palladium with spindle-like nitrogen donor groups, 1,4-diaza-bicyclo[2.2.2]octane, has been successfully prepared and applied for homocoupling of terminal alkynes. The catalyst exhibited very high activity for terminal alkynes carrying various substitution groups, yields ranging from 70% to 94%, with a significant advantage that air acted as the oxidant. It also showed good reusability, could be easily recovered through filtration and washing, and reused at least five times with virtually no evident loss of catalytic performance. Furthermore, it was also proved to be an effective and air-stable heterogeneous catalyst for Suzuki coupling of aryl halides (X = I, Br) with arylboronic acids. The catalyst was systematically characterized by elemental analysis, X-ray photoelectron spectroscopy, high-resolution transmission electron microscope, nitrogen physical adsorption, Brunauer–Emmett–Teller method and X-ray powder diffraction. The analyses indicated that the mesoporous structure of the materials was retained during the immobilization process.

An amine-functionalized mesoporous silica SBA-15 supported palladium catalyst was prepared and characterized. For the first time, this supported palladium has been used as an efficient phosphine-free and reusable catalyst for the cross-coupling of haloalkynes with terminal alkynes. A variety of haloalkynes and aromatic/aliphatic terminal alkynes were selectively coupled to afford unsymmetrical 1,4-disubstituted 1,3-diynes in good yields.

The carbonylative Suzuki cross-coupling reactions of boronic acids with aryl iodides catalyzed by Pd 2 (dba) 3 as a ligand-free catalyst under atmospheric pressure of carbon monoxide has been firstly developed. Under mild reaction conditions, a broad range of aryl/heteroaryl iodides and aryl/heteroaryl boronic acids were selectively coupled to afford the corresponding diaryl ketones in good to excellent yields at low catalyst loadings (0.05 to 2mol-%). Moreover, the catalyst can also be recycled.

An air-and moisture-stable monodentate sulfur-ligand was synthesized. The ligand was found to be effective in Pd-catalyzed cross-coupling reactions of various aryl halides with arylboronic acids under aerobic conditions. This catalytic system is tolerant of a wide range of functional groups. The new complex structure of the sulfur-ligand/PdII has been determined by single-crystal X-ray diffraction. An air-and moisture-stable monodentate sulfur-ligand was synthesized and found to be effective in Pd-catalyzed cross-coupling reactions of various aryl halides with arylboronic acids under aerobic conditions. The new complex structure of the sulfur-ligand/PdII has been determined by single-crystal X-ray diffraction.

The critical curves for binary systems of methane combined with nitrogen, carbon monoxide, carbon dioxide, ethane, propane, butane and water at temperatures from 125 K to 650 K and pressures from 3.5 MPa to 250 MPa were calculated by using Heilig-Franck equation of state. This equation of state contains a repulsion term and an attraction term for intermolecular interaction. With pairwise combination rules for these potentials, three adjustable parameters are needed. The results showed that the critical curves of the former six binary systems belonged to type I, and CH4+H2O system belonged to type III. The calculated data were compared with the experimental data, which yielded good results for the pressure-temperature, pressure-composition and temperature-composition behaviors of the seven systems. Moreover, the values of the adjustable parameters were obtained from the calculation of the critical curves. They can also be used for other relevant calculation.

Zirconia supported platinum and tungstophosphoric acid (TPA) metal-acid bifunctional catalysts modified with lanthanum were prepared and tested in the reaction involving the production of branched-chain alkanes by skeletal isomerization of n -pentane. The prepared samples were characterized by XRD, FT-IR, H 2 -TPR and XPS. The catalytic performance was evaluated at 200 °C under atmospheric pressure. According to the conversion and selectivity a promotion effect of La on the activity of Pt-TPA/ZrO 2 was found and the optimal doping amount of La depended strongly on the Pt loadings. Simultaneously, cerium was also found to have the similar effect that was weaker than that of La.

A series of metal–acid bifunctional catalysts with varying quantities of platinum and tungstophosphoric acid (TPA) supported on zirconium oxide were prepared by co-impregnation method. In skeletal isomerization of n-pentane using catalyst with 1% Pt and 30% TPA loadings the conversion of the reactant which was close to the equilibrium conversion reached ca. 65% and the selectivity towards the product was as high as ca. 97% at atmospheric pressure and relatively low reaction temperature (200 °C). The phase structure, chemical structure, surface physicochemical properties, surface element oxidation states and hydrogen reduction behavior of the catalysts were well-characterized via XRD, FT-IR, N2 adsorption–desorption determination (BET), XPS and TPR. The effects of Pt and TPA loadings, calcination temperature, reaction temperature and weight hourly space velocity (WHSV) on the catalytic performance were investigated. In addition, a long period catalytic stability test of the catalyst with optimal Pt and TPA loadings was carried out, which indicated that the bifunctional catalyst was in possession of good stability in skeletal isomerization along with high catalytic activity under the experimental conditions.

Cyclic thiourea has been first utilized as an efficient ligand in palladium-catalyzed Hiyama cross-coupling reactions. In the presence of palladium(II) acetate, N, N′-bis(2,5-di- TERT-butylphenyl)- N, N′-ethylenethiourea, tetrabutylammonium fluoride, and dioxane, aryl halides (X = I, Br, Cl) underwent smooth cross coupling with trimethoxy(phenyl)silane to afford the corresponding biaryl products in moderate to excellent yields. Furthermore, the thiourea can be recovered by column chromatography and reused with negligible loss in catalytic activity.