This study deals with hierarchical porous carbons from bacterial cellulose (BC), having a layered structure for high-performance application, such as supercapacitor electrodes, fabricated from a composite monolith with unique microscopic/macroscopic morphology. A poly(methyl methacrylate) (PMMA)/BC composite monolith was first synthesized by thermally induced phase separation using ethanol and deionized water as solvents, where BC acts as the main carbon source as well as matrix and PMMA acts as the activator source producing the necessary activation material. Scanning electron microscopy analysis showed that a monolithic skeleton of PMMA was loaded uniformly on the nanofibers of BC to form a three-dimensional entangled structure of the PMMA skeleton and BC nanofibers, as observed in the microscopic view. Furthermore, the macroscopic two-dimensional layered structure of BC remained in the as-obtained composite. The specific surface area, structural features, and thermal stability were investigated by Brunauer–Emmett–Teller, X-ray diffraction, and thermogravimetric analysis studies. The resulting PMMA/BC composite was carbonized and activated by KOH at 850 °C. The electrochemical properties were characterized by cyclic voltammetry, galvanostatic charge–discharge, and electrochemical impedance spectroscopy showing that the carbonization product of the composite displayed a high specific capacitance of 266 F g–1 at a current density of 0.50 A g–1 and the energy density reached a maximum of 23.6 W h kg–1 at a power density of 200 W kg–1. Moreover, 95% of the capacitance was retained after 10,000 charge–discharge cycles, which implies exceptionally high cyclic stability. This compatible and excellent electrochemical performance of the composite, in terms of the energy density and capacitance retention, can be contributed to the characteristic porous structure of the precursor composite monolith. The present research delineates a new approach to fabricate high-performance supercapacitor materials and low-cost energy storage devices from inexpensive bioresources.Keywords: Bacterial cellulose; Composite; Monolith; Poly(methyl methacrylate); Supercapacitor;

•Thiol-maleimide click reaction was firstly adopted to prepare capillary monoliths.•Ultra-high column efficiency (180,500 N/m) was acquired on poly(BMI-co-3SH).•The tryptic digests of BSA and HeLa were positively identified in cLC–MS.One-step thiol-maleimide polymerization reaction was firstly adopted for direct preparation of polymeric monoliths via alkaline-catalyzed reaction of 4,4′-bis(maleimidophenyl)methane (BMI) and trimethylolpropane tris(3-mercaptopropionate) (3SH)/pentaerythriol tetra(3-mercaptopropionate) (4SH) in the presence of a small amount of triethylamine (TEA). The polymerization could be performed within 3 h, which was faster than thermal-initiated free radical polymerization. Two kinds of monoliths, poly(BMI-co-3SH) (marked as I) and poly(BMI-co-4SH) (marked as II), were characterized with scanning electron microscopy (SEM), attenuated total reflection Fourier-transformed infrared spectroscopy (ATR-FTIR), thermal gravimetric analysis (TGA) and mercury intrusion porosimetry (MIP). Satisfactory chromatographic separation ability and column efficiency were gained for analysis of small molecular compounds such as alkylbenzenes, polynuclear aromatic hydrocarbons (EPA 610) and phenols in reversed-phase capillary liquid chromatography (cLC). High column efficiency (180,500 N/m) for butylbenzene was acquired on poly(BMI-co-3SH) column I-2, which was higher than those on most reported polymeric monoliths. A retention-independent efficient performance of small molecules was obtained by plotting of plate height (H) of alkylbenzenes versus the linear velocity (u). A term values in van Deemter equation of I-2 (1.72-0.24 μm) and poly(BMI-co-4SH) column II-2 (5.28-4.14 μm) were smaller than those of traditional organic/hybrid monoliths. Finally, as a practical application, 53 and 2184 unique peptides from the tryptic digests of bovine serum albumin (BSA) and HeLa cell proteins were positively identified with poly(BMI-co-3SH) monolith in cLC–MS.

Protein glycosylations play important roles in various biological processes and in the disease progression of organisms. The development of specific enrichment materials and strategies before mass spectrometric analysis was a prerequisite to glycoproteomic analysis due to the difficulty caused by substoichiometric levels of glycoproteins. In this work, novel magnetic covalent organic frameworks (denoted as Fe3O4@TpPa-1) were first developed using only a two-step solvothermal reaction and then applied in the hydrophilic enrichment of glycopeptides. Sea urchin-type composites with super-paramagnetic properties were constructed by in situ growth of TpPa-1 covalent organic frameworks on the surface of magnetic nanoparticles. A total of 37 and 22 glycopeptides could be easily detected from IgG and HRP digests, respectively, by hydrophilic enrichment with the newly developed materials. An ultralow detection limit (28 fmol), satisfactory selectivity and high recovery could be achieved using Fe3O4@TpPa-1. The material's excellent enrichment performance was also demonstrated using glycopeptide analysis in real complex samples. Within three independent replicates, 228 glycopeptides corresponding to 114 glycoproteins could be detected from human serum digests, which is better than the performance obtained by commercial HILIC materials. The results suggest that covalent organic frameworks show potential for application in glycoproteomic studies.

Deep and efficient proteolysis is the critical premise in mass spectrometry-based bottom-up proteomics. It is difficult for traditional in-solution digestion to meet the requirement unless prolonged digestion time and enhanced enzyme dosage are employed, which makes the whole workflow time-consuming and costly. The abovementioned problems could be effectively ameliorated by anchoring many proteases on solid supports. In this work, covalent organic framework-coated magnetic graphene (MG@TpPa-1) was designed and prepared as a novel enzyme carrier for the covalent immobilization of trypsin with a high degree of loading (up to 268 μg mg−1). Profiting from the advantages of magnetic graphene and covalent organic frameworks, the novel trypsin bioreactor was successfully applied for the enzymatic digestion of a model protein with dramatically improved digestion efficiency, stability, and reusability. Complete digestion could be achieved in a time period as short as 2 min. For the digestion of proteins extracted from Amygdalus pedunculata, a total of 2833 protein groups were identified, which was slightly more than those obtained by 12 h of in-solution digestion (2739 protein groups). All of the results demonstrate that MG@TpPa-1-trypsin is an excellent candidate for sample preparation in a high-throughput proteomics analysis.

•A hydrophilic hybrid monolith was synthesized via thiol-ene click reaction.•The obtained columns exhibited good separation ability for neutral polar compounds.•The matrix was modified into hydrazide material for glycopeptides enrichment.A macroporous hydrophilic organic-silica hybrid monolithic column was synthesized via photoinitiated thiol-ene click polymerization reaction of 1-thioglycerol-modified polyhedral oligomeric vinylsilsesquioxane (vinylPOSS) and dithiothreitol (DTT) in a binary porogenic system consisting of tetrahydrofuran (THF) and dodecanol. 1-Thioglycerol was used to modify vinylPOSS in order to form a precursor with good solubility in the binary porogenic system. The influences of both the ratio of 1-thioglycerol/vinylPOSS and the porogenic solvents on the morphology and permeability of hybrid monoliths were studied in detail. The physical properties of hybrid monolith were characterized by scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) spectroscopy and nitrogen adsorption/desorption measurement. The chromatographic performance was evaluated by separation of neutral polar compounds in capillary liquid chromatography (cLC). The resulting column possessed homogeneous macroporous structure and showed hydrophilic interaction liquid chromatography (HILIC) separation mechanism with high efficiency of 65,000 N m−1 for formamide. Ultimately, the hybrid matrix was grafted with hydrazine groups and then exhibited the ability of glycopeptides enrichment.

•A novel covalent organic framework-based IMAC material was flexibly synthesized.•Titanium ions were directly immobilized in the nitrogen-rich frameworks of TpPa-2 COFs.•The enrichment performance was investigated and compared with commercial TiO2 materials.•All results provided high sensitivity and satisfactory selectivity for phosphopeptide enrichment.To date, plenty of new alternative materials for phosphopeptides enrichment prior to mass spectrometry (MS) analysis appear, especially immobilized metal ion affinity chromatography (IMAC) materials. The variable combinations with different metal ions, chelating ligands and solid supports offer full of optionality for IMAC. However, further improvement was predicted by the tedious and complex synthetic process. In this work, a novel covalent organic framework (COF)-based IMAC material (denoted TpPa-2-Ti4+) was prepared simply by direct immobilizing Ti (IV) into TpPa-2 COFs without any extra chelating ligands. The structure and composition of as-prepared composites were confirmed by PXRD, FT-IR and XPS, and a new flower-shaped Ti4+-IMAC with regular micro-nano hierarchical structure was observed in the SEM and TEM images. The obtained titanium (IV) ion-modified covalent organic frameworks demonstrated low limit of detection (4 fmol) and largely-satisfactory selectivity (β-casein: BSA=1:100) for phosphopeptide capturing from β-casein. Similarly, 18 and 17 phosphopeptides could be easily detected in the tryptic digest of α-casein or the digest mixture of α-casein and BSA (1:50). They were also successfully applied for enrichment of phosphopeptides from non-fat milk and HeLa cells with high sensitivity and satisfactory selectivity. All above results showed that the new titanium (IV) ion-modified covalent organic framework is expected to be a potential IMAC for phosphopeptide enrichment in large-scale phosphoproteomics studies.

•A highly crosslinked polymeric monolith was fast prepared with a multi-acrylate monomer as crosslinker within 5 min.•The addition of thiol eliminated the major obstacle of oxygen inhibition in the thiol-ene (acrylate/methacrylate) polymerization.•Poly(ODT-co-DPEPA) monolith exhibited efficient chromatographic performance for separation of alkylbenzenes and tryptic digest of proteins.A facile approach was exploited for fast preparation of polymer-based monoliths in UV-transparent fused-silica capillaries via “one-pot” photo-initiated thiol-acrylate polymerization reaction of dipentaerythritolpenta-/hexaacrylate (DPEPA) and 1-octadecanethiol (ODT) in the presence of porogenic solvents (1-butanol and ethylene glycol). Due to relative insensitivity of oxygen inhibition in thiol-ene free-radical polymerization, the polymerization could be performed within 5 min. The effects of composition of prepolymerization solution on the morphology and permeability of poly(ODT-co-DPEPA) monoliths were investigated in detail by adjusting the content of monomer and binary porogen ratio. The physical properties of poly(ODT-co-DPEPA) monoliths were characterized by Fourier transform infrared spectroscopy (FT-IR), mercury intrusion porosimetry (MIP) and nitrogen adsorption/desorption measurement. The evaluation of chromatographic performance was carried out by capillary liquid chromatography (cLC). The results indicated that the poly(ODT-co-DPEPA) monolith was homogeneous and permeable, and also possessed a typical reversed-phase retention mechanism in cLC with high efficiency (∼75,000 N m−1) for separation of alkylbenzenes. Eventually, the further separation of tryptic digest of proteins by cLC tandem mass spectrometry (cLC-MS/MS) demonstrated its potential in the analysis of biological samples.

One-dimensional (1D) bimetallic nanowire materials have attracted much more attention in electroanalysis because of their unique physical and chemical properties. In this work, we further extended the application field of the PdPt bimetallic alloy nanowires (PdPt BANWs) structure and successfully fabricated a novel PdPt BANWs-based electrochemical sensor for sensitive detection of ascorbic acid (AA). It was found that the PdPt BANWs on the electrode exhibited remarkable electrocatalytic activity toward AA oxidation and could be used for sensitive detection of AA in a wide linear range (0.01–0.97 mM) with a high sensitivity of 467.9 μA mM−1 cm−2. The detection limit is as lower as 0.2 μM (S/N = 3). Moreover, the electrochemical sensor also exhibited good selectivity, reproducibility and stability, and had been successfully applied to detection of AA in serum samples and commercial vitamin C tablets with satisfactory results.

A new method for determination of glutathione (GSH) was carried out with acetaminophen (AAP) mediation on a NiPd nanoparticle modified electrode. The as-prepared sensor exhibited excellent electrocatalytic activity for determining GSH with a good linear correlation with GSH concentration in a broad range from 0.5 to 3000 μM, a high detection sensitivity (481.69 μA mM−1 cm−2), and a low detection limit of 0.5 μM. The mechanism for GSH oxidation was also investigated by cyclic voltammetry and linear sweep voltammetry. In addition, the proposed sensor was also successfully employed to detect GSH in real samples.

•Novel yeast extract-stabilized fluorescent Cu NCs were synthesized.•The Cu NCs can be applied as a fluorescent turn-on sensor for detection of S2−.•A wide linear range is obtained from 0.02–0.8 µM, and detection limit of 10 nM.In this work, we have presented a novel strategy to utilize as-synthesized yeast extract-stabilized Cu nanoclusters (Cu NCs) for sensitive and selective detection of S2−. The fluorescence intensity of Cu NCs was enhanced significantly in the presence of both Na2S2O8 and S2−. By virtue of this specific response, a Cu NC-based fluorescent turn-on sensor was developed, which allows the detection of S2− in the range of 0.02–0.8 μM with a detection limit of 10 nM. The enhancing mechanism was also discussed based on fluorescence decay, transmission electron microscopy (TEM) and dynamic light scattering (DLS) studies, indicating that S2− enhanced the Cu NCs emission mainly through sulfide-induced aggregation of Cu NCs. Furthermore, we demonstrated the usability of the present approach for the detection of S2− in water samples, which illustrates its great potential for the environmental monitoring and water quality inspection fields.

•Analyze an edible plant in desert, compare with other five vegetables.•Investigate the gastrointestinal prokinetic efficacy of water extract of the plant.•Assess the nutritional and medicinal values of Pugionium cornutum (L.) Gaertn.•Develop its economic values as well as ecological values.Pugionium cornutum (L.) Gaertn. (PCG) is a desert plant with edible and medicinal value. The contents of proximate composition, amino acids and vitamins of fresh and pickled PCG were analyzed. PCG is rich in dietary fiber, protein and vitamins. PCG is a dietary source of potassium and calcium, with low levels of fat and sugar. PCG contains all the 18 hydrolyzed amino acids. Pickled PCG protein is a high quality protein. A large quantity of vitamins are lost during the pickling process. The type and number of mice dejections, gastric emptying and intestinal propulsion were investigated using the water extract of fresh and pickled PCG (WEFP and WEPP) to determine their gastrointestinal prokinetic efficacy. The low-dose WEFP and WEPP promoted the gastrointestinal dynamics and the WEFP and WEPP promoted gastrointestinal activity and act as nonviolent drugs. The results indicate that PCG has great potential as a new functional food source.

•High quality Cu2Se films prepared on electroless Cu coated p-Si by EC-ALD•The deposited Cu2Se films have good photoelectric properties.•A promising method for electrodepositing compound semiconductor films on p-SiCuprous selenide (Cu2Se) nanocrystalline thin films are grown onto electroless Cu coating on p-Si (100) substrates using electrochemical atomic layer deposition (EC-ALD), which includes alternate electrodeposition of Cu and Se atomic layers. The obtained films were characterized by X-ray diffraction (XRD), field emission scanning electronic microscopy (FE-SEM), FTIR, and open-circuit potential (OCP) studies. The results show the higher quality and good photoelectric properties of the Cu2Se film, suggesting that the combination of electroless coating and EC-ALD is an ideal method for deposition of compound semiconductor films on p-Si.

Carbon-supported PdNi (PdNi/C) and PdCo (PdCo/C) nanoparticles (NPs) were synthesized and modified on a glassy carbon electrode (GCE) to fabricate highly sensitive amperometric nitrite sensors. Cyclic voltammetry (CV) and an amperometric i–t curve were used to characterize the electrochemical behavior of the electrodes in the presence of nitrite. From the results, both the PdNi/C- and PdCo/C NPs-modified electrodes exhibited better electrochemical properties than the commercial Pd/C catalyst with equal metal content (10%). Moreover, both the PdNi and PdCo sensors exhibited remarkable sensitivity of 5.23 and 5.52 mA mM−1 cm−2, respectively. Interference studies showed that the modified electrodes exhibited excellent selectivity toward nitrite. In addition, the proposed sensors were applied to determine the nitrite content in several foods and moat water with satisfactory results.

A new spectrofluorimetric method for the determination of cytochrome c using spirocyclic rhodamine B hydrazide (RBH) as fluorogenic reagent in the presence of sodium dodecylbenzene sulfonate (SDBS) surfactant micelles was developed. The method was based on the reaction of cytochrome c with RBH, a colorless, nonfluorescent spirolactam of rhodamine B in SDBS micelles to give highly fluorescent rhodamine B and hence led to a large increase in fluorescence intensity. The dynamic range and detection limit for the determination of cytochrome c are 4.0–120 ng ml−1 and 0.87 ng ml−1 (3σ), respectively. The optimal conditions for the detection of cytochrome c were evaluated and the possible detection mechanism was also discussed.

•Refolding the recombinant histidine-tagged cdMMP-13 using size exclusion chromatography (SEC).•The catalytic domain of collagenase-3 is a 23 kDa protein.•Analysis the inhibitory activity of metal ions to cdMMP-13 in vitro.•K3[Fe(CN)6] exhibit cdMMP-13 inhibitory potential with a half maximal inhibitory concentration (IC50) of 1.3 μM.•Develop the medicinal value of K3[Fe(CN)6] for future drug screening.Collagenase-3 (MMP-13) inhibitors have attracted considerable attention in recent years and have been developed as a therapeutic target for a variety of diseases, including cancer. Matrix metalloproteinases (MMPs) can be inhibited by a multitude of compounds, including hydroxamic acids. Studies have shown that materials and compounds containing trivalent metal ions, particularly potassium hexacyanoferrate (III) (K3[Fe(CN)6]), exhibit cdMMP-13 inhibitory potential with a half maximal inhibitory concentration (IC50) of 1.3 μM. The target protein was obtained by refolding the recombinant histidine-tagged cdMMP-13 using size exclusion chromatography (SEC). The secondary structures of the refolded cdMMP-13 with or without metal ions were further analyzed via circular dichroism and the results indicate that upon binding with metal ions, an altered structure with increased domain stability was obtained. Furthermore, isothermal titration calorimetry (ITC) experiments demonstrated that K3[Fe(CN)6]is able to bind to MMP-13 and endothelial cell tube formation tests provide further evidence for this interaction to exhibit anti-angiogenesis potential. To the best of our knowledge, no previous report of an inorganic compound featuring a MMP-13 inhibitory activity has ever been reported in the literature. Our results demonstrate that K3[Fe(CN)6] is useful as a new effective and specific inhibitor for cdMMP-13 which may be of great potential for future drug screening applications.

Carbon-supported PdNi (PdNi/C) and PdCo (PdCo/C) nanoparticles (NPs) were synthesized and modified on a glassy carbon electrode (GCE) to fabricate highly sensitive amperometric nitrite sensors. Cyclic voltammetry (CV) and an amperometric i–t curve were used to characterize the electrochemical behavior of the electrodes in the presence of nitrite. From the results, both the PdNi/C- and PdCo/C NPs-modified electrodes exhibited better electrochemical properties than the commercial Pd/C catalyst with equal metal content (10%). Moreover, both the PdNi and PdCo sensors exhibited remarkable sensitivity of 5.23 and 5.52 mA mM−1 cm−2, respectively. Interference studies showed that the modified electrodes exhibited excellent selectivity toward nitrite. In addition, the proposed sensors were applied to determine the nitrite content in several foods and moat water with satisfactory results.

Protein glycosylations play important roles in various biological processes and in the disease progression of organisms. The development of specific enrichment materials and strategies before mass spectrometric analysis was a prerequisite to glycoproteomic analysis due to the difficulty caused by substoichiometric levels of glycoproteins. In this work, novel magnetic covalent organic frameworks (denoted as Fe3O4@TpPa-1) were first developed using only a two-step solvothermal reaction and then applied in the hydrophilic enrichment of glycopeptides. Sea urchin-type composites with super-paramagnetic properties were constructed by in situ growth of TpPa-1 covalent organic frameworks on the surface of magnetic nanoparticles. A total of 37 and 22 glycopeptides could be easily detected from IgG and HRP digests, respectively, by hydrophilic enrichment with the newly developed materials. An ultralow detection limit (28 fmol), satisfactory selectivity and high recovery could be achieved using Fe3O4@TpPa-1. The material's excellent enrichment performance was also demonstrated using glycopeptide analysis in real complex samples. Within three independent replicates, 228 glycopeptides corresponding to 114 glycoproteins could be detected from human serum digests, which is better than the performance obtained by commercial HILIC materials. The results suggest that covalent organic frameworks show potential for application in glycoproteomic studies.