Spontaneous exciton dissociation in organic photocatalyst under ambient conditions for highly efficient synthesis of hydrogen peroxide.

SignificanceHydrogen peroxide is a highly competitive ready-to-use product for solar energy transformation. Nevertheless, the contemporary photosynthetic systems are not efficient enough, due to severe charge recombination caused by high activation energy and binding energy of the exciton. Herein, we achieve spontaneous exciton dissociation at room temperature. Moreover, the photosynthesis of H2O2 reaches between 9,366 and 12,324 µmol·g-1 from 9 AM to 4 PM in ambient conditions, that is, sunlight irradiation, real water including fresh water and seawater, room temperature, and open air. The ultrahigh photocatalytic efficiency in ambient conditions allows the solar-to-chemical conversion in a real cost-effective and sustainable way, which represents an important step toward real applications.

On-Site Ratiometric Analysis of UO22+ with High Selectivity.

Uranyl ions (UO22+) are recognized as important indicators for monitoring sudden nuclear accidents. However, the interferences coexisting in the complicated environmental matrices impart serious constraints on the reliability of current on-site monitoring methods. Herein, a novel ratiometric method for the highly sensitive and selective detection of UO22+ is reported based on a [Eu(diaminoterephthalic acid)] (Eu-DATP) metal-organic framework. Benefiting from the unique chemical structure of Eu-DATP, energy transfer from DATP to UO22+ was enabled, resulting in the up-regulated fluorescence of UO22+ and the simultaneous down-regulated fluorescence of Eu3+. The limit of detection reached as low as 2.7 nM, which was almost 2 orders of magnitude below the restricted limit in drinking water set by the United States Environmental Protection Agency (130 nM). The Eu-DATP probe showed excellent specificity to UO22+ over numerous interfering species, as the intrinsic emissions of UO22+ were triggered. This unprecedentedly high selectivity is especially beneficial for monitoring UO22+ in complicated environmental matrices with no need for tedious sample pretreatment, such as filtration and digestion. Then, by facilely equipping a Eu-DATP-based sampler on a drone, remotely controlled sampling and on-site analysis in real water samples were realized. The concentrations of UO22+ were determined to be from 16.5 to 23.5 nM in the river water of the Guangzhou downtown area, which was consistent with the results determined by the gold-standard inductively coupled plasma mass spectrometry. This study presents a reliable and convenient method for the on-site analysis of UO22+.

A solar-to-chemical conversion efficiency up to 0.26% achieved in ambient conditions.

Artificial photosynthesis in ambient conditions is much less efficient than the solar-to-biomass conversion (SBC) processes in nature. Here, we successfully mimic the NADP-mediated photosynthetic processes in green plants by introducing redox moieties as the electron acceptors in the present conjugated polymeric photocatalyst. The current artificial process substantially promotes the charge carrier separation efficiency and the oxygen reduction efficiency, achieving a photosynthesis rate for converting Earth-abundant water and oxygen in air into hydrogen peroxide as high as 909 µmol⋅g-1⋅h-1 and a solar-to-chemical conversion (SCC) efficiency up to 0.26%. The SCC efficiency is more than two times higher than the average SBC efficiency in nature (0.1%) and the highest value under ambient conditions. This study presents a strategy for efficient SCC in the future.

Highly efficient photosynthesis of hydrogen peroxide in ambient conditions.

Photosynthesis of hydrogen peroxide (H2O2) in ambient conditions remains neither cost effective nor environmentally friendly enough because of the rapid charge recombination. Here, a photocatalytic rate of as high as 114 µmol⋅g-1⋅h-1 for the production of H2O2 in pure water and open air is achieved by using a Z-scheme heterojunction, which outperforms almost all reported photocatalysts under the same conditions. An extensive study at the atomic level demonstrates that Z-scheme electron transfer is realized by improving the photoresponse of the oxidation semiconductor under visible light, when the difference between the Fermi levels of the two constituent semiconductors is not sufficiently large. Moreover, it is verified that a type II electron transfer pathway can be converted to the desired Z-scheme pathway by tuning the excitation wavelengths. This study demonstrates a feasible strategy for developing efficient Z-scheme photocatalysts by regulating photoresponses.

Two-Dimensional Conductive Metal-Organic Framework for Small-Molecule Sensing in Aqueous Solution.

Two-dimensional (2D) conductive metal-organic frameworks (cMOFs) have emerged as powerful transducers for electrochemical sensing. However, electrochemical sensing in aqueous solutions remains at a very early stage for 2D cMOFs. Herein, the interfacial capacitances of a 2D cMOF are utilized for electrochemical sensing for the first time. Various redox-innocent compounds along with redox-active compounds in aqueous solutions are successfully detected based on the responses of two capacitance peaks at low voltages. The quantitative sensitivity to ascorbic acid is even an order of magnitude higher than the previous voltammetric method. Further investigation demonstrates that the responses are rooted in the pseudocapacitances of the 2D cMOF, i.e., the transitions among the multiple redox states of the ligands. The analytes are suggested to alert the d-p conjugation and exchange electrons with the 2D cMOF. These deep insights in response mechanisms represent an important step for promoting the application of 2D cMOFs in chemical sensing.

Noncovalent Tagging for Identifying Unknown Contaminants of Specific Bioactivity in Environmental Water.

Identifying contaminants of specific bioactivities from complicated environmental matrices remains costly and time-consuming, as it requires us to not only resolve their structures but also determine their bioactivities. Herein, a novel noncovalent tagging method is integrated in mass spectrometry for identifying unknown contaminants that target dopamine (DA) receptors. Via proteolysis of bovine serum albumin, a stereoselective hexapeptide (ACFAVE) is selected for noncovalently tagging the contaminants that possess the stereostructural characteristics of binding to DA receptors. The tagged contaminants can be readily distinguished from the coexisting species for subsequent structural analysis based on the tagging-induced shifts of the mass-to-charge ratios. Thus, both bioactivity evaluation and structure analysis are accomplished via mass spectrometry. By using this method, 1,3-diphenylguanidine (DPG), a widely used additive in rubber and plastics, is successfully identified out of 2495 features detected in the Pearl River water, with its concentration determined as only 9.8 µg L-1. Furthermore, DPG is confirmed as a potential disrupter to the DA receptors via a simulated docking experiment, which has not been reported before. The present noncovalent tagging method provides a cost-effective and time-efficient way of identifying bioactive molecules in complicated matrices. And proteolysis of proteins is promising for developing more taggants with other desired stereoselectivities in the future.

Novel solid-phase microextraction fiber coatings: A review.

The materials used for the fabrication of solid-phase microextraction fiber coatings in the past five years are summarized in the current review, including carbon, metal-organic frameworks, covalent organic frameworks, aerogel, polymer, ionic liquids/poly (ionic liquids), metal oxides, and natural materials. The preparation approaches of different coatings, such as sol-gel technique, in-situ growth, electrodeposition, and glue methods, are briefly reviewed together with the evolution of the supporting substrates. In addition, the limitations of the current coatings and the future development directions of solid-phase microextraction are presented.

Facile Synthesis of a Fluorinated-Squaramide Covalent Organic Framework for the Highly Efficient and Broad-Spectrum Removal of Per- and Polyfluoroalkyl Pollutants.

The escalating contamination by per- and polyfluoroalkyl substances (PFAS) has become an urgent issue in recent years, and the structural diversity of PFAS is the major challenge for effective pollution control. Herein, we take the intrinsic advantages of squaramide and prepare a new two-dimensional covalent organic framework (FSQ-1) that exhibits broad-spectrum PFAS affinity. The tailor-made linker forges hydrogen-bond donors, hydrogen-bond acceptors, and fluorophilic segments into one framework. The obtained material exhibits multipoint and multitype affinity to PFAS with different structures, by which high-efficient and broad-spectrum removal of various PFAS can be simultaneously achieved. Notably, the thermodynamic profiles provided by isothermal titration calorimetry (ITC) experiments further illustrate the underlying mechanism of the broad-spectrum affinity. FSQ-1 can also be applied for efficient PFAS extraction in trace-level PFAS analysis.

Noncovalently Tagged Gas Phase Complex Ions for Screening Unknown Contaminant Metabolites in Plants.

Screening the metabolites of emerging organic contaminants (EOCs) from complicated biological matrices is an important but challenging task. Although stable isotope labeling (SIL) is frequently used to facilitate the identification of contaminant metabolites from redundant interfering components, the isotopically labeled reagents are expensive and difficult to synthesize, which greatly constrains the application of the SIL method. Herein, a new online noncovalent tagging method was developed for screening the metabolites of 1H-benzotriazol (BT) based on the characteristic structural moieties reserved in the metabolites. By selecting ß-cyclodextrin (ß-CD) as a macrocyclic tagging reagent, metabolites with the reserved moiety were expected to exhibit a characteristic shift of the mass-to-charge ratio (Δm/z = 1134.3698) after being noncovalently tagged by ß-CD. Based on the characteristic mass shift, the suspected features were reduced by 1 order of magnitude, as numerous interfering species that could not be effectively tagged by ß-CD were excluded. From these suspected features, two metabolites of BT that have not been reported before were successfully screened out. The significant characteristic mass shift caused by the noncovalent tagging method is easier to identify with more confidence than the previously reported SIL method. Besides, noncovalent tagging reagents can be much more accessible and less expensive than isotopically labeled reagents. Hence, this online noncovalent tagging method can be an intriguing alternative to the conventional SIL method.

Polymer Ligand-Sensitized Lanthanide Metal-Organic Frameworks for an On-Site Analysis of a Radionuclide.

Herein, a new strategy to increase the sensitivity of a lanthanide metal-organic framework (Ln-MOF) to UO22+ was proposed by using polymeric ligands. By utilizing [Tb(1,3,5-benzenetrisbenzoate)]n (Tb-TBT) MOF as the host, preloaded 2-vinyl terephthalic acid (VTP) was polymerized in situ, which produced a novel fluorescent composite denoted as PVTP⊂Tb-TBT. Benefiting from the coordination of PVTP to the Tb nodes, the polymeric chains performed both as molecular scaffolds that improved the water stability of the framework and as additional antennae that sensitized the photoluminescence of the Tb nodes. More importantly, the detection sensitivity and selectivity of PVTP⊂Tb-TBT to UO22+ were much improved compared to those of Tb-TBT. Detailed characterizations indicated that the incorporation of PVTP efficiently enriched UO22+ in the probe, which promoted the energy dissipation to UO22+. Besides, UO22+ was also supposed to release PVTP from PVTP⊂Tb-TBT and, thus, exposed the open metal sites to water molecules, which interrupted the sensitization effect of PVTP and induced a nonradiative energy dissipation. A limit of detection (LOD) as low as 0.75 nm was recorded by suspending the PVTP⊂Tb-TBT probe in a water sample, far below the limit in drinking water set by the United States Environmental Protection Agency (130 nm). Furthermore, a remotely controlled sampling and an on-site analysis of real water samples were realized by facilely loading PVTP⊂Tb-TBT on thin films (TFs). The LOD for UO22+ was 2.5 nm by using the TFs. This study reports a new strategy for boosting the sensitivity and selectivity of Ln-MOF to monitor UO22+ and expands the application of the strategy to an on-site analysis.

Graphene Oxide-Supported Lanthanide Metal-Organic Frameworks with Boosted Stabilities and Detection Sensitivities.

The photoluminescent (PL) properties of lanthanide metal-organic frameworks (Ln-MOFs) are intrinsically subtle to water molecules, which remains the major challenge that severely limits their applications as fluorescent probes in aqueous samples. Herein novel composite fluorescent probes were prepared by growing Ln-MOFs (Tb-MOF, Eu-MOF, and Tb/Eu-MOF) on carboxylated porous graphene oxide (PGO-COOH). The 3D thorny composites presented significantly longer fluorescent lifetimes and higher quantum yields than that of the bare Ln-MOFs and exhibited long-term PL stabilities in aqueous samples up to 15 days. The stable and improved PL properties demonstrated that the highly hybrid composite structures protected the MOF components from the adverse effects of water. Furthermore, the unexpected antenna effect of the PGO-COOH substrate on Ln3+ was supposed to be another reason for the improved PL properties. The composites present ultralow detection limits as low as 5.6 nM for 2,4-dinitrotoluene and 2.3 nM for dipicolinic acid as turn-off and ratiometric fluorescent probes, respectively, which was attributed to the incoporation of PGO-COOH that dramatically enahnced inner filter effects and effectively protected the energy transfer process in the MOF components from the interference of the surrounding water. This work presents an effective strategy for creating ultrasensitive and stable fluorescent probes based on Ln-MOFs for applications in aqueous samples.

Dynamic changes in human HLA-DRA gene expression and Th cell subsets in sepsis: Indications of immunosuppression and associated outcomes.

BACKGROUND: Sepsis is a life-threatening disease that is an immune disorder response that causes multiple organ dysfunction. In this study, we investigated the dynamic changes in mRNA expression of HLA-DRA gene and the specific transcription factor of helper T cell subsets to explore long-term immunophenotyping and its relationship with prognosis. METHODS: Seventy-eight sepsis patients and twelve healthy controls were recruited in this study. Blood samples were collected at eight-time points during their septic course and were assayed for the gene expression of HLA-DRA and T helper cell subset-specific transcription factors (T-bet: Th1, GATA3: Th2, Foxp3: Treg, RORC: Th17). RESULTS: The levels of HLA-DRA in survivors gradually increased but were maintained at lower levels in non-survivors. The specific transcription factor of Th1 and Th2 cells, T-bet and GATA-3 were significantly lower in sepsis patients than in normal controls, and the non-survivors showed significantly lower levels than the survivors (P < .05). RORC and FOXP3, the specific transcription factor of Treg and Th17 were significantly higher in survivors than in non-survivors and normal controls (P < .05). T-bet and GATA-3 had a linear correlation with HLA-DRA expression (P < .01). CONCLUSIONS: The dynamic changes in HLA-DRA expression in peripheral blood could accurately reflect the immune status of sepsis patients, and the reduction in HLA-DRA may be an important reason for abnormal T cell differentiation. The sustained low levels of the Th cell subsets (Th1 and Th2) suggest the suppression of adaptive immunity, and this persistent immunosuppression may be the leading cause of death in septic patients.

Determination of the mass transfer coefficients in direct immersion solid-phase microextraction.

Diffusion of the analytes across the diffusion boundary layers and subsequently through the fiber coatings determines the extraction kinetics of solid-phase microextraction in aqueous matrices. Besides, the matrix effects can distort the behaviors of the analytes transferring across the diffusion boundary layers. However, these processes were always studied via certain simplification, which often left the mass transfer through the fiber coatings unconsidered and the matrix effects partially investigated. Herein, a comprehensive study on the mass transfer processes in direct immersion solid-phase microextraction was presented. Under different agitation speeds, it was determined that the mass transfer coefficients across the diffusion boundary layers were three to six orders larger than those through the fiber coatings. However, the mass transfer across the diffusion boundary layers was generally the major rate-limiting step. In addition, the shuttle effect and the barrier effect, which were responsible for accelerating and retarding the extraction kinetics, respectively, were found to be the dominant matrix effect alternately under different agitation speeds. This study comprehensively illustrated the major rate-limiting step and the dominant matrix effects through recording the mass transfer coefficients.

Exosomes derived from plasma of septic patients inhibit apoptosis of T lymphocytes by down-regulating bad via hsa-miR-7-5p.

Immunosuppression is currently a vital pathophysiological characteristic and core problem of sepsis. Apoptosis of T lymphocyte contribute to immunosuppression by decreasing immune effector cells. A report has recently revealed the potential regulatory role of exosomal miRNAs derived from plasma of septic patients on immune system, but the underlying mechanism is unclear. We discovered the antiapoptotic effect of circulating exosomes derived from plasma of septic patients (Sepsis-Exos) on T lymphocytes and further investigated the molecular mechanism. Next-generation sequencing (NGS) indicated that sepsis induces prominent change of exosomal miRNA expression profile, including the overexpressed hsa-miR-7-5p. Gene Bad, which is in the cGMP-PKG signaling pathway, was negatively regulated by hsa-miR-7-5p by dual luciferase reporter assay. Sepsis-Exos were demonstrated to downregulate the mRNA and protein levels of proapoptotic gene Bad, active Caspase-3 and Bax, while upregulate that of antiapoptotic gene Bcl-2 via hsa-miR-7-5p, thus inhibited apoptosis of T lymphocytes induced by lipopolysaccharide (LPS) in vitro. Furthermore, Sepsis-Exos was verified to inhibit T lymphocytes apoptosis during sepsis in vivo, reducing mortality rate of septic model mice. In conclusion, we provide evidence that Sepsis-Exos participate in ameliorating apoptosis of T lymphocytes by directly suppressing Bad via hsa-miR-7-5p.

An in-needle solid-phase microextraction device packed with etched steel wires for polycyclic aromatic hydrocarbons enrichment in water samples.

A novel, low-cost and effective in-needle solid-phase microextraction device was developed for the enrichment of trace polycyclic aromatic hydrocarbons in water samples. The in-needle solid-phase microextraction device could be easily assembled by inserting hydrofluoric acid-etched wires, which were used as adsorbent, into a 22-gauge needle tube within spring supporters. Compared with the commercial solid-phase microextraction fiber, the developed device has higher efficiency for the extraction of polycyclic aromatic hydrocarbons with four to six rings from water samples using the optimized extraction conditions. With gas chromatography equipped with a flame ionization detector, the limits of detection for the polycyclic aromatic hydrocarbons with four to six rings ranged from 0.0020 to 0.0067 ng/mL. The relative standard deviations for one needle and needle-to-needle extractions were in the range of 5.2-9.9% (n = 5) and 3.4-12.3% (n = 5), respectively. The spiked recoveries of the polycyclic aromatic hydrocarbons in tap water samples ranged from 73.2 to 95.4%. This in-needle solid-phase microextraction device could be a good field sampler because of the low sample loss over a long storage time.

Improving the Sensitivity of Solid-Phase Microextraction by Reducing the Volume of Off-Line Elution Solvent.

Solid-phase microextraction (SPME) coupled with liquid chromatograph (LC) is widely used to detect polar and ionic organic compounds, including various pharmaceuticals and endogenous bioactive compounds. In this study, a small-sized insert tube for use in the commercial autosampler vial was designed for eluting the extracted analytes from SPME fibers for LC analysis. By using this custom-made insert tube as an alternative to the commercial insert tube, the volume of the elution solvent was reduced by four-fifths. Even though smaller fractions of the analytes were eluted from the fiber coatings, the analyte concentrations in the elution solutions were substantially increased by using the custom-made insert tube. Therefore, larger amounts of the analytes could be injected to LC and higher signal-to-noise ratios could be achieved, even at smaller injection volumes. Since the elution in the custom-made insert tube was nonexhaustive, four strategies were developed to figure out the extracted amounts in the fiber coatings. In combination with the sampling-rate calibration method, these strategies were successfully used to determine the concentrations of fluoxetine in living tilapias. This study provides a simple but effect way for improving the analytical sensitivity when coupling SPME with LC.

Efficient and Versatile Pipet Microextraction Device Based on a Light-Heatable Sorbent.

Miniaturized sample pretreatment platforms have simplified analytical tasks in diverse disciplines. Herein, a novel pipet microextraction (PME) device is reported by making use of the photothermal property of a light-heatable sorbent (LHS) for the first time. Efficient and staining-free heating treatment of small volumes of liquids confined in the PME device is now enabled through light illumination. The light-induced heating treatment is capable of dramatically accelerating solvent elution rates, effectively unlocking bound toxin from its antibody, and rapidly quenching enzymatic activities, thus, provides PME with higher efficiencies and enables its new applications in antibody-intermediated sampling of targeted toxin from stained food surfaces and powders, as well as in accurate revelation of enzymatic reaction kinetics. This study offers a new perspective of designing efficient and versatile microextraction platforms and demonstrates their potential applications in different fields including public security, new drug development, and environmental protection.

Synthesis and application of magnetic molecularly imprinted polymers in sample preparation.

Magnetic molecularly imprinted polymers (MMIPs) have superior advantages in sample pretreatment because of their high selectivity for target analytes and the fast and easy isolation from samples. To meet the demand of both good magnetic property and good extraction performance, MMIPs with various structures, from traditional core-shell structures to novel composite structures with a larger specific surface area and more accessible binding sites, are fabricated by different preparation technologies. Moreover, as the molecularly imprinted polymer (MIP) layers determine the affinity, selectivity, and saturated adsorption amount of MMIPs, the development and innovation of the MIP layer are attracting attention and are reviewed here. Many studies that used MMIPs as sorbents in dispersive solid-phase extraction of complex samples, including environmental, food, and biofluid samples, are summarized. Graphical abstract The application of magnetic molecularly imprinted polymers (MIPs) in the sample preparation procedure improves the analytical performances for complex samples. MITs molecular imprinting technologies.

Study on the Diffusion-Dominated Solid-Phase Microextraction Kinetics in Semisolid Sample Matrix.

Solid-phase microextraction (SPME) kinetics in semisolid samples should be different from that in aqueous and gaseous samples, as convection is negligible in semisolid samples but dominates mass transfer in bulk phases of aqueous and gaseous samples. This study developed a mathematical model for describing SPME kinetics in semisolid samples by considering the diffusion of analytes in two compartments, i.e., the fiber coating and the ever-increasing diffusion domain in the sample matrix. The mathematical model predicted that SPME and the desorption of preloaded analytes from the fiber would be isotropic in semisolid samples, while SPME in semisolid samples would not follow the first order kinetics as in aqueous and gaseous samples. The predictions were proven true in the experiment of four pharmaceuticals in agarose gel. In return, it was observed in the experiment that SPME kinetics would deviate more significantly from the first order kinetics for the analytes with higher partition coefficients between the fiber and the sample matrix, which was well explained by the mathematical model developed in this study. In addition, SPME kinetics predicted by the model coincided well with the experimental results when the diffusion coefficients were at reasonable levels, which demonstrated that the model could be satisfactory for describing SPME kinetics in semisolid samples. The illustration of the nonfirst order SPME kinetics in semisolid samples can be valuable for evaluating the applicability of the existing pre-equilibrium calibration methods in semisolid samples.

Bioinspired Polyelectrolyte-Assembled Graphene-Oxide-Coated C18 Composite Solid-Phase Microextraction Fibers for In Vivo Monitoring of Acidic Pharmaceuticals in Fish.

A novel solid-phase microextraction (SPME) fiber was prepared by gluing poly(diallyldimethylammonium chloride) (PDDA) assembled graphene oxide (GO)-coated C18 composite particles (C18@GO@PDDA) onto a quartz fiber with polyaniline (PANI). The fiber surface coating was sequentially modified with bioinspired polynorepinephrine, which provided a smooth biointerface and makes the coating suitable for in vivo sampling. The novel custom-made coating was used to extract acidic pharmaceuticals, and high-performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) was employed for analysis. The custom-made coating exhibited a much higher extraction efficiency than the previously used commercial polydimethylsiloxane (PDMS) and polyacrylate (PA) coatings. The custom-made coating also possessed satisfactory stability (the relative standard deviations (RSDs) ranged from 1.60% to 10.3% for six sampling-desorption cycles), interfiber reproducibility (the RSDs ranged from 2.61% to 11.5%), and resistance to matrix effects. The custom-made fibers were used to monitor the presence of acid pharmaceuticals in dorsal-epaxial muscle of living fish, and satisfactory sensitivities (limits of detection ranged from 0.13 ng/g to 7.56 ng/g) were achieved. The accuracies were verified by the comparison with liquid extraction. Moreover, the novel fibers were successfully used to monitor the presence of acidic pharmaceuticals in living fish, which demonstrated that the custom-made fibers were feasible for possible long-term in vivo continuous pharmaceutical monitoring.