Groundwater remediation using Magnesium-Aluminum alloys and in situ layered doubled hydroxides.

In situ remediation of groundwater by zerovalent iron (ZVI)-based technology faces the problems of rapid passivation, fast agglomeration, limited range of pollutants and secondary contamination. Here a new concept of Magnesium-Aluminum (Mg-Al) alloys and in situ layered double hydroxides on is proposed for the degradation and removal of a wide variety of inorganic and organic pollutants from groundwater. The Mg-Al alloy provides the electrons for the chemical reduction and/or the degradation of pollutants while released Mg2+, Al3+ and OH- ions react to generate in situ LDH precipitates, incorporating other divalent and trivalent metals and oxyanions pollutants and further adsorbing the micropollutants. The Mg-Al alloy outperforms ZVI for treating acidic, synthetic groundwater samples contaminated by complex chemical mixtures of heavy metals (Cd2+, Cr6+, Cu2+, Ni2+ and Zn2+), nitrate, AsO33-, methyl blue, trichloroacetic acid and glyphosate. Specifically, the Mg-Al alloy achieves removal efficiency ≥99.7% for these multiple pollutants at concentrations ranging between 10 and 50 mg L-1 without producing any secondary contaminants. In contrast, ZVI removal efficiency did not exceed 90% and secondary contamination up to 220 mg L-1 Fe was observed. Overall, this study provides a new alternative approach to develop efficient, cost-effective and green remediation for water and groundwater.

Enhanced Oral Absorption of Icaritin by Using Mixed Polymeric Micelles Prepared with a Creative Acid-Base Shift Method.

The purpose of this study was to develop mixed polymeric micelles with high drug loading capacity to improve the oral bioavailability of icaritin with Soluplus® and Poloxamer 407 using a creative acid-base shift (ABS) method, which exhibits the advantages of exclusion of organic solvents, high drug loading and ease of scaling-up. The feasibility of the ABS method was successfully demonstrated by studies of icaritin-loaded polymeric micelles (IPMs). The prepared IPMs were characterized to have a spherical shape with a size of 72.74 ± 0.51 nm, and 13.18% drug loading content. In vitro release tests confirmed the faster release of icaritin from IPMs compared to an oil suspension. Furthermore, bioavailability of icaritin in IPMs in beagle dogs displayed a 14.9-fold increase when compared with the oil suspension. Transcellular transport studies of IPMs across Caco-2 cell monolayers confirmed that the IPMs were endocytosed in their intact forms through macropinocytosis, clathrin-, and caveolae-mediated pathways. In conclusion, the results suggested that the mixed micelles of Soluplus® and Poloxamer 407 could be a feasible drug delivery system to enhance oral bioavailability of icaritin, and the ABS method might be a promising technology for the preparation of polymeric micelles to encapsulate poorly water-soluble weakly acidic and alkaline drugs.

Preparation, Characterization, and In Vivo Evaluation of Amorphous Icaritin Nanoparticles Prepared by a Reactive Precipitation Technique.

Icaritin is a promising anti-hepatoma drug that is currently being tested in a phase-III clinical trial. A novel combination of amorphization and nanonization was used to enhance the oral bioavailability of icaritin. Amorphous icaritin nanoparticles (AINs) were prepared by a reactive precipitation technique (RPT). Fourier transform infrared spectrometry was used to investigate the mechanism underlying the formation of amorphous nanoparticles. AINs were characterized via scanning electron microscopy, X-ray powder diffraction, and differential scanning calorimetry. Our prepared AINs were also evaluated for their dissolution rates in vitro and oral bioavailability. The resultant nanosized AINs (64 nm) were amorphous and exhibited a higher dissolution rate than that derived from a previous oil-suspension formulation. Fourier transform infrared spectroscopy (FTIR) revealed that the C=O groups from the hydrophilic chain of polymers and the OH groups from icaritin formed hydrogen bonds that inhibited AIN crystallization and aggregation. Furthermore, an oral administration assay in beagle dogs showed that Cmax and AUClast of the dried AINs formulation were 3.3-fold and 4.5-fold higher than those of the oil-suspension preparation (p < 0.01), respectively. Our results demonstrate that the preparation of amorphous drug nanoparticles via our RPT may be a promising technique for improving the oral bioavailability of poorly water-soluble drugs.

Preparation of Poly(glycidyl methacrylate) (PGMA) and Amine Modified PGMA Adsorbents for Purification of Glucosinolates from Cruciferous Plants.

Glucosinolates (GLs) are of great interest for their potential as antioxidant and anticancer compounds. In this study, macroporous crosslinked copolymer adsorbents of poly (glycidyl methacrylate) (PGMA) and its amine (ethylenediamine, diethylamine, triethylamine)-modified derivatives were prepared and used to purify the GLS glucoerucin in a crude extract obtained from a cruciferous plant. These four adsorbents were evaluated by comparing their adsorption/desorption and decolorization performance for the purification of glucoerucin from crude plant extracts. According to the results, the strongly basic triethylamine modified PGMA (PGMA-III) adsorbent showed the best adsorption and desorption capacity of glucoerucin, and its adsorption data was a good fit to the Freundlich isotherm model and pseudo-second-order kinetics; the PGMA adsorbent gave the optimum decolorization performance. Furthermore, dynamic adsorption/desorption experiments were carried out to optimize the purification process. Two glass columns were serially connected and respectively wet-packed with PGMA and PGMA-III adsorbents so that glucoerucin could be decolorized and isolated from crude extracts in one process. Compared with KCl solution, aqueous ammonia was a preferable desorption solvent for the purification of glucoerucin and overcame the challenges of desalination efficiency, residual methanol and high operation costs. The results showed that after desorption with 10% aqueous ammonia, the purity of isolated glucoerucin was 74.39% with a recovery of 80.63%; after decolorization with PGMA adsorbent, the appearance of glucoerucin was improved and the purity increased by 11.30%. The process of using serially connected glass columns, wet-packed with PGMA and PGMA-III, may provide a simple, low-cost, and efficient method for the purification of GLs from cruciferous plants.

Investigating the strategies for microbial production of trehalose from lignocellulosic sugars.

Trehalose, a multi-functional and value-added disaccharide, can be efficiently biosynthesized from glucose by using a synergetic carbon utilization mechanism (SynCar) which coupled phosphoenolpyruvate (PEP) generation from the second carbon source with PEP-dependent phosphotransferase system (PTS) to promote non-catabolic use of glucose. Considering glucose and xylose present in large amounts in lignocellulosic sugars, we explored new strategies for conversion of both sugars into trehalose. Herein, we first attempted trehalose production from xylose directly, based on which, synergetic utilization of glucose, and xylose prompted by SynCar was implemented in engineered Escherichia coli. As the results, the final titer of trehalose reached 5.55 g/L in shake flask experiments. The conversion ratio or utilization efficiency of glucose or xylose to trehalose was around fourfold higher than that of the original strain (YW-3). This work not only demonstrated the possibility of directly converting xylose (C5 sugar) into trehalose (C12 disaccharide), but also suggested a promising strategy for trehalose production from lignocellulosic sugars for the first time.

A Cheap and Convenient Method of Liposome Preparation Using Glass Beads as a Source of Shear Force.

Liposomes, the biocompatible lipid bilayer vesicles, have attracted immense attention due to their distinctive features such as efficient vehicle for the delivery of a wide range of therapeutic agents, adjustable formulation properties, and high drug entrapment efficiency. In this contribution, we present a simple method for the preparation of liposomes using glass beads and compared the potential of this method with conventional methods of liposome preparation. The prepared liposomes were characterized by different analytical techniques (HPLC, DLS, TEM, differential scanning calorimetry, and in vitro drug release). Our findings revealed that the particle size of liposomes is mainly dependent on the size of the glass beads and the glass bead shearing time. An average liposome size of 67.7 ± 25.5 nm was obtained using 2-mm glass beads after 24-h incubation at 200 rpm. The liposomes prepared under the optimized conditions exhibited a high encapsulation efficiency of 92.1 ± 1.7% with 31.08% drug release after 360 min at 37°C. In conclusion, the developed method is a simple and convenient process of liposome preparation of different sizes with desirable entrapment efficiency capacity.

Preparation of multi-enzyme co-immobilized nanoparticles by bis-aryl hydrazone bond conjugation.

A novel multi-enzyme co-immobilized nanoparticle was prepared by the bis-aryl hydrazone conjugation strategy for enhancing the overall reaction efficiency and specificity. It can be seen that the molar substitution ratios of succinimidyl 6-hydrazinonicotinamid acetone hydrazone or succinimidyl 4-formylbenzoate to glucose oxidase (GOX) or horseradish peroxidase (HRP) increased with the concentration of the linking reagents. The amount of the immobilized conjugates on the support was measured to be 22.8 ± 1.6 mg/g-particle, and it meant that more than 90% of the GOX-HRP conjugates were successfully attached onto the polystyrene (PS) nanoparticles. Moreover, the immobilized bi-enzymes conjugate on the PS nanoparticles increased about 1.6-fold compared with that of free enzymes.

Enhanced humoral and cell-mediated immune responses generated by cationic polymer-coated PLA microspheres with adsorbed HBsAg.

Surface-engineered particulate delivery systems for vaccine administration have been widely investigated in experimental and clinical studies. However, little is known about charge-coated microspheres as potential recombinant subunit protein antigen delivery systems in terms of adsorption and related immune responses. In the present study, cationic polymers, including chitosan (CS), chitosan chloride (CSC), and polyethylenimine (PEI), were used to coat PLA microspheres to build positively charged surfaces. Antigen adsorption capacity was enhanced with increased surface charge of coated microspheres. In macrophages, HBsAg adsorbed on the surface of cationic microspheres specifically enhanced antigen uptake and augmented CD86, MHC I, and MHC II expression and IL-1ß, IL-6, TNF-α, and IL-12 release. Antigens were more likely to localize independent of lysosomes after phagocytosis in antigen-attached cationic microsphere formulations. After intraperitoneal immunization, cationic microsphere-based vaccine formulations generated a rapid and efficient humoral immune response and cytokine release as compared with aluminum-adsorbed vaccine and free antigens in vivo. Moreover, microspheres coated with cationic polymers with relatively high positive charges and higher antigen adsorption exhibited strong stimulation of the Th1 response. In conclusion, PLA microspheres coated with cationic polymers may be a potential recombinant antigen delivery system to induce strong cell and humoral immune responses.

A novel cleaning process for industrial production of xylose in pilot scale from corncob by using screw-steam-explosive extruder.

Steam explosion is the most promising technology to replace conventional acid hydrolysis of lignocellulose for biomass pretreatment. In this paper, a new screw-steam-explosive extruder was designed and explored for xylose production and lignocellulose biorefinery at the pilot scale. We investigated the effect of different chemicals on xylose yield in the screw-steam-explosive extrusion process, and the xylose production process was optimized as followings: After pre-impregnation with sulfuric acid at 80 °C for 3 h, corncob was treated at 1.55 MPa with 9 mg sulfuric acid/g dry corncob (DC) for 5.5 min, followed by countercurrent extraction (3 recycles), decoloration (activated carbon dosage 0.07 g/g sugar, 75 °C for 40 min), and ion exchange (2 batches). Using this process, 3.575 kg of crystal xylose was produced from 22 kg corncob, almost 90 % of hemicellulose was released as monomeric sugar, and only a small amount of by-products was released (formic acid, acetic acid, fural, 5-hydroxymethylfurfural, and phenolic compounds were 0.17, 1.14, 0.53, 0.19, and 1.75 g/100 g DC, respectively). All results indicated that the screw-steam-explosive extrusion provides a more effective way to convert hemicellulose into xylose and could be an alternative method to traditional sulfuric acid hydrolysis process for lignocellulose biorefinery.

Enhanced Electrochemical Impedance Spectroscopy Analysis of Microbial Biofilms on an Electrochemically In Situ Generated Graphene Interface.

Biofilms can cause many bacterial diseases, such as dental disease. An in vitro detection of biofilms may help to screen antibiofilm drugs. An impedance measurement based on an Au electrode has been successfully used for in vitro real-time monitoring of animal and human cell growth. However, microbial growth on the Au electrode produced a poor signal because of the small size of microbial cells. We have recently demonstrated that graphene derivatives can be produced on a carbon electrode through facile electrochemical activation, thus forming a reduced graphene oxide-carbon electrode (rGO-CE). Based on this fact, we hypothesized that an in vitro formed rugose graphene layer of rGO-CE may provide a large surface area for the growth of microbial biofilms and can therefore produce a strong impedance signal in response to a change in the biomass. In this study, three oral bacteria, Streptococcus mutans (S. mutans), Actinomyces viscosus (A. viscosus), and Lactobacillus fermentum (L. fermentum), were cultured on the surfaces of rGO-CE. As a result, the impedance response signal of the rGO-CE for the growth of S. mutans and A. viscosus was found to be 3.3 times and 6.0 times stronger than that of the Au electrode at 1.17 and 54.7 kHz, respectively. In particular, the poorly adhering strain of L. fermentum also produced a detectable signal on the graphene electrode but not on the Au electrode at 1.17 kHz. Furthermore, destructions of the biofilms grown on the rGO-CE by cetylpyridinium chloride were successfully monitored by impedance changes. Overall, it is promising to develop a graphene-based impedance biosensor platform for biofilm study and antibiofilm drug screening.

A rapid microwave-assisted phosphoric-acid treatment on carbon fiber surface for enhanced cell immobilization in xylitol fermentation.

A rapid microwave-assisted phosphoric-acid treatment (MP) was applied to modify the surface of carbon fibers (CFs) for cell immobilization and fermentation. After the novel treatment, the surface of CFs subjected to MP (CF-MP) contained the CPO and COP bonds and the surface area and hydrophilicity were enhanced, which improved the cell adhesion and growth compared with the raw CF. Because of these structural advantages, the biocompatibilities of the CF-MP as a cell carrier were improved according to the immobilization behavior of microorganisms and batch fermentation. The optimized immobilization efficiency of Candida tropicalis on the CF-MP was improved to 0.587 g g-1, and the maximum xylitol yield and volumetric productivity were 67.15% and 1.16 g h-1 L-1, respectively, which were substantially higher than that in case of the untreated CF. This indicated that the biocompatibility of CF improved after the favorable MP surface treatment, resulting in the enhancement of immobilized efficiency and xylitol fermentation.

Preparation and antimicrobial activity of oregano essential oil Pickering emulsion stabilized by cellulose nanocrystals.

An effective antimicrobial system was developed by using oregano essential oil (OEO) Pickering emulsion. The Pickering emulsion was stabilized by cellulose nanocrystals (CNCs), which were from microcrystalline cellulose (MCC) by selective oxidization ammonium persulfate. Factors affecting the stability of OEO Pickering emulsions, such as oil/water ratio, CNCs concentration, ionic concentration and pH, were studied and analysed by the measurement of the droplet sizes and Zeta potential. The results showed that the emulsions had good stability at higher CNCs concentration and pH values, or at lower oil/water ratio and salt concentration. In addition, the antimicrobial efficacy of OEO Pickering emulsions against four food-related microorganisms was evaluated by determining the minimal inhibitory concentration (MIC). The results showed that prepared OEO Pickering emulsions could efficiently inhibit the growth of four tested microorganisms by destroying the integrity of the cells' membrane. The research would have a certain leading meaning on the design and use of OEO Pickering emulsions stabilized by CNCs for the delivery of antimicrobial essential oils in the food and other industries.

Investigation of the Synergetic Effect of Xylose Metabolic Pathways on the Production of Glutaric Acid.

Efficient utilization of lignocellulose is pivotal for economically converting renewable feedstocks into value-added products. Xylose is the second most abundant sugar in lignocellulose, but it is quite challenging to ferment xylose as efficiently as glucose by microorganisms. Here, we investigated the metabolic potential of three xylose catabolic pathways (isomerase, Weimberg, and Dahms pathways) and illustrated the synergetic effect between the isomerase pathway and Weimberg pathway for the synthesis of chemicals derived from 2-ketoglutarate and acetyl-CoA. When using glutaric acid as the target product, employment of such synergetic pathways in combination resulted in an increased glutaric acid titer (602 mg/L) compared with using each pathway alone (104 or 209 mg/L), and this titer even outcompetes that obtained from the glucose catabolic pathway for glutaric acid synthesis (420 mg/L). This work validates a novel and powerful strategy for xylose metabolic utilization to overcome the inefficiency of using a single xylose metabolic pathway for the synthesis of TCA cycle derived chemicals.

Biodegradable Poly(amino acid)-Gold-Magnetic Complex with Efficient Endocytosis for Multimodal Imaging-Guided Chemo-photothermal Therapy.

Gold complexes can serve as efficient photothermal converters for cancer therapy, but their non-biodegradability hinders clinical bioapplications. Although enormous effort has been devoted, the conventionally adopted synthetic methods of biodegradation are characterized by high cost and complicated procedures, which delay the process of further clinical translation of gold complexes. Here, we report a multifunctional poly(amino acid)-gold-magnetic complex with self-degradation properties for synergistic chemo-photothermal therapy via simple and green chemistry methods. Nanoparticles of ∼3 nm in the biodegradation product were observed in simulated body fluid in 4 days. The biodegradability mainly benefits from the weakened internal electrostatic interaction of the poly(amino acid) by the ions in simulated body fluid. It is demonstrated that the poly(amino acid)-gold-magnetic complex has great cellular endocytosis by taking advantage of the guanidine group in arginine and possesses multimodal imaging and efficient tumor ablation (94%). This study reports a possibility for gold-magnetic complexes composed of poly(amino acid) to serve as a biodegradable nanotherapeutic for clinical applications.

Comparison of general rate model with a new model--artificial neural network model in describing chromatographic kinetics of solanesol adsorption in packed column by macroporous resins.

Herein, two models, the general rate model taking into account convection, axial dispersion, external and intra-particle mass transfer resistances and particle size distribution (PSD) and the artificial neural network model (ANN) were developed to describe solanesol adsorption process in packed column using macroporous resins. First, Static equilibrium experiments and kinetic experiments in packed column were carried out respectively to obtain experimental data. By fitting static experimental data, Langmuir isotherm and Freundlich isotherm were estimated, and the former one was used in simulation coupled with general rate model considering better correlative coefficients. The simulated results showed that theoretical predictions of general rate model with PSD were well consistent with experimental data. Then, a new model, the ANN model, was developed to describe present adsorption process in packed column. The encouraging simulated results showed that ANN model could describe present system even better than general rate model. At last, by using the predictive ability of ANN model, the influence of each experimental parameter was investigated. Predicted results showed that with the increases of particle porosity and the ratio of bed height to inner column diameter (ROHD), the breakthrough time was delayed. On the contrary, an increase in feed concentration, flow rate, mean particle diameter and bed porosity decreased the breakthrough time.

Deconstruction of corncob by steam explosion pretreatment: Correlations between sugar conversion and recalcitrant structures.

In this work, acid-catalyzed steam explosion was carried out as a pretreatment to hydrolyze hemicellulose and increase the enzymatic digestibility of corncob. Pretreatment conditions were varied to achieve structural alterations in a wide range: type of acids (sulfuric acid and oxalic acid), acid concentration (0.1-1.5wt.%) and pressure (1.0-1.8MPa). The pretreated residues were analyzed by chemical analysis, surface area measurement and x-ray diffraction. Biomass and cellulose crystallinity, lignin content and specific surface area were obtained and their correlations with sugar conversion were compared. The results suggested that these parameters were coupled together and they explained in part the diversity of the literature data that improves understanding of steam explosion pretreatment.

Magnetic Iron Oxide Nanoparticle Seeded Growth of Nucleotide Coordinated Polymers.

The introduction of functional molecules to the surface of magnetic iron oxide nanoparticles (NPs) is of critical importance. Most previously reported methods were focused on surface ligand attachment either by physisorption or covalent conjugation, resulting in limited ligand loading capacity. In this work, we report the seeded growth of a nucleotide coordinated polymer shell, which can be considered as a special form of adsorption by forming a complete shell. Among all of the tested metal ions, Fe(3+) is the most efficient for this seeded growth. A diverse range of guest molecules, including small organic dyes, proteins, DNA, and gold NPs, can be encapsulated in the shell. All of these molecules were loaded at a much higher capacity compared to that on the naked iron oxide NP core, confirming the advantage of the coordination polymer (CP) shell. In addition, the CP shell provides better guest protein stability compared to that of simple physisorption while retaining guest activity as confirmed by the entrapped glucose oxidase assay. Use of this system as a peroxidase nanozyme and glucose biosensor was demonstrated, detecting glucose as low as 1.4 µM with excellent stability. This work describes a new way to functionalize inorganic materials with a biocompatible shell.

Antibacterial Adhesion of Poly(methyl methacrylate) Modified by Borneol Acrylate.

Poly(methyl methacrylate) (PMMA) is a widely used biomaterial. But there is still a challenge facing its unwanted bacterial adhesion because the subsequent biofilm formation usually leads to failure of related implants. Herein, we present a borneol-modified PMMA based on a facile and effective stereochemical strategy, generating antibacterial copolymer named as P(MMA-co-BA). It was synthesized by free radical polymerization and studied with different ratio between methyl methacrylate (MMA) and borneol acrylate (BA) monomers. NMR, GPC, and EA, etc., were used to confirm their chemical features. Their films were challenged with Escherichia coli (Gram-negative) and Bacillus subtilis (Gram-positive), showing a BA content dependent antibacterial performance. The minimum effective dose should be 10%. Then in vivo subcutaneous implantations in mice demonstrated their biocompatibilities through routine histotomy and HE staining. Therefore, P(MMA-co-BA)s not only exhibited their unique antibacterial character but also suggested a potential for the safe usage of borneol-modified PMMA frame and devices for further implantation.

Effect of sulfonated lignin on enzymatic activity of the ligninolytic enzymes Cα-dehydrogenase LigD and ß-etherase LigF.

NAD+-dependent Cα-dehydrogenase LigD and glutathione-dependent ß-etherase LigF which selectively cleave the ß-O-4 aryl ether linkage present in lignin, are key-enzymes for the biocatalytic depolymerization of lignin. However, the catalytic efficiency of the two enzymes is low when they are used to break down the ß-aryl ether linkage in natural lignin. When sulfonated lignin was added to LigF hydrolysis reactions, the conversion rate of MPHPV decreased significantly from 99.5% to 32.6%. On the contrary, sulfonated lignin has little affection on LigD, which the conversion rate of GGE only decreased from 41.7% to 41%. The strong nonspecific interactions of enzymes onto sulfonated lignin detected by surface plasmon resonance (SPR) and isothermal titration calorimetric (ITC) was obvious and universal, which can reduce enzyme activity of many enzymes, including ligninolytic enzyme ß-etherase LigF. To elucidate the exact mechanisms by which ß-etherase LigF interact with lignin, molecular modeling was applied. Finally, analysis on catalytic efficiency of LigD and LigF in different concentrations and molecular weights of sulfonated lignin, solution ionic strength, pH, temperature and concentration of Tween 80 revealed that electrostatic interactions and hydrophobic interactions play important roles in absorption between LigF and sulfonated lignin.

The stability and degradation kinetics of Sulforaphene in microcapsules based on several biopolymers via spray drying.

Sulforaphene (SFE) was extracted from the radish seeds and the purity of SFE extracted by our laboratory was 95%. It is well known that SFE can prevent cancers. It is also known that SFE is unstable to heat. To overcome the problem, SFE microcapsules using natural biopolymers were prepared by spray drying. The results indicated that SFE microcapsules using hydroxypropyl-ß-cyclodextrin (HP-ß-CD), maltodextrin (MD) and isolated soybean protein (SPI) as wall materials could effectively improve its stability against heat, especially SFE-loaded HP-ß-CD and MD microcapsules. The amount of SFE in the microcapsules was found 20% higher than that of the non-encapsulated SFE under 90 °C in 168 h. Our finding suggested that the rate of degradation of the non-encapsulated and encapsulated SFE with HP-ß-CD, MD and SPI followed the first-order kinetics. The speed of the degradation of the encapsulated SFE in biopolymers increased from SFE with HP-ß-CD, to SFE with MD, and to SFE-SPI. The non-encapsulated SFE degrades fastest.