Constructing chemical groups on cell membranes through metabolic glycoengineering of unnatural sugars is an effective means to solve the issue of insufficient or even lack of targets in cancer theranostics. Herein, we address the limitations by developing a tetrazine precursor (SiaTz) based on a nonO-acetylated sialic acid scaffold and then utilizing it to create unnatural tetrazine triggers on the surface of cancer cells. SiaTz exhibits a good balance between the stability and reaction kinetics under physiological conditions and can be efficiently converted into corresponding tetrazine trigger through bypassing several size-limiting steps in metabolic glycoengineering process. We also prepare a proof-of-concept theranostic combination of a trans-cyclooctene derivative (CyTCO) and a thermal-sensitive drug 2,2'-azobis[2-(2-imidazolin-2-yl) propane]-dihydrochloride (AIPH) to verify the activation function of tetrazine triggers in theranostics of orthotopic and metastatic tumors. In the presence of tetrazine triggers, CyTCO can be activated via bio-orthogonal reaction to induce optoacoustic signal enhancement, enabling high-contrast diagnostic imaging and precise tumor localization to guide subsequent treatments. Tetrazine trigger-activated CyTCO displays high photo-to-heat conversion efficiency, which can cause an obvious increase in temperature under laser irradiation and then initiate AIPH decomposition to produce toxic radicals for combined therapy.
Isobaric vapor-liquid Equilibrium (VLE) data for dimethyl oxalate + methanol and methanol + 1,2-butanediol binary systems, as well as the VLE for dimethyl oxalate + methanol + 1,2-butanediol ternary system have been determined using an Ellis equilibrium distiller at 101.325 kPa. The vapor pressure of 1,2-butanol was measured with a Rose equilibrium apparatus under pressure of 0.34 kPa to atmospheric pressure. The thermodynamic consistency tests of the two binary experimental VLE data for dimethyl oxalate + methanol and methanol + 1,2-butanediol were performed according to a statistical method. The two binary experimental data were correlated by the Wilson, non-random two-liquid (NRTL) and universal quasi-chemical (UNIQUAC) activity coefficient models integrated in the authorized Aspen Plus software with the maximum average absolute deviations of 1.42 K for temperature and 0.0153 for vapor phase composition, the binary component interaction parameters were also obtained by this regression. On the basis of these calculated results, the corresponding binary interaction parameters of the dimethyl oxalate and 1,2-butanediol was then regressed from experimental ternary (dimethyl oxalate + methanol +1,2-butanediol) VLE data. These experimental and calculated data are valuable for the separation process design and optimization of dimethyl oxalate hydrogenation to ethylene glycol.
Nonan-2-one is a novel solvent with extremely low solubility in water to extract dihydroxy benzene from coal gasification wastewater. In this work, the liquid-liquid equilibrium (LLE) data for the ternary (nonan-2-one + benzene-1,2-diol/benzene-1,3-diol/benzene-1,4-diol + water) systems were determined at 298.15, 313.15, 323.15 and 333.15 K under 101.3 kPa. According to calculation, distribution coefficients show that nonan-2-one can offer good extraction performance and selectivity parameters. The NRTL and UNIQUAC models were used to correlate the experimental data and the binary interaction parameters were obtained. The root mean square deviation values of the two models are similar and lower than 0.021, which means the two models can estimate the LLE data accurately. Nonan-2-one is an efficient extractant for separating dihydroxy benzenes from wastewater.
Background: Nutritional intervention and gut microbiota have emerged as potential strategies to strengthen intestinal barrier. Herein, we investigated the positive effects of pentagalloyl glucose (PGG) on improving intestinal dysfunction.Methods: The effects of PGG on enhancing intestinal barrier were investigated by mice and Caenorhabditis elegans models. Fecal microbiota transplantation (FMT) and probiotic screening projects were conducted to explain the importance of gut microbiota in regulating intestine barrier integrity.Findings: The findings demonstrated PGG effectively ameliorated lipid metabolism, relieved liver and intestinal damage, balanced gut microbiota and stimulated short chain fatty acids (SCFAs) production. Meanwhile, PGG promoted the SCFAs-related bacterium abundance, including Alloprevotella, Blautia, Butyricmonas, Alistipes, Acetatifactor and Enterococcus genus. Moreover, the FMT experiments confirmed the gut microbiota derived from PGG-treated mice could improve intestinal damage and mitochondria dysfunction in C. elegans.The Enterococcus faecalis, expanded by PGG, strengthened intestinal barrier through upregulating the zoo-1, gly-5 and ifb-2 expression and downregulating ajm-1 and hmp-1. Furthermore, with increase of SCFAs levels, the inflammation and barrier damage of intestine were mitigated by PGG through increasing the expression of tight junction protein and mucin-2, and decreasing inflammation-related protein MCP-1 and nuclear factor-κB (NF-κB) levels.Interpretation: PGG effectively mitigated the intestinal dysfunction by improving the gut microbiota balance and metabolism. These observations provided vital evidences for polyphenols as a competent candidate in maintaining intestinal homeostasis.Funding: This research was supported by the General project of the Natural Science Foundation of Guangdong Province, China (2022A1515010907; 2023A1515011266) and the National Natural Science Foundation of China (31700501).Declaration of Interest: No potential conflict of interest was reported by the author(s)..Ethical Approval: All animal experiments were approved by the Laboratory Animal Center of South China Agricultural University (Guangdong, China) under permit no. 2020b005 and 2020b085 (Guangdong, China). In this study, all experimental methods were conducted in accordance with the regulations of South China Agricultural University on experimental animals.
Organic small-molecule contrast agents have attracted considerable attention in the field of multispectral optoacoustic imaging, but their weak optoacoustic performance resulted from relatively low extinction coefficient and poor water solubility restrains their widespread applications. Herein, we address these limitations by constructing supramolecular assemblies based on cucurbit[8]uril (CB[8]). Two dixanthene-based chromophores (DXP and DXBTZ) are synthesized as the model guest compounds, and then included in CB[8] to prepare host-guest complexes. The obtained DXP-CB[8] and DXBTZ-CB[8] display red-shifted and increased absorption as well as decreased fluorescence, thereby leading to a substantial enhancement in optoacoustic performance. Biological application potential of DXBTZ-CB[8] is investigated after co-assembly with chondroitin sulfate A (CSA). Benefiting from the excellent optoacoustic property of DXBTZ-CB[8] and the CD44-targeting feature of CSA, the formulated DXBTZ-CB[8]/CSA can effectively detect and diagnose subcutaneous tumors, orthotopic bladder tumors, lymphatic metastasis of tumors and ischemia/reperfusion-induced acute kidney injury in mouse models with multispectral optoacoustic imaging.
Polymerization in living systems has become an effective strategy to regulate cell functions and behavior. However, the requirement of high concentrations of monomers, the existence of complicated intracorporal interferences, and the demand for extra external stimulations hinder their further biological applications. Herein, a nanocompartment-confined strategy that provides a confined and secluded environment for monomer enrichment and isolation is developed to achieve high polymerization efficiency, reduce the interference from external environment, and realize broad-spectrum polymerizations in living systems. For exogenous photopolymerization, the light-mediated free-radical polymerization of sodium 4-styrenesulfonate induces a 2.7-fold increase in the reaction rate with the protection of a confined environment. For endogenous hydrogen peroxide-responsive polymerization, p‑aminodiphenylamine hydrochloride embedded in a nanocompartment not only performs a 6.4-fold higher reaction rate than that of free monomers, but also activates an effective second near-infrared photoacoustic imaging-guided photothermal immunotherapy at tumor sites. This nanocompartment-confined strategy breaks the shackles of conventional polymerization, providing a universal platform for in vivo synthesis of polymers with diverse structures and functions.
Cancer immunotherapy is revolutionizing oncology. The marriage of nanotechnology and immunotherapy offers a great opportunity to amplify antitumor immune response in a safe and effective manner. Here, electrochemically active Shewanella oneidensis MR-1 can be applied to produce FDA-approved Prussian blue nanoparticles on a large-scale. We present a mitochondria-targeting nanoplatform, MiBaMc, which consists of Prussian blue decorated bacteria membrane fragments having further modifications with chlorin e6 and triphenylphosphine. We find that MiBaMc specifically targets mitochondria and induces amplified photo-damages and immunogenic cell death of tumor cells under light irradiation. The released tumor antigens subsequently promote the maturation of dendritic cells in tumor-draining lymph nodes, eliciting T cell-mediated immune response. In two tumor-bearing mouse models using female mice, MiBaMc triggered phototherapy synergizes with anti-PDL1 blocking antibody for enhanced tumor inhibition. Collectively, the present study demonstrates biological precipitation synthetic strategy of targeted nanoparticles holds great potential for the preparation of microbial membrane-based nanoplatforms to boost antitumor immunity.
Although photothermal immunotherapy (PTI) is a compelling strategy for tumor therapy, the development of promising photothermal agents to overcome the insufficient immunogenicity of tumor cells and the poor immune response encountered in PTI is still challenging. Herein, commercial small-molecule-based organic metal adjuvants (OMAs) are presented, with second near-infrared photoacoustic and photothermal properties as well as the ability to perturb redox homeostasis to potentiate immunogenicity and immune responsiveness. OMAs, assembled from charge-transfer complexes and characterized by a broad substrate scope, high accessibility, and flexibly tuned optical properties, demonstrate strong phototherapeutic and adjuvant abilities via the depletion of glutathione and cysteine, and subsequently elicit systemic immunity by evoking immunogenic cell death, promoting dendritic cell maturation, and increasing T cell infiltration. Furthermore, programmed cell death protein 1 antibody can be employed to synergize with OMAs to suppress tumor immune evasion and ultimately improve the treatment outcomes. This study unlocks new paradigms to provide a versatile OMA-based scaffold for future practical applications.
由液液相平衡(LLE)测定数据回归得到的二元交互作用参数是准确进行萃取脱酚及溶剂回收过程模拟的基础数据.针对溶剂萃取废水处理中甲酚过程,测定了25和50℃下异丙叉丙酮-邻(间、对)甲酚-水三元液液相平衡数据.采用Hand方程和Othmer-Tobias方程对实验数据的可靠性进行检验,由图可看出拟合效果优异,具有良好的可靠性.而后采用非随机双液模型(NRTL)和通用准化学模型(UNIQUAC)对测定数据进行拟合回归,获得相应的二元交互作用参数.通过计算实验数据和模型数据的均方根误差(RMSE),发现两种模型对实验数据均能进行精确关联,RMSE均低于0.01443%.为了预测其他温度下的LLE值,利用四参数的NRTL模型进行回归,发现RMSE最大只有0.01208%,小于单温度NRTL模型RMSE值.
Abstract Antibiotics pose a great threat to ecological environment and human health, which should remove with an efficient innovative treatment method. Here in, a photoelectrocatalytic strategy for persulfate activation by BiVO4 photoanode had been systematically researched in this work. In the presence of PS, the degradation efficiency of sulfamethoxazole (SMX) reached to 97.3% within 100 min, whereas the kinetic rate constant was 0.0388 min− 1, which was about 7.05 times higher than no addition of PS (0.0055 min− 1). Open circuit potential (OCP), electrochemical impedance spectroscopy (EIS) and linear sweep voltammetry (LSV) were measured, suggesting that PS played a photoelectron acceptor for improving the separation of photogenerated holes and electrons and accelerating charge transfer. The radical quenching experiments and EPR tests indicated that holes and superoxide were dominant reactive oxidation species by directly oxidation pollutants. Indirect transfer pathway of S2O82− for producing hydroxyl radicals played a minor role, while only a small amount of sulfate radical was produced. Mixed pollutants with three antibiotics (ciprofloxacin (CIP), tetracycline (TC) and SMX) had been further degraded. Results showed that the degradation of SMX was inhibited in a content compared to a single pollutant, but both TC and CIP showed satisfactory removal effects, especially in natural water. Liquid chromatography-mass spectroscopy (LC-MS) was used to determine the intermediates of SMX (with 7 intermediates), CIP (with 11 intermediates) and TC (with 19 intermediates) in the PEC system. This work provides an eco-friendly and efficient method for antibiotic removal, which has good application prospect in the degradation of mixed pollutants.
Due to different energy consumption characteristics in different regions, the planning of single regional energy system will lead to limited equipment capacity, low renewable energy penetration and poor regional economy. In response to the above problems, this article proposes a multi-regional joint planning method based on the interconnection of electricity and hydrogen. Firstly, the model of multi-regional electricity-hydrogen interconnected energy system is established. And then the optimal solution of multi-regional energy station collaborative planning is limited in the feasible region through interconnected cable power constraints, hydrogen transportation constraints, interconnected power balance constraints, interconnected power line loss constraints, etc. Finally, taking the functional areas with different energy supply and consumption characteristics as the research object, the effectiveness of the proposed method in improving system economy and promoting renewable energy consumption is verified.
甲基异丁基甲酮(MIBK)是高浓煤化工含酚废水处理中萃取脱酚优选萃取剂.总结了与溶剂萃取脱酚紧密相连的甲基异丁基甲酮-酚/有机酸-水液液相平衡研究现状.也对围绕甲基异丁基甲酮萃取脱酚为核心的酚氨回收流程变革过程进行回顾,同时对酚氨回收设计及MIBK相关的萃取运行及研究提出思路,为极大稳定后续生化处理的操作提供方便.
Solvent extraction plays a significant role as an energy-efficient treatment method in the recovery of phenol from wastewater, and a key step is to screen a promising extraction agent with a highly efficiency and good chemical stability. In this study, dibutyl ether (DBE) with low solubility and good stability was selected as the potential solvent to remove phenol from aqueous phase. Liquid-liquid equilibrium data for the (water + phenol + DBE) were determined at T= (298.15, 313.15, 323.15 and 333.15) K under ambient pressure. Effect of temperature on distribution coefficients and separation factors were investigated. The measured results were satisfactorily correlated by the NRTL and UNIQUAC models. The reliability of the tie-lie data was evaluated by the Othmer-Tobias and Hand equations. The Gibbs minor common tangent test was investigated according to previous published method. Moreover, DBE's extraction performance is further analysed by a-profile which can reflect the molecular interaction energy. (C) 2020 Elsevier Ltd.
The applicability of 2-octanone as solvent for the liquid phase extraction of phenol from aqueous solution was investigated in this work. The liquid liquid equilibrium (LLE) for the ternary systems {2-octanone + phenol + water} was experimentally determined at 298.15 K, 318.15 K and 338.15 K under atmospheric pressure. Distribution coefficients and separate factors calculated from the experimental LLE data were used to judge if 2-octanone can be used as potential solvent to extract phenol from aqueous solution. Distribution coefficients and separation factors of 2-octanone were also compared with other extractants and results show that 2-octanone has excellent extraction performance. Binary interaction parameters were regressed by the NRTL and UNIQUAC methods, and related physical meaning is explained by interaction forces. The root mean squared deviations (RMSDs) show that both models can well describe phase equilibrium behavior of ternary system {2-octanone + phenol + water}. In order to predict ternary LLE data at other temperatures, the NRTL model was used to simultaneously regress ternary experimental data at all temperatures and the largest RMSD is 0.49%. (C) 2018 Elsevier B.V. All rights reserved.
Liquid liquid equilibrium (LLE) data for ternary systems of methyl isopropyl ketone (MIPK) + 2,3-/3,4-/3,5-dimethylphenol + water was determined from 298.15 K to 338.15 K under 101.3 kPa in this work. Distribution coefficient and selectivity were calculated to investigate solvent extraction efficiency of dimethylphenol from water and their high values indicated that MIPK could extract dimethylphenols well. The NRTL and UNIQUAC models were applied to correlate experimental LLE data and related root-mean square deviations (RMSDs) were less than 0.5%. Additionally, the experimental data was predicted by COSMO-SAC model, and the corresponding RMSD values demonstrated that COSMO-SAC model can be applied as a predictive tool to calculate LLE data of the investigated ternary systems. (C) 2019 Elsevier Ltd.
The study investigated ciprofloxacin (CIP) adsorption capacity of the novel biomaterials prepared from banyan aerial roots by simple thermochemical modification. Pretreated banyan aerial root fibers were modified with a green reagent citric acid (1 M) at 90, 120 and 150 degrees C, which enhanced the fiber adsorption capacity revealed by characterization and adsorption tests. Several characterization methods were applied to exploring the surface morphologies and physicochemical properties of unmodified banyan aerial roots (UBARs) and modified banyan aerial roots (T-MBARs, T stands for the modification temperature). Based on SEM images and N2 adsorption/desorption isotherms, the modification resulted in decrease of the specific surface area owing to cellulose molecular linking. In that case, the improved CIP adsorption of MBARs might be attributed to the larger carboxyl quantity and stronger electronegativity manifested via FTIR spectra and zeta potential analysis. Through the adsorption experiments, the optimal pH value of 8 and the suitable absorbent dosage of 0.03 g were obtained. The simulation results showed that the Freundlich model can fit the adsorption thermodynamic data quite well, while the kinetic data was simulated preferably by the pseudo-second-order kinetic equation signifying the chemical adsorption process, and the intra-particle diffusion was involved in the adsorption consisted of three stages. The findings of batch experiments under diverse operations represented that MBARs purified aqueous CIP better than UBARs, closely related to the superior electronegativity. Both characterization and adsorption studies illustrated the dominant role of electrostatic interaction during CIP removal, accompanied by hydrogen bonding and diffusion interaction besides. The present work suggested that MBAR fibers could possess a promising application to ciprofloxacin potent removal from aqueous solutions. (C) 2019 Elsevier B.V. All rights reserved.
It is necessary to study the contamination of antibiotics in natural water bodies and assess its impact on ecological and human risks because of the large-scale use in the world. The occurrence and distribution characteristics of 45 antibiotics in reservoirs in Dongguan were investigated. Approximately, 77.8% of the detectable concentration of 35 antibiotics were found in the evaluation samples with concentration ranged from not detected (ND) to 729.59 ng/L, and dehydrated erythromycin was the highest one that appeared in Tongsha Reservoir. Fluoroquinolones and tetracyclines were the most abundant antibiotics with the detection frequency of 100% at sum concentration of 7.23–212.43 ng/L and 13.46–72.66 ng/L, respectively. Macrolides had a lower detected frequency but with highest concentration level at five kinds of antibiotics. Sulfamethoxazole, lincomycin, dehydrated erythromycin, pefloxacin, and panofloxacin were selected as important evaluation indicators. Sulfaguanidine, sulfamethoxazole, sulfisoxazole, dehydrated erythromycin, and clarithromycin that showed a significant correlation with Cl− and SO42− indicated that the pollution source of these antibiotics may be related to wastewater treatment plants. Among detected antibiotics, trimethoprim, norfloxacin, sarafloxacin, lincomycin, oxytetracycline, novobiocin, dehydrated erythromycin, and clarithromycin presented high risk to aquatic ecosystem in the reservoirs. There was no risk to humans at different ages of detected antibiotics, but it should attract attention because of the cumulative effects of antibiotics, which may cause potential risks to the human body.
In this work, tangerine peel oil extraction is carried out by applying the supercritical carbon dioxide (scCO(2)) extraction. The effect of extraction parameters on extraction yield was dis-cussed, at particle size of 0.2-1.0mm, temperature of 35-55 degrees C, pressure of 10-30MPa and extraction time of 0-180min. And the response surface methodology (RSM) with a BoxBehnken Design (BBD) was applied to obtain the optimal extraction conditions. Based on this investigation, it is indicated that the optimized operation conditions for tangerine peel oil extraction was temperature 45 degrees C, pressure 14MPa and extraction time 147min, and the largest experimental yield of tangerine peel oil was 1.34%. Moreover, a gas chromatography mass spectrometry (GC-MS) analysis was used to determine the chemical composition of tangerine peel oil. The major compounds found in the tangerine peel oil were n-hexadecanoic acid (14.62%), linoleic acid (32.3%) and oleic acid (20.42%). Finally, two kinetic models were used to correlate the experimental results, and the parameters in both models have been optimized by simulating annealing (SA) algorithm. The results show that the overall average absolute relative deviation (AARD) values of model I and model II are 3.42% and 2.76%, respectively. The AARD value of model II is smaller and the application of model II is more extensive. The extraction parameters optimization, chemical composition analysis and kinetics modelling can provide theoretical basis for industrialization of extraction of tangerine peel oil. (c) 2020 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.