Chameleon-like Response Mechanism of Gold-Silver Bimetallic Nanoclusters Stimulated by Sulfur Ions and Their Application in Visual Fluorescence Sensing.

Herein, 2-mercapto-5-benzimidazolesulfonate acid sodium salt dihydrate (MBZS)-protected gold-silver bimetallic nanoclusters, named MBZS-AuAg NCs, were synthesized. Interestingly, we found that MBZS-AuAg NCs solutions can exhibit different fluorescence color changes under sulfide stimulation. A series of modern analytical testing techniques were used to explore the interaction mechanism between MBZS-AuAg NCs and sulfide. Sulfide ions can not only cause MBZS-AuAg NCs to exhibit rich fluorescence color changes similar to those of a chameleon but also have four linear relationships between the response intensity and sulfide concentration. A wide-range sulfide fluorescence sensing platform was constructed based on four linear segments with different fluorescence color responses. This sensing platform can be directly used for the determination of S2- with a detection limit as low as 11 nM. The portable test paper based on MBZS-AuAg NCs can realize the visual and rapid detection of gaseous hydrogen sulfide with a detection limit of 100 ppb (v/v). The wide detection range of the proposed method not only allows it to be used as an alternative method for sulfide detection in environmental samples but also has potential applications in the rapid detection and early warning of hydrogen sulfide gas in industrial and mining scenarios.

Sensitive determination of bisphenols in environmental samples by magnetic porous carbon solid-phase extraction combined with capillary electrophoresis.

Bisphenol compounds exist widely in the environment and pose potential hazards to the environment and human health, which has aroused widespread concern. Therefore, there is an urgent need for an efficient and sensitive analytical method to enrich and determine trace bisphenols in environmental samples. In this work, magnetic porous carbon (MPC) was synthesized by one-step pyrolysis combined with a solvothermal method for magnetic solid-phase extraction of bisphenols. The structural properties of MPC were characterized by field emission scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, and saturation magnetization analysis. Its adsorption properties were evaluated by adsorption kinetics and adsorption isotherm studies. By optimizing the magnetic solid-phase extraction and capillary electrophoresis separation conditions, a capillary electrophoresis separation and detection method for four bisphenols was successfully constructed. The results showed that the detection limits of the proposed method for the four bisphenols were 0.71-1.65 ng/mL, the intra-day and inter-day precisions were 2.27-4.03% and 2.93-4.42%, respectively, and the recoveries were 87.68%-108.0%. In addition, the MPC could be easily recycled and utilized, and even if the magnetic solid-phase extraction was repeated 5 times, the extraction efficiency could still be kept above 75%.

Determination of trace bisphenols in milk based on Fe3O4@NH2-MIL-88(Fe)@TpPa magnetic solid-phase extraction coupled with HPLC.

Herein, a covalent organic framework (COF) was grown on a magnetic metal-organic framework (MOF) by a solvothermal method for the efficient extraction of bisphenols (BPs). The magnetic solid-phase extraction (MSPE) of four bisphenols (bisphenol A, bisphenol B, bisphenol AF and bisphenol C) was carried out without adjusting the pH and salt concentration. When 30 mg Fe3O4@NH2-MIL-88(Fe)@TpPa was used to adsorb for 25 min, 6 mL methanol was used to elute for 20 min, and the extract was detected by high-performance liquid chromatography (HPLC). The proposed method has a low detection limit of 0.011-0.036 ng mL-1, a wide linear range of 0.05-100 ng mL-1, and a correlation coefficient (R2) of 0.9980-0.9998. The intra-day and inter-day precisions are 0.74-2.54% and 1.68-3.72%, respectively. Bisphenol A was determined by applying the proposed method to the determination of actual milk samples. The standard addition experiment showed that the relative recovery of the four bisphenols was 85.70-119.7%. Pseudosecond-order, first-order, Langmuir and Freundlich models were applied to explore the adsorption characteristics of Fe3O4@NH2-MIL-88(Fe)@TpPa. In general, the established Fe3O4@NH2-MIL-88(Fe)@TpPa-MSPE-HPLC-UV method exhibits attractive sensitivity, simple manipulation, and excellent reusability, and it has excellent prospects for the detection of trace BPs in complex milk matrices.

Fabrication of Two Luminescent Imidazolyl Cadmium-Organic Frameworks and Their Sensing Mechanism for 2,6-Dichloro-4-nitroaniline.

2,6-Dichloro-4-nitroaniline, alias dicloran (DCN), is a broad-spectrum pesticide that can cause irreversible damage to the human body. Therefore, it is of great significance to develop a technology for the rapid and convenient detection of DCN. Luminescent metal organic frameworks have attracted extensive attention in the field of sensing and detection due to their excellent optical properties. In this study, two kinds of 2D Cd-MOFs (CdMOF-1 and CdMOF-2) were developed for the detection of residual DCN in the environment. Both CdMOFs exhibit excellent solvent and acid-base stability and can respond to DCN quickly and sensitively in a short time (30 s). CdMOFs not only have good selectivity and anti-interference toward DCN but also have good reusability. Under the conditions of DCN concentrations of 1-15 and 0.3-30 µM, the change in fluorescence intensity of CdMOF-1 and CdMOF-2 showed a good linear relationship with DCN concentration (R2 = 0.999/0.991), and the detection limits were 0.36 and 0.12 µM, respectively. Through ultraviolet-visible absorption spectroscopy (UV-Vis), X-ray photoelectron spectroscopy, fluorescence lifetime, and density functional theory calculations, it is revealed that the fluorescence quenching mechanisms of DCN for two kinds of Cd-MOFs are competitive absorption and photoinduced electron transfer, and there may be a weak π-π interaction. Finally, it is demonstrated that by using two types of fluorescent CdMOFs to make the fluorescent test paper and detect actual soil, these can be applied to the actual scene and achieve onsite real-time detection.

Determination of nitroimidazole antibiotics based on dispersive solid-phase extraction combined with capillary electrophoresis.

For a long time, the detection of nitroimidazole antibiotics (NIABs) has been a research focus in environmental analytical chemistry. In this work, a novel technique for the analysis of nitroimidazoles was established based on capillary electrophoresis (CE). UiO-66, synthesized using a solvothermal method, was utilized as an adsorbent in the dispersive solid-phase extraction (DSPE) of five different NIABs. The separation and detection of NIABs in environmental water samples were accomplished using the CE diode array detection method. The optimal extraction conditions were obtained after systematically studying the effects of adsorption time, the amount of extractant, and elution solvent on extraction efficiency. According to the results of the study, the limit of detections of the five NIABs were between 16 and 97 ng/mL, the relative standard deviations were between 0.32% and 0.55%, and the spike recoveries were between 87.43% and 104.8%. This study presents a novel technique for measuring NIABs in complex water samples.

A gold-silver bimetallic nanocluster-based fluorescent probe for cysteine detection in milk and apple.

Noble metal nanoclusters have attracted much attention due to their excellent optical properties. In the present work, a silver-doped gold-based bimetallic nanoclusters (Au/Ag NCs) were reasonably designed and prepared through a one-pot method by using 5-mercapto-1-tetrazolea-acetic acid sodium salt (MTAS) as a protector and capping agent. In comparison with the monometallic nanoclusters, Ag-doped metallic nanoclusters show better performance. The particle size of the MTAS-Au/Ag NCs is slightly larger than that of the undoped Au NCs by about 1.86 ± 0.5 nm, and the MTAS-Au/Ag NCs exhibit an emission peak at 635 nm with a quantum yield (QY) of 3.05%. The presence of cysteine (Cys) induces efficient quenching of the photoluminescence of the obtained Au/Ag NCs, achieving the sensitive detection of Cys with a detection limit of 16 nM. The fluorescence quenching rate of the nano fluorescent probe has a linear relationship with the cysteine concentration. Under the best detection conditions, the linear range for Cys detection with MTAS-Au/Ag NCs as a probe is 0.05-25.0 µM. Moreover, this probe has been successfully applied to the analysis of Cys in milk and apples, and a satisfactory recovery rate has been obtained, indicating the effectiveness and reliability of the sensor system for the detection of actual samples.

Construction of hierarchically porous monoliths from covalent organic frameworks (COFs) and their application for bisphenol A removal.

Subject to synthetic conditions, covalent organic frameworks (COFs) are usually in powder form. Herein, taking an azine-linked COF as an example, detailed characterizations indicated that accessible aldehyde groups and hydrazine groups (CNNH2, 88 µmol g-1) concurrently existed on its surface. Intrigued by such feature, we have developed an approach based on ring-opening polymerization to shape COF powder into monoliths. The crystallinity and micropore of COF in monoliths were well remained, meanwhile, the ring-opening polymerization remarkably generated macropores ranging from 0.43 to 3.51 µm, indicating a hierarchically porous structure. The BET surface area of resultant monoliths with different COF mass fractions of 16%, 28% and 43% ranged from 105 to 281 m2 g-1. Due to the π-π interaction and hydrogen bond interaction, COF-based monoliths exhibited strong retention and rapid adsorption for bisphenol A (BPA) in aqueous medium. When 29 mL BPA solution (22.8 mg L-1) passed through COF-based monolith (28%), the adsorption capacity was up to 61.3 mg g-1. Furthermore, the COF-based monolith demonstrated excellent cycle use for catalyzing Suzuki-Miyaura coupling reaction after being coordinated with palladium acetate.

Palladium catalyst imbedded in polymers of intrinsic microporosity for the Suzuki-Miyaura coupling reaction.

Polymers of intrinsic microporosity (PIMs) are porous polymers with rigid ladder-type chain structures. Synthesizing these polymers usually involves the step polymerization of two types of monomer, namely, active fluorine-substituted aromatic ring monomers and phenolic monomers. Herein, we report a new PIMs preparation method using self-synthesized fluorinated monomers and common monomer 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl spirobisindane. The fluorinated monomers were synthesized through the imidization of tetrafluorophthalic anhydride and aromatic diamines. The resulting PIMs served as a support for palladium, with the formed catalyst showing potential for application in the Suzuki-Miyaura coupling reaction.

SH2 Superbinder Modified Monolithic Capillary Column for the Sensitive Analysis of Protein Tyrosine Phosphorylation.

In this study, we present a method to specifically capture phosphotyrosine (pTyr) peptides from minute amount of sample for the sensitive analysis of protein tyrosine phosphorylation. We immobilized SH2 superbinder on a monolithic capillary column to construct a microreactor to enrich pTyr peptides. It was found that the synthetic pTyr peptide could be specifically enriched by the microreactor from the peptide mixture prepared by spiking of the synthetic pTyr peptide into the tryptic digests of α-casein and ß-casein with molar ratios of 1:1000:1000. The microreactor was further applied to enrich pTyr peptides from pervanadate-treated HeLa cell digests for phosphoproteomics analysis, which resulted in the identification of 796 unique pTyr sites. In contrast, the conventional SH2 superbinder-based method identified 41 pTyr sites for the same sample, only 5.2% of the number achieved by the microreactor. Finally, this microreactor was also applied to analyze the pTyr in Shc1 complex, an immunopurified protein complex, which resulted in the identification of 15 pTyr sites. Together, this technique is best fitted to analyze the pTyr in minute amount of sample and will have broad application in fields where only a limited amount of sample is available.

Tailor-Made Stable Zr(IV)-Based Metal-Organic Frameworks for Laser Desorption/Ionization Mass Spectrometry Analysis of Small Molecules and Simultaneous Enrichment of Phosphopeptides.

Although thousands of metal-organic frameworks (MOFs) have been fabricated and widely applied in gas storage/separations, adsorption, catalysis, and so on, few kinds of MOFs have been used as adsorption materials while simultaneously serving as matrixes to analyze small molecules for laser desorption/ionization mass spectrometry (LDI-MS). Herein, a new concept is introduced to design and synthesize MOFs as both adsorption materials and matrixes according to the structure of ligands and common matrixes. The proof of concept design was demonstrated by selection of 2,5-pyridinedicarboxylic acid (PDC) and 2,5-dihydroxyterephthalic acid (DHT) as ligands for synthesis of MOFs. Two Zr(IV)-based MOFs of UiO-66-PDC and UiO-66-(OH)2 were synthesized and applied for the first time as new matrixes for analysis of small molecules by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). Both of them showed low matrix interferences, high ionization efficiency, and good reproducibility when used as matrixes. A variety of small molecules, including saccharides, amino acids, nucleosides, peptides, alkaline drugs, and natural products, were analyzed. In addition, UiO-66-(OH)2 exhibited potential for application in the quantitative determination of glucose and pyridoxal 5'-phosphate. Furthermore, thanks to its intrinsically large surface area and highly ordered pores, UiO-66-(OH)2 also showed sensitive and specific enrichment of phosphopeptides prior to MS analysis. These results demonstrated that this strategy can be used to efficiently screen tailor-made MOFs as matrixes to analyze small molecules by MALDI-TOF-MS.

Improving permeability and chromatographic performance of poly(pentaerythritol diacrylate monostearate) monolithic column via photo-induced thiol-acrylate polymerization.

A simple approach was developed for rapid preparation of polymeric monolithic columns in UV-transparent fused-silica capillaries via photoinitiated thiol-acrylate polymerization of pentaerythritol diacrylate monostearate (PEDAS) and trimethylolpropane tris(3-mercaptopropionate) (TPTM) within 10min, in which the acrylate homopolymerized and copolymerized with the thiol simultaneously. The morphology, permeability and chromatographic performance of the resulting poly(PEDAS-co-TPTM) monoliths were studied. It could be observed from SEM that the morphology of poly(PEDAS-co-TPTM) monolith was rather different from that of poly(PEDAS) monolith, which was fabricated via photo-induced free radical polymerization using PEDAS as the sole monomer. Compared with poly(PEDAS) monolith, poly(PEDAS-co-TPTM) monolith possessed better permeability when they were fabricated under the same preparation conditions. By adjusting the composition of porogenic solvents, poly(PEDAS-co-TPTM) monolith exhibited lower plate heights (15.7-17.7µm) than poly(PEDAS) monolith (19.1-37.9µm) in µLC. In addition, 66 unique peptides were positively identified on poly(PEDAS-co-TPTM) monolith when tryptic digest of four proteins was separated by µLC-MS/MS, demonstrating its potential in proteome analysis.

Preparation of well-controlled three-dimensional skeletal hybrid monoliths via thiol-epoxy click polymerization for highly efficient separation of small molecules in capillary liquid chromatography.

Two kinds of hybrid monoliths were first prepared via thiol-epoxy click polymerization using a multi-epoxy monomer, octaglycidyldimethylsilyl POSS (POSS-epoxy), and two multi-thiols, trimethylolpropanetris(3-mercaptopropionate) (TPTM) and pentaerythritoltetrakis(3-mercaptopropionate) (PTM), respectively, as the precursors. The resulting two hybrid monoliths (assigned as POSS-epoxy-TPTM and POSS-epoxy-PTM) not only possessed high thermal, mechanical and chemical stabilities, but also exhibited well-controlled 3D skeletal microstructure and high efficiency in capillary liquid chromatography (cLC) separation of small molecules. The highest column efficiency reached 182,700N/m (for butylbenzene) on the monolith POSS-epoxy-PTM at the velocity of 0.75mm/s. Furthermore, the hybrid monolith POSS-epoxy-PTM was successfully applied for cLC separations of various samples, not only standard compounds such as alkylbenzenes, PAHs, phenols and dipeptides, as well as intact proteins, but also complex samples of EPA 610 and BSA digest.

A novel polymeric monolith prepared with multi-acrylate crosslinker for retention-independent efficient separation of small molecules in capillary liquid chromatography.

Low column efficiency for small molecules in reversed-phase chromatography is a major problem commonly encountered in polymer-based monoliths. Herein, a novel highly crosslinked porous polymeric monolith was in situ prepared by using a multi-acrylate monomer, dipentaerythritol penta-/hexa-acrylate (DPEPA), as crosslinker, which copolymerized with lauryl methacrylate (LMA) as functional monomer in a UV-transparent fused-silica capillary via photo-initiated free-radical polymerization within 5 min. The mechanical stability and permeability of the resulting poly(LMA-co-DPEPA) monolith were characterized in detail. One series of highly crosslinked poly(LMA-co-DPEPA) columns were prepared with relatively higher content of crosslinker (63.3%) in the precursor. Although they exhibited lower permeability, high column efficiency for alkylbenzenes was acquired in cLC, and the minimum plate height (column B) was in the range of 6.04-9.00 µm, corresponding to 111,000-165,000 N m(-1). Meanwhile, another series of poly(LMA-co-DPEPA) columns prepared with relatively lower content of crosslinker (52.7%) in the precursor exhibited higher permeability, but the minimum plate height (column E) was relatively low in the range of 10.75-20.04 µm for alkylbenzenes, corresponding to 50,000-93,000 N m(-1). Compared with common poly(LMA-co-EDMA) columns previously reported, the highly crosslinked poly(LMA-co-DPEPA) columns using a multi-acrylate monomer as crosslinker possessed remarkably high column efficiency for small molecules in cLC. By plotting of plate height (H) of alkylbenzenes versus the linear velocity (u) of mobile phase, the results revealed a retention-independent efficient performance of small molecules in the isocratic elution, indicating that the use of multi-functional crosslinker possibly prevents the generation of gel-like micropores in the poly(LMA-co-DPEPA) monolith, reducing the mass transfer resistance (C-term).

Fast preparation of a highly efficient organic monolith via photo-initiated thiol-ene click polymerization for capillary liquid chromatography.

A novel organic monolith was firstly prepared in a UV-transparent fused-silica capillary by a single-step approach via photo-initiated thiol-ene click polymerization reaction of 1,2,4-trivinylcyclohexane (TVCH) and pentaerythriol tetra(3-mercaptopropionate) (4SH) within 10min. The effects of both composition of prepolymerization solution and polymerization time on the morphology and permeability of monolithic column were investigated in detail. Then, the optimal condition was acquired to fabricate a homogeneous and permeable organic monolith. The chemical groups of the monolithic column were confirmed by Fourier transform infrared spectroscopy (FT-IR). The SEM graphs showed the organic monolith possessed a uniform porous structure, which promotes the highest column efficiency of ∼133,000 plates per meter for alkylbenzenes at the linear velocity of 0.65mm/s in reversed-phase liquid chromatography. Finally, the organic monolithic column was further applied for separation of basic compounds, pesticides and EPA610, indicating satisfactory separation ability.

The drivers of corporate environment inputs: Based on neo-institution theory evidence from Chinese listed biological and other companies.

From corporate internal governance structure and external institutional environment, this study uses a legitimacy perspective of intuitional theory to analyze the main influence factors on corporate environmental protection inputs and propose some hypotheses. With the establishment of empirical models, it analyzes the data of 2004-2009 listed biological and other companies in China to test the hypotheses. The findings are concluded that in internal institutional environment, the nature of the controlling shareholder, the proportion of the first shareholder in the ownership structure, the combination of chairman and general manager in board efficiency and the intensity of environmental laws and regulations of the industry in external institutional environment have an significant impact on the behaviors of corporate environmental protection inputs.