The relationship between anxiety and depression in adolescent depression patients: The mediating effect of hope level and coping modes.

Background: Adolescents diagnosed with depression are particularly susceptible to anxiety and depressive symptoms, this vulnerability often diminishes their future expectations and overall outlook on life. The objective of this research was to scrutinize the associated risk factors of adolescent depression and delineated the interplay between anxiety and depressive symptoms. Concurrently, it sought to ascertain the latent mediating effects of hope levels and coping strategies within this framework. Methods: A mixed-methods research approach was employed. For the qualitative component, 18 adolescents with depression were interviewed following a semi-structured interview guide, with sessions audio-recorded. The data were subsequently transcribed and subjected to thematic content analysis. In the quantitative phase, a cross-sectional online survey was administered to 210 adolescents diagnosed with depression using Questionnaire Star, with data analysis performed using SPSS25.0 and AMOS 24.0. Results: The qualitative analysis identified three major themes and nine categories as key risk factors influencing the onset of adolescent depression. Three major themes were generated: school factors, family factors, and other factors. Nine categories were generated: heavy academic load, strained peer, and teacher-student relationships; unstable family structures, internal familial conflicts, and high parental expectations; a strong sense of social isolation, insufficient sexual education, and prevalent suicidal ideation or attempts. A nurturing and supportive school environment significantly bolsters adolescents' sense of hope and coping abilities, while a warm and encouraging family setting effectively mitigates psychological stress. Conversely, heightened loneliness and the onset of suicidal ideation are frequently linked to diminished hope and the adoption of maladaptive coping strategies. Hence, to comprehensively understand the intricate interplay of these factors, this study concentrated on the levels of hope and coping mechanisms, investigating their potential mediating role in adolescent anxiety and depression. Quantitative analysis revealed a positive correlation between anxiety and depression (r = 0.767, p＜0.01). Additionally, it was found that hope levels and coping strategies mediated the relationship between anxiety and depressive symptoms (ß = -0.24-0.84 = 0.20, p < 0.001; ß = 0.19-0.51 = -0.10, p < 0.01), with the mediating influence of hope levels being more significant than that of coping strategies. Conclusion: Enhancing hope levels and fostering positive coping strategies are instrumental in aiding adolescents with depression to alleviate their anxiety and depressive symptoms. Moreover, this study underscored the importance of focusing on adolescents' mental health and providing them with emotional support, thereby increasing their hope levels and encouraging the adoption of positive coping mechanisms to effectively address their challenges.

Antimony isotopic fractionation induced by Sb(V) adsorption on ß-MnO2.

Antimony (Sb) isotopes hold immense promise for unraveling Sb biogeochemical cycling in environmental systems. Mn oxides help control the fate of Sb via adsorption reactions, yet the behavior and mechanisms of Sb isotopic fractionation on Mn oxides are poorly understood. In this study, we examine the Sb isotopic fractionation induced by adsorption on ß-MnO2 in different experiments (kinetic, isothermal, effect of pH). We observe that adsorption on ß-MnO2 surfaces preferentially enriches lighter Sb isotopes through equilibrium fractionation, with Δ123Sbaqueous-adsorbed of 0.55-0.79 ‰. Neither the pH or surface coverage affects the fractionation magnitude. The analysis of extended X-ray absorption fine structure (EXAFS) demonstrates that the enrichment of light isotope results from the adsorption of inner-sphere complexation on solids. Our finding of this study enhances our comprehension of the impact of ß-MnO2 on Sb isotopic fractionation behavior and mechanism and facilitate the applicability of Sb isotopes as effective tracers to elucidate the origins and pathways of Sb contamination in environmental systems, as well as provide a new insight into forecasting the isotopic fractionation of other similar metals adsorbed by manganese oxides.

Antimony mobility in soil near historical waste rock at the world's largest Sb mine, Central China.

Soil near waste rock often contains high concentrations of antimony (Sb), but the mechanisms that mobilize Sb in a soil closely impacted by the waste rock piles are not well understood. We investigated these mobility mechanisms in soils near historical waste rock at the world's largest Sb mine. The sequential extraction (BCR) of soil reveal that over 95 % Sb is present in the residual fraction. The leached Sb concentration is related to the surface protonation and deprotonation of soil minerals. SEM-EDS shows Sb in the soil is associated with Fe and Ca. Moreover, X-ray absorption spectroscopy (XAS) results show Sb is predominantly present as Sb(V) and is associated with Fe in the form of tripuhyite (FeSbO4) as well as edge- and corner-sharing complexes on ferrihydrite and goethite. Thus, Fe in soils is important in controlling the mobility of Sb via surface complexation and co-precipitation of Sb by Fe oxides. The initially surface-adsorbed Sb(V) or co-precipitation is likely to undergo a phase transformation as the Fe oxides age. In addition, Sb mobility may be controlled by small amounts of calcium antimonate. These results further the understanding of the effect of secondary minerals in soils on the fate of Sb from waste rock weathering and inform source treatment for Sb-contaminated soils.

[Health Benefit Assessment of Coal-to-electricity Policy on PM2.5 Pollution in Beijing-Tianjin-Hebei Region].

To accurately assess the health benefits of the coal-to-electricity policy during the heating period in the Beijing-Tianjin-Hebei(BTH) Region, the premature deaths caused by PM2.5 before and after the implementation of the coal-to-electricity policy during the heating period in each district and county of the BTH Region were estimated, and the corresponding health loss values were calculated using the willingness to pay method. The results showed that the implementation of the coal-to-electricity policy in the BTH Region brought 1745 cases(95% CI:1443-1907) of health benefits and 2.38 billion yuan(95% CI:1.45-3.06) in economic benefits. In Beijing, Tianjin, and Hebei there were 495 cases(95% CI:436-554), 296 cases(95% CI:238-354), and 954 cases(95% CI:693-1076) of health benefits, respectively. The economic benefits were 0.35 billion yuan(95% CI:0.30-0.39), 0.33 billion yuan(95% CI:0.27-0.40), and 1.70 billion yuan(95% CI:0.88-2.28), respectively, accounting for 0.01%, 0.02%, and 0.04% of GDP in each region. The number of premature deaths due to COPD, LC, ALRI, IHD, and STROKE decreased by 187 cases(95% CI:165-224), 318 cases(95% CI:178-458), 193 cases(95% CI:115-204), 506 cases(95% CI:232-780), and 542 cases(95% CI:463-621), respectively. Areas with relatively high environmental PM2.5 concentrations and concentrated population-intensive pollution emissions can achieve significant health and economic benefits.

Sources of antimony contamination and its migration into water systems of Xikuangshan, China: Evidence from hydrogeochemical and stable isotope (H, O, S, and Sr) signatures.

The Xikuangshan (XKS) mine was selected for a comprehensive Sb-related hydrogeochemical study because of its significant Sb contamination in water systems. Hydrochemical data, specifically multi-isotope (H, O, S, and Sr) data, were conducted to elucidate the primary sources and migration processes of Sb responsible for water system contamination. At the XKS Sb mine, water is near-neutral to alkaline and is characterized by high concentrations of SO42- and Sb. Sb occurs as Sb(OH)6- (the dominant species) in these oxidized waters. The hydrochemistry is mainly controlled by carbonate dissolution and silicate weathering. δ2HH2O and δ18OH2O values indicate that the infiltration recharge of mine water and mining activities regulate the migration of Sb in groundwater. δ34SSO4 and δ18OSO4 values indicate that dissolved SO42- and Sb primarily come from stibnite oxidation, bacterial SO42- reduction has either not occurred or is extremely weak, and the reductive dissolution of Fe (III) hydroxides does not significantly affect Sb migration in water. The 87Sr/86Sr ratios further indicate that the discharge of solid mine wastes leaching and smelting water is a crucial source of Sb contamination in groundwater. In addition, the relationship between δ34SSO4 and δ87Sr values suggests the complexity of the contamination source and migration of Sb in water. Finally, a robust conceptual hydrogeochemical model was developed using isotopic tools in combination with detailed hydrogeological and hydrochemistry characterization to describe the contamination source and migration of Sb in water systems at the XKS Sb mine.

Antimony Isotope Fractionation Revealed from EXAFS during Adsorption on Fe (Oxyhydr)oxides.

A lack of knowledge about antimony (Sb) isotope fractionation mechanisms in key geochemical processes has limited its environmental applications as a tracer. Naturally widespread iron (Fe) (oxyhydr)oxides play a key role in Sb migration due to strong adsorption, but the behavior and mechanisms of Sb isotopic fractionation on Fe (oxyhydr)oxides are still unclear. Here, we investigate the adsorption mechanisms of Sb on ferrihydrite (Fh), goethite (Goe), and hematite (Hem) using extended X-ray absorption fine structure (EXAFS) and show that inner-sphere complexation of Sb species with Fe (oxyhydr)oxides occurs independent of pH and surface coverage. Lighter Sb isotopes are preferentially enriched on Fe (oxyhydr)oxides due to isotopic equilibrium fractionation, with neither surface coverage nor pH influencing the degree of fractionation (Δ123Sbaqueous-adsorbed). Limited Fe atoms are present in the second shell of Hem and Goe, resulting in weaker surface complexes and leading to greater Sb isotopic fractionation than with Fh (Δ123Sbaqueous-adsorbed of 0.49 ± 0.004, 1.12 ± 0.006, and 1.14 ± 0.05‰ for Fh, Hem, and Goe, respectively). These results improve the understanding of the mechanism of Sb adsorption by Fe (oxyhydr)oxides and further clarify the Sb isotope fractionation mechanism, providing an essential basis for future application of Sb isotopes in source and process tracing.

Cleaning efficacy of EDDY versus ultrasonically-activated irrigation in root canals: a systematic review and meta-analysis.

BACKGROUND: Ultrasonically-activated irrigation (UAI) is effective in root canal irrigation but may damage canal walls. EDDY is a sonic activation system with flexible working tips that cause no harm to dentinal walls. This review explores the intracanal cleaning efficacy of EDDY compared with UAI in vitro. METHODS: The systematic review was registered in the PROSPERO database (CRD42021235826). A literature search was conducted in six electronic databases. In vitro studies that compared the removal of smear layer, debris, soft tissue or microbes in root canals between EDDY and UAI were included. Data extraction and quality assessment were performed. Meta-analyses were conducted on smear layer removal and debris elimination with the standardized mean difference (SMD). Heterogeneity was measured using the I2 test and the Chi2 test. The random-effect model was used when I2 > 50%, or p < 0.1, otherwise the fixed-effect model was applied. The level of significance was set at p < 0.05. RESULTS: 19 articles were included in this systematic review and 7 articles were included in meta-analyses. Meta-analyses on smear layer removal showed unimportant differences between EDDY and UAI at any canal third (coronal [SMD = 0.08, 95% confidence interval (95%CI): -0.29 to 0.45; p = 0.44, I2 = 0%]; middle [SMD = 0.02, 95% CI: -0.44 to 0.47; p = 0.94, I2 = 0%]; apical [SMD = 0.01, 95%CI: -0.35 to 0.38; p = 0.70, I2 = 0%]). Meta-analyses on debris removal evaluated by scanning electron microscope (coronal [SMD = 0.03, 95% CI: -0.41 to 0.46; p = 0.27, I2 = 23%]; middle [SMD = -0.24, 95% CI: -0.83 to 0.35; p = 0.80, I2 = 0%]; apical [SMD = 0.24, 95%CI: -0.20 to 0.67; p = 0.36, I2 = 2%]) and micro-CT (SMD = 0.36, 95% CI: -0.67 to 1.40; p = 0.03, I2 = 70%) both found insignificant differences. No meta-analysis was undertaken on soft-tissue removal and disinfection due to the various study designs, but the qualitative analyses implied that EDDY achieved similar performance to UAI in both aspects. CONCLUSIONS: Limited evidence indicated that EDDY was comparable to UAI in removing smear layer, debris, soft tissue and microbes ex vivo. Considering UAI may damage canal walls, EDDY might be a substitute for UAI in irrigation activation. But more randomized clinical trials are required to explore the clinical extrapolation of the results in this review.

Analysis of nutrients in Apriona germari and treatment of diarrhea in mice fed with insect powder.

The insect larvae of Apriona germari, Apriona swainsoni and other closely related species are related to the insects that bore through the stems of the Caesalpinia decapetala. Because of therich nutritional as well as medicinal value of edible A. germari, it is often used to nourish the body, enhance immunity, and to treat ailments such as diarrhea. The soluble protein content of A. germari was determined using Kjeldahl and Soxhlet extraction methods. The crude fat content and the content of various fatty acids was determined by the normalization method, normalization method refers to that after the fat in the sample is extracted by hydrolysis ether solution, it is saponified and methylated under alkaline conditions to generate fatty acids and methyl esters, which are analyzed by capillary column gas chromatography and quantitatively measured by area normalization method. Amino acid content determined using an amino acid analyzer after acid hydrolysis showed 17 kinds of amino acids. A diarrhea mouse model was established by injecting a suspension of Escherichia coli into the abdominal cavity of mice. The mice were then fed with A. germari fodders at dose concentrations of 12%, 8%, 4% and 0%. The number of E. coli was determined from the intestinal tracts of mice; the activities of antioxidant enzymes and digestive enzymes in the serum were determined. Eleven kinds of fatty acids were detected in A. germari; unsaturated fatty acids accounted for 71.87% of the total fatty acids. A. germari is an edible resource insect with high nutritional value. Mice fed with A. germari showed an increase in the activity of antioxidant enzymes and digestive enzymes in the serum, which helped in the effective inhibition and reduction in the total number of intestinal bacteria and E. coli. The results indicate that A. germari has high nutritional value; A. germari also has a certain therapeutic effect on diarrhea caused by E. coli in mice.

Antimony (Sb) isotopic signature in water systems from the world's largest Sb mine, central China: Novel insights to trace Sb source and mobilization.

The Xikuangshan (XKS) mine, the world's largest antimony (Sb) mine, was chosen for a detailed Sb isotopic signature study owing to its historical Sb contamination of water systems. Hydrochemical data, in particularδ123Sb values, were analyzed to identify the Sb source and predominant geochemical processes that affect Sb mobilization in different waters. The δ123Sb values of waters from the XKS Sb mine range from - 0.20‰ to + 0.73‰. In particular, the δ123Sb values of the main Feishuiyan stream do not significantly vary (+0.19‰-+0.24‰), while those of groundwater in different aquifers (-0.08‰ to +0.73‰) and mine water in different adits (-0.20‰ to +0.37‰) vary over a wide range. The relationships between δ123Sb values and Sb concentrations indicate that a simple dilution of Sb and a weak Sb adsorption onto Fe/Mn suspended particles and sediments in the Feishuiyan stream may occur, oxidative weathering and leaching infiltration of Sb-containing waste rocks and slags may cause variations in the δ123Sb values in groundwater, and Sb mobilization in the mine water is influenced by a combination of processes (oxidative dissolution, adsorption of Fe/Mn (hydr)oxides, and mixing). A conceptual hydrogeochemical model was summarized to elucidate the Sb source and mobilization in water systems from the XKS Sb mine.

Effects of oxygen on the adsorption/oxidation of aqueous Sb(III) by Fe-loaded biochar: An X-ray absorption spectroscopy study.

Fe-loaded biochar (FeBC) has been considered for Sb(III) adsorption, but the effects of oxygen (O2) on the adsorption need further investigation. Liquid-/solid-phase analyses were conducted to investigate the role of O2 in the Sb(III) adsorption by FeBC. The adsorption was best described by the pseudo-second-order (PSO) model for kinetic results and by the Langmuir model for thermodynamic results. More than 96.8 % of Sb(III) was adsorbed by FeBC, and available O2 increased the liquid-phase Sb(III) oxidation efficiency by 2.1-7.5 times. The peak changes at ~1640 and 3450 cm-1 in FTIR spectra indicated the occurrence of inner-sphere complexation between Sb(III)/Sb(V) and hydroxyl (-OH)/carboxyl (-COOH) groups in FeBC under aerobic and anaerobic conditions. Fe/Sb X-ray absorption spectroscopy (XAS) analysis results showed aqueous Sb(III) complexed to the edge-sharing Fe(III)-O-Fe(III) in FeBC. Regardless of whether O2 was available or not, solid-phase edge-sharing Fe(III)-O-Sb(V) complexes (~3.05 Å), which had lower toxicity and migration ability than aqueous Sb(III), formed through a ligand-to-metal charge-transfer (LMCT) process. More than 91 % of adsorbed Sb(III) was oxidized to edge-sharing Fe(III)-O-Sb(V) complexes in 3 h. Additionally, the Sb(V) from liquid-phase oxidation could also directly complex to the Fe(III)-O-Fe(III) and form edge-sharing Fe(III)-O-Sb(V) complexes. These results provide evidence to inform further FeBC application for the Sb-contaminated water treatment.

Antimony isotope fractionation during adsorption on aluminum oxides.

The environmental fate of antimony (Sb) is often strongly affected by adsorption, and the Sb isotope fractionation mechanism during adsorption has not been reported. Four batch experiments (kinetic, isothermal, effect of pH, and effect of coexisting anions) were conducted to evaluate the mechanism of Sb(V) adsorption to γ-Al2O3 and the fractionation of Sb isotopes. Extended X-ray absorption fine structure (EXAFS) analyses show Sb(V) adsorption on γ-Al2O3 occurs via outer-sphere surface complexation. The triple-layer model (TLM) effectively predicted the theoretical Sb adsorption amount under different pH conditions. The Sb isotope fractionation in the adsorption process can be divided into an initial kinetic stage (Rayleigh model, αadsorbed-aqueous = 0.99975 ± 0.00003) and subsequent isotopic equilibrium stage due to isotope exchange; however, no significant equilibrium isotope fractionation (Δ123Sbaqueous-adsorbed = ~0 ± 0.08‰) was evident by the end of the experiments. We propose the lack of significant equilibrium isotope fractionation in the effect of pH and isothermal experiments is due to Sb forming an outer-sphere complex on γ-Al2O3. This study reveals Sb equilibrium isotope fractionation does not occur during Sb(V) adsorption onto γ-Al2O3, providing a reference for the future study of Sb isotopes and furthering understanding of the Sb isotope fractionation mechanism.

Reduction of antimony mobility from Sb-rich smelting slag by Shewanella oneidensis: Integrated biosorption and precipitation.

The dissimilatory Fe(III)-reducing bacteria play a significant role in the mobility of antimony (Sb) under reducing environment. Sb-rich smelting slag is iron (Fe)-containing antimonic mine waste, which is one of the main sources of antimony pollution. In this study, the soluble antimony reacted with Fe(III) by S. oneidensis (Shewanella oneidensis strain MR-1) was performed in reduction condition, then the dissolution behavior of the Sb-rich smelting slag with S. oneidensis was investigated. The results showed that the released Sb was immobilized by S. oneidensis and the strain adsorbed Sb(III) preferentially. Sb(V) can be reduced by S. oneidensis without aqueous Fe. In the presence of Fe(III), S. oneidensis mediated Sb bio-adsorption and the chemical redox of Sb-Fe occurred simultaneously. Sb was co-precipitated with Fe to form the Sb(V)-O-Fe(III) secondary mineral, which was identified as the bidentate mononuclear edge-sharing structure by extended X-ray absorption fine structure (EXAFS) analysis. These results suggest that S. oneidensis has a positive effect on the immobilization and minimizing toxicity of antimony in anoxic soil and groundwater, which provides a theoretical basis for the treatment of antimony contamination.

Strain-Induced Bandgap Enhancement of InSe Ultrathin Films with Self-Formed Two-Dimensional Electron Gas.

Atomically thin indium selenide (InSe) is a representative two-dimensional (2D) family that have recently attracted extensive interest for their intriguing emerging physics and potential optoelectronic applications with high-performance. Here, by utilizing molecular beam epitaxy and scanning tunneling microscopy, we report a controlled synthesis of InSe thin films down to the monolayer limit and characterization of their electronic properties at atomic scale. Highly versatile growth conditions are developed to fabricate well crystalline InSe films, with a reversible and controllable phase transformation between InSe and In2Se3. The band gap size of InSe films, as enhanced by quantum confinement, increases with decreasing film thickness. Near various categories of lattice imperfections, the band gap becomes significantly enlarged, resulting in a type-I band alignments for lateral heterojunctions. Such band gap enhancement, as unveiled from our first-principles calculations, is ascribed to the local compressive strain imposed by the lattice imperfections. Moreover, InSe films host highly conductive 2D electron gas, manifesting prominent quasiparticle scattering signatures. The 2D electron gas is self-formed via substrate doping of electrons, which shift the Fermi level above the confinement-quantized conduction band. Our study identifies InSe ultrathin film as an appealing system for both fundamental research and potential applications in nanoelectrics and optoelectronics.

Rapid and high-capacity loading of IgG monoclonal antibodies by polymer brush and peptides functionalized microspheres.

Fast-throughput and cost reduction of current purification platforms are becoming increasing requests during antibody manufacture. The macroporous-matrix absorbents have presented extensive potentiality in improving operational throughput during purification of macromolecule. And meanwhile the peptide ligand has become a promising alternative to recombinant protein ligands for cost reduction of chromatographic purification. Therefore, here we designed a functionalized microspheres resin with both macroporous matrix of polymerized glycidyl methacrylate and ethylene glycol dimethacrylate (PGMA-EDMA) and peptide ligand of hexapeptide (FYEILH). In order to circumvent the steric effect of peptides and amplify the binding sites on macroporous matrix, the peptide ligand was coupled on a liner PGMA polymer brushes grafted on microspheres. Comparing to the conventional agarose-matrix resin and the general peptide-grafted microspheres, the functionalized microspheres presented excellent permeability and high capacity to rapid loading hIgG by maintaining a stable level of dynamic binding capacity at fast flow rate above 110 column volume per hour (cv/h) and very short residence time below 0.5 min. Such functionalized microspheres provide a facile and broadly applicable strategy to develop the attractive candidate for rapid and cost-reduced purification of antibody.

In Vitro and In Vivo Metabolic Activation of Obacunone, A Bioactive and Potentially Hepatotoxic Constituent of Dictamni Cortex.

Obacunone is one of the major bioactive constituents from Dictamni cortex, a traditional Chinese medicine widely used in China. Oral administration of obacunone or Dictamni cortex extract has been shown to cause liver injury in rats. Given that obacunone contains a furan ring, which is a structural alert, metabolic activation might be responsible for obacunone-induced liver injury. In this study, bioactivation pathways of obacunone in rat and human liver microsomes were investigated. Obacunone was first metabolized into cis-butene-1,4-dial, and then cis-butene-1,4-dial was captured by glutathione, N-acetyl-cysteine, and N-acetyl-lysine in the microsomal incubation system. A total of 13 adducts derived from the reaction of cis-butene-1,4-dial with glutathione and/or N-acetyl-lysine were detected and structurally identified by liquid chromatography coupled to high-resolution tandem mass spectrometry. The major metabolite (M7) was identified to be the cyclic mono-glutathione conjugate of cis-butene-1,4-dial, which was detected in bile and urine of obacunone-treated rats. M9 and M10, obacunone-derived glutathione-cis-butene-1,4-dial-NAL conjugates, were detected in the microsomal incubations of obacunone fortified with glutathione and N-acetyl-lysine as trapping agents. M3 and M4, pyrroline-2-one derivatives, were also detected in microsomal incubations. Further phenotyping studies indicated that ketoconazole showed a strong inhibitory effect on the production of cis-butene-1,4-dial in a concentration-dependent manner. CYP3A4 was demonstrated to be the primary enzyme responsible for the bioactivation of obacunone by using individual recombinant human CYP450 enzymes. The current study provides an overview of CYP450-dominated bioactivation of obacunone and contributes to the understanding of the role of bioactivation in obacunone-induced liver injury.

Fabrication of rigid and macroporous agarose microspheres by pre-cross-linking and surfactant micelles swelling method.

A novel combined method of pre-cross-linking and surfactant micelles swelling was proposed in this study to fabricate highly cross-linked and macroporous agarose (HMA) microspheres. Agarose was chemically modified by allylglycidyl ether (AGE) as heterobifunctional cross-linker via its active glycidyl moieties before gel formation and pre-cross-linking was achieved. By this means, the effective concentration of cross-linker presented in agarose gel increased significantly, and thus cross-linking with a high-efficiency was achieved. Further to enhance the intraparticle mass transfer of agarose microspheres, the surfactant micelles swelling method was utilized to create interconnected macropores. Under the optimal condition, HMA microspheres with homogeneous reticular structure and pore size of hundreds nanometers were successfully prepared. They exhibited a low backpressure with a flow velocity as high as 1987 cm/h, which was much higher than that of commercial Sepharose 4 F F. HMA microspheres were then derivatized with carboxymethyl (CM) groups and applied in ion-exchange chromatography. As expected, CM-HMA column separated model proteins effectively even at a flow velocity three times higher than that of commercial CM-4 F F. Visualization of dynamic protein adsorption by confocal laser scanning microscope (CLSM) revealed that the intraparticle mass transfer of CM-HMA microspheres was intensified due to its macroporous structure. All of the results indicated the newly developed agarose microspheres were a promising medium for high-speed chromatography.

A novel strategy for the preparation of porous microspheres and its application in peptide drug loading.

A new strategy is developed to prepare porous microspheres with narrow size distribution for peptides controlled release, involving a fabrication of porous microspheres without any porogens followed by a pore closing process. Amphiphilic polymers with different hydrophobic segments (poly(monomethoxypolyethylene glycol-co-d,l-lactide) (mPEG-PLA), poly(monomethoxypolyethylene glycol-co-d,l-lactic-co-glycolic acid) (mPEG-PLGA)) are employed as microspheres matrix to prepare porous microspheres based on a double emulsion-premix membrane emulsification technique combined with a solvent evaporation method. Both microspheres possess narrow size distribution and porous surface, which are mainly caused by (a) hydrophilic polyethylene glycol (PEG) segments absorbing water molecules followed by a water evaporation process and (b) local explosion of microspheres due to fast evaporation of dichloromethane (MC). Importantly, mPEG-PLGA microspheres have a honeycomb like structure while mPEG-PLA microspheres have a solid structure internally, illustrating that the different hydrophobic segments could modulate the affinity between solvent and matrix polymer and influence the phase separation rate of microspheres matrix. Long term release patterns are demonstrated with pore-closed microspheres, which are prepared from mPEG-PLGA microspheres loading salmon calcitonin (SCT). These results suggest that it is potential to construct porous microspheres for drug sustained release using permanent geometric templates as new porogens.

Thermo- and pH-responsive polymer brushes-grafted gigaporous polystyrene microspheres as a high-speed protein chromatography matrix.

Dual thermo- and pH-responsive chromatography has been proposed using poly(N-isopropylacrylamide-co-butyl methacrylate-co-N,N-dimethylaminopropyl acrylamide) (P(NIPAM-co-BMA-co-DMAPAAM)) brushes grafted gigaporous polystyrene microspheres (GPM) as matrix. Atom transfer radical polymerization (ATRP) initiator was first coupled onto GPM through Friedel-Crafts acylation with 2-bromoisobutyryl bromide. The dual-responsive polymer brushes were then grafted onto GPM via surface-initiated ATRP. The surface composition, gigaporous structure, protein adsorption and dual-responsive chromatographic properties of the matrix (GPM-P(NIPAM-co-BMA-co-DMAPAAM) were characterized in detail. Results showed that GPM were successfully grafted with thermoresponsive cationic polymer brushes and that the gigaporous structure was well maintained. A column packed with GPM-P(NIPAM-co-BMA-co-DMAPAAM presented low backpressure, good permeability and appreciable thermo-responsibility. By changing pH of the mobile phase and temperature of the column in turn, the column can separate three model proteins at the mobile phase velocity up to 2528cmh(-1). A separation mechanism of this matrix was also proposed. All results indicate that the dual thermo- and pH-responsive chromatography matrix has great potentials in 'green' high-speed protein chromatography.

Improved Stability of Emulsions in Preparation of Uniform Small-Sized Konjac Glucomanna (KGM) Microspheres with Epoxy-Based Polymer Membrane by Premix Membrane Emulsification.

Uniform small-sized (<10 µm) Konjac glucomanna (KGM) microspheres have great application prospects in bio-separation, drug delivery and controlled release. Premix membrane emulsification is an effective method to prepare uniform small-sized KGM microspheres. However, since KGM solution bears strong alkalinity, it requires the membrane to have a hydrophobic surface resistant to alkali. In this study, uniform small-sized KGM microspheres were prepared with epoxy-based polymer membrane (EP) we developed by premix membrane emulsification. It was found that emulsion coalescence and flocculation occurred frequently due to the high interface energy and sedimentation velocity of KGM emulsions. Emulsion stability had a significant influence on the uniformity and dispersity of the final KGM microspheres. To improve the stability of the emulsions, the effects of the concentration of the emulsifier, the viscosity of the KGM solution, the oil phase composition and the feeding method of epoxy chloropropane (EC) on the preparation results were studied. Under optimal preparation conditions (emulsifier 5 wt % PO-5s, KGM III (145.6 mPa·s), weight ratio of liquid paraffin (LP) to petroleum ether (PE) 11:1), uniform and stable KGM emulsions (d = 7.47 µm, CV = 15.35%) were obtained and crosslinked without emulsion-instable phenomena.

Towards A Deeper Understanding of the Interfacial Adsorption of Enzyme Molecules in Gigaporous Polymeric Microspheres.

Compared with the one immobilized in the conventional mesoporous microspheres, the enzyme immobilized in gigaporous microspheres showed much higher activity and better stability. To gain a deeper understanding, we herein selected lipase as a prototype to comparatively analyze the adsorption behavior of lipase at interfaces in gigaporous and mesoporous polystyrene microspheres at very low lipase concentration, and further compared with the adsorption on a completely flat surface (a chip). Owing to the limited space of narrow pores, lipase molecules were inclined to be adsorbed as a monolayer in mesoporous microspheres. During this process, the interaction between lipase molecules and the interface was stronger, which could result in the structural change of lipase molecular and compromised specific activity. In addition to monolayer adsorption, more multilayer adsorption of enzyme molecules also occurred in gigaporous microspheres. Besides the adsorption state, the pore curvature also affected the lipase adsorption. Due to the multilayer adsorption, the excellent mass transfer properties for the substrate and the product in the large pores, and the small pore curvature, lipase immobilized in gigaporous microspheres showed better behaviors.