Mo-based catalysts for CH4/H2S reforming to hydrogen production: effect of hydroxyl concentration of the support.

High concentration of H2S in acidic natural gas will lead to poisoning of catalysts for hydrogen production by methane steam reforming, thus limiting the further use of natural gas. Reforming CH4 by H2S can be considered as an alternative route to hydrogen production from methane. This process not only achieves the removal of H2S but also obtains chemical raw material CS2 and clean energy H2. By impregnating the Mo source on SiO2 treated with hydrogen peroxide and then using the catalyst in the CH4/H2S reforming reaction, we surprisingly found that the conversion rate of CH4 and H2S increased from 28 and 32% to 34% and 43%, respectively, after hydrogen peroxide treatment. The H2 production rate and the yield of CS2 increased from 20 mmolH2/(gMo*min) and 52% to 30 mmolH2/(gMo*min) and 65%, respectively. Combining with characterization methods such as X-ray diffraction (XRD), hydrogen temperature programmed reduction (H2-TPR), 1H-based solid-state nuclear magnetic resonance (1H MAS NMR), X-ray photoelectron spectroscopy (XPS), Raman spectra (RS), and transmission electron microscopy (TEM), we found that the hydroxyl concentration of the support increased after hydrogen peroxide treatment, which led to the strengthening of the force between the metal and the support, which was easy to form low-level and small-size MoS2, exposing more active sites, and further improving the catalytic activity. This method provides a new idea for hydrogen production by CH4/H2S reforming and the development of high-performance MoS2-based catalysts.

Integrating Target-Triggered Aptamer-Capped HRP@Metal-Organic Frameworks with a Colorimeter Readout for On-Site Sensitive Detection of Antibiotics.

Colorimetric analytical strategies exhibit great promise in developing on-site detection methods for antibiotics, while substantial recent research efforts remain problematic due to dissatisfactory sensitivity. Taking this into account, we develop a novel colorimetric sensor for in-field detection of antibiotics by using aptamer (Apt)-capped and horseradish peroxidise (HRP)-embedded zeolitic metal azolate framework-7 (MAF-7) (Apt/HRP@MAF-7) as target recognition and signal transduction, respectively. With the substrate 3,3',5,5'-tetramethylbenzidine (TMB)-impregnated chip attached on the lid, the assay can be conveniently operated in a tube and reliably quantified by a handheld colorimeter. Hydrophilic MAF-7 can not only prevent HRP aggregation but also enhance HRP activity, which would benefit its detection sensitivity. Besides, the catalytic activity of HRP@MAF-7 can be sealed through assembling with Apt and controllably released based on the bioresponsivity via forming target-Apt complexes. Consequently, a significant color signal can be observed owing to the oxidation of colorless TMB to its blue-green oxidized form oxTMB. As a proof-of-concept, portable detection of streptomycin was favorably achieved with excellent sensitivity, which is superior to most reported methods and commercial kits. The developed strategy affords a new design pattern for developing on-site antibiotics assays and immensely extends the application of enzyme embedded metal-organic framework composites.

Endophytic fungi, host genotype, and their interaction influence the growth and production of key chemical components of Dendrobium catenatum.

To examine how host plant genotype, endophytic fungal species, and their interaction may affect growth and key chemical content and composition in an important orchid species, we assessed four Dendrobium catenatum cultivars co-cultured with three fungi previously isolated from D. catenatum. Fungal endophytes (Tulasnella sp., Leptosphaeria microscopica, and Guignardia sp.) specifically affected the growth and chemical composition of the four cultivars. Fungal infection significantly increased certain growth traits, especially mid-stem thickness, stem biomass, stem polysaccharide and ethanol-soluble extractive content, and leaf flavonoid and phenol content. Presence or abundance of some key chemical components was also altered by fungal treatment. These increases and alterations were highly dependent on the host genotype. The findings of this study contribute to our understanding of Dendrobium and endophytic fungi interactions, and provide vital information for improving the development and use of endophytic fungi in D. catenatum breeding.

l-Pyroglutamic Acid-Modified CdSe/ZnS Quantum Dots: A New Fluorescence-Responsive Chiral Sensing Platform for Stereospecific Molecular Recognition.

Stereoselective recognition of amino acids is extremely important due to its high chirality-dependent interactions and physiological activities in life activities. We herein report a novel functionalized chiral fluorescent nanosensor prepared from surface modification of CdSe/ZnS quantum dots (QDs) with pyroglutamic acid derivatives, which could serve as a chiral recognition module for fluorescence detection of chiral molecules. The sensor exhibited a unique stereoselective fluorescence response to histidine (His), glutamate (Glu), and dihydroxyphenylalanine (Dopa) and had preferable response performance to l-enantiomers. The enantiomeric fluorescence difference ratios of His, Glu, and Dopa enantiomers were 3.90, 3.40, and 2.49, respectively. The mechanism for the enantiomeric fluorescence recognition was systematically studied through a fluorescence spectrum, fluorescence life, and density functional theory (DFT) calculation. Presumably, the different hydrogen bonding capacity of the chiral recognition module with two enantiomers mainly contributed to the difference in fluorescence signals. As a result, a broader application of the pyroglutamic acid derivative-coated QDs as a fluorescence-responsive chiral sensing platform for enantiomeric detection would be expected.

"Pomegranate-Like" Plasmonic Nanoreactors with Accessible High-Density Hotspots for in Situ SERS Monitoring of Catalytic Reactions.

Noble metal nanoparticles (NPs) have enabled surface-enhanced Raman scattering (SERS) for in situ monitoring of NPs-catalyzed reactions. However, it still remains a great challenge to ensure that analytes without plasmonic metal surface-affinity groups (such as thiol and amino groups) can be located into hotspots and detected by SERS. Here, we report a novel sacrificial template method for the fabrication of "pomegranate-like" plasmonic nanoreactors (PPNs), in which high-density embedded AuNPs simultaneously generated SERS enhancement and catalytic performance. Once the analytes entering PPNs are catalyzed and meanwhile located into the hotspots, in situ SERS monitoring of catalytic reactions can be achieved. The intense hotspots of localized electric fields of PPNs were evaluated by finite-difference time-domain simulation. By using PPNs as a substrate, SERS signals of molecules without Au surface-affinity groups were obtained, such as p-naphthoquinone and 4-nitrophenol. The PPNs showed high catalytic activities in the reduction of 4-nitrothiophenol to 4-aminothiophenol and 4-nitrophenol to 4-aminophenol, respectively. Besides, the SERS spectra of both 4-nitrophenol and 4-aminophenol during the reduction reaction of 4-nitrophenol with NaBH4 were first obtained, demonstrating their utilization in the detection of catalytic reactions.

Intelligent Platform for Simultaneous Detection of Multiple Aminoglycosides Based on a Ratiometric Paper-Based Device with Digital Fluorescence Detector Readout.

A digital fluorescence detector (DFD), a handheld fluorescence detection device, can convert the fluorescence signal of samples into the corresponding fluorescer concentration. Herein, by adopting a DFD as the readout, a novel intelligent platform was developed based on a ratiometric paper-based device (RPD) for multiple aminoglycoside detection. There are five layers and four parallel channels contained in the designed RPD, functioning as reagent storage, fluidic path control and signal processing, respectively. The rationale of this design lies in the fact that aptamer/graphitic carbon nitride nanosheet (Apt/g-C3N4 NS) modified layers can catalyze o-phenylenediamine to fluorescent 2,3-diaminophenazine (DAP) in the presence of H2O2. When Apt was removed from nanosheets via the Apt-target reaction, the peroxidase-like activity would be decreased, thus decreasing the production of DAP. All the changes of the fluorescence DAP signal can be read out using a portable DFD. Based on the DFD signal change related to the concentration of the target, a quantitative reaction platform was established. Furthermore, the sample flow and Apt-target reaction time can be reasonably regulated using the H2O2-cleavable hydrophobic compound modified layer placed between the target recognition region and detection region. Then, the practicality of this platform was verified through realizing sensitive analysis of streptomycin, tobramycin, and kanamycin simultaneously. Overall, with merits including portability and ease of operation, the platform shows great potential in on-site simultaneous detection of multiple targets, especially in resource-limited settings.

[Study on tissue culture system of Polygonatum cyrtonema].

In order to accelerate the breeding of the excellent seedlings of Polygonatum cyrtonema,tissue culture system of P. cyrtonema was established through the comprehensive regulation of key factors( leaf age,leaf location,basic media and plant growth regulators) and cytological basis of callus formation and differentiation was analyzed through paraffin section. The results showed that the 30-day-old leaf base explanton medium MS+6-BA 1. 50 mg·L~(-1)+2,4-D 0. 20 mg·L~(-1) had the highest induction rate( 80. 00%). The callus was initiated from cells on leaf base epidermis and near cortex,formed by the differentiation of middle vascular bundle cells. The optimal medium for adventitious bud differentiation was MS+ 6-BA 4. 00 mg·L~(-1)+ 2,4-D 0. 20 mg·L~(-1) with the differentiation rate of90. 33%,and the average number of buds was 5. 16. The adventitious buds had two origin types: exogenous and endogenous origin,formed by callus proximal cells and callus internal meristemoid. The adventitious bud proliferation medium was screened by orthogonal design,which determined the optimum combination was MS+ 6-BA 2. 00 mg·L~(-1)+NAA 0. 10 mg·L~(-1) and MS+ 6-BA 2. 00 mg·L~(-1)+NAA 0. 20 mg·L~(-1). The tubers with three leaves were cut and inoculated in the medium 1/2 MS+IBA 2. 00 mg·L~(-1),showing the highest rooting rate of 94. 00%. The rooting seedlings transplanted into the peat-vermiculite( 1 ∶ 1) matrix grew healthy and the survival rate was over 85. 00%. This research provided a novel solution for large-scale cultivation of P. cyrtonema seedling.

Separation of α-glucosidase inhibitors from Potentilla kleiniana Wight et Arn using solvent and flow-rate gradient high-speed counter-current chromatography target-guided by ultrafiltration HPLC-MS screening.

INTRODUCTION: Potentilla kleiniana Wight et Arn is widely used as a herbal medicine to treat type 2 diabetes. However, detailed information about its active compounds is lacking. OBJECTIVE: To develop an efficient method for the rapid screening and separation of α-glucosidase inhibitors from Potentilla kleiniana Wight et Arn. METHODOLOGY: Potential α-glucosidase inhibitors from Potentilla kleiniana Wight et Arn were rapidly screened out through ultrafiltration high-performance liquid chromatography mass spectrometry (HPLC-MS), and then followed by a target-guided high-speed counter-current chromatography (HSCCC) separation using two-phase solvent systems composed of n-hexane/ethyl acetate/methanol/water (1:10:1:10, v/v/v/v and 1:10:5:6, v/v/v/v), and adopting increasing flow-rate from 1.5 to 3.0 mL/min after 200 min. Their structures were identified by ultraviolet (UV), MS, proton nuclear magnetic resonance (1 H-NMR) and carbon-13 (13 C)-NMR, and their α-glucosidase inhibitory activities were assessed by in vitro assay. RESULTS: Five α-glucosidase inhibitors including gallic acid (25.7 mg, 98.2%, 1), brevifolincarboxylic acid (9.86 mg, 95.3%, 2), ethyl evifolincarboxylate (13.26 mg, 97.6%, 3), 3,3'-di-O-methylellagic acid-4'-O-ß-d-glucopyranoside (16.26 mg, 95.1%, 4), and 3,3'-di-O-methylellagic acid (10.54 mg, 96.8%, 5) were successfully purified from 250 mg n-butanol extract in a single run. Compounds 1, 2, 4 and 5 exhibited stronger α-glucosidase inhibitory activities[half maximal inhibition concentration (IC50 ) values at 173.41 ± 6.35, 323.46 ± 8.08, 44.63 ± 2.50, and 20.73 ± 2.56 µM, respectively] than acarbose (IC50 value at 332.12 ± 5.52 µM, reference compound). CONCLUSIONS: Notably, compounds 2-5 were reported in the Potentilla kleiniana Wight et Arn for the first time. The results indicated that the proposed method could be applied for the rapid screening and preparative separation of α-glucosidase inhibitors from a complex matrix.

[Cloning and function analysis of promoter of DcCDPK8 from Dendrobium catenatum].

DcCDPK8 involved in abiotic stress such as low temperature and signal transduction of hormones ABA and MeJA,but the transcriptional regulation is still unclear. In order to study the core promoter region of DcCDPK8 gene in Dendrobium catenatum and explore its transcriptional regulation mechanism,the DcCDPK8 gene promoter sequence was cloned by PCR from D. catenatum. Promoter sequence function was studied by fusion of 5 'terminal deletion and GUS gene. The results showed that the promoter sequence of DcCDPK8 gene has a low-temperature responsive element( LTR) between~(-1) 749 bp and-614 bp,two MeJA responsive elements between~(-1) 749 bp and-230 bp,and one ABA responsive elements between-614 bp and-230 bp. Three 5'-end different deletion fragments were constructed to fuse the eukaryotic expression vectors p BI121 with GUS,which were transformed into tobacco leaves. The GUS activity under cold stress treatment was DcCDPK8-p1>DcCDPK8-p2>DcCDPK8-p3. GUS activity under exogenous ABA induction was DcCDPK8-p1>DcCDPK8-p2>DcCDPK8-p3,and GUS activity under exogenous MeJA induction was DcCDPK8-p1>DcCDPK8-p2>DcCDPK8-p3. It is speculated that the ABA response element( ARE) in the promoter sequences of DcCDPK8 is positive regulatory role in response to exogenous ABA,the MeJA cis-acting element plays a negative role in response to exogenous MeJA.