Showing papers by "Guanghui Ma published in 2014"

Peptide-Induced Hierarchical Long-Range Order and Photocatalytic Activity of Porphyrin Assemblies

Abstract: Long-range structural order and alignment over different scales are of key importance for the regulation of structure and functionality in biology. However, it remains a great challenge to engineer and assemble such complex functional synthetic systems with order over different length scales from simple biologically relevant molecules, such as peptides and porphyrins. Herein we describe the successful introduction of hierarchical long-range order in dipeptide-adjusted porphyrin self-assembly by a thermodynamically driven self-orienting assembly pathway associated with multiple weak interactions. The long-range order and alignment of fiber bundles induced new properties, including anisotropic birefringence, a large Stokes shift, amplified chirality, and excellent photostability as well as sustainable photocatalytic activity. We also demonstrate that the aligned fiber bundles are able to induce the epitaxially oriented growth of Pt nanowires in a photocatalytic reaction.

Multifunctional Porous Microspheres Based on Peptide-Porphyrin Hierarchical Co-Assembly

Abstract: Photocatalytically active, multi-chambered, biomolecule-based microspheres were prepared by hierarchical co-assembly of simple dipeptides and porphyrins The colloidal microspheres are highly hydrated and consist of a network of J-aggregate nanoscale substructures that serve as light-harvesting antennae with a relatively broad spectral cross-section and considerable photostability These optical properties can be exploited in photocatalytic reactions involving inorganic or organic species Taken together, these structural and functional features suggest that soft porous biomolecule-based colloids are a plausible photosynthetic model that could be developed towards demonstrating aspects of primitive abiotic cellularity

Nanoengineering of Stimuli-Responsive Protein-Based Biomimetic Protocells as Versatile Drug Delivery Tools

Abstract: We present a general strategy to nanoengineer protein-based colloidal spheres (biomimetic protocells) as versatile delivery carriers with stimuli responsiveness by the electrostatic assembly of binary components (proteins and polypeptides) in association with intermolecular disulfide cross-linking. The size of the colloidal spheres, ranging from nanoscale to microscale, is readily tuned through parameters like protein and polypeptide concentration, the ratio between both, pH, and so on. Moreover, such colloidal spheres show versatile encapsulation of various guest molecules including small organic molecules and biomacromolecules. The pH and redox dual-responsiveness facilitates the rapid release of the payload in an acidic and reductant-enriched ambient such as in lysosomes. Thus, nanoengineering of protein-based biomimetic protocells opens a new alternative avenue for developing delivery vehicles with multifunctional properties towards a range of therapeutic and diagnostic applications.

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

Abstract: 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 PIA 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-1 beta, IL-6, TNF-alpha, 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.

Systematic studies of Pickering emulsions stabilized by uniform-sized PLGA particles: preparation and stabilization mechanism

Abstract: Pickering emulsions stabilized by solid particles have been widely studied in the past decades due to improved stability and reduced use of small molecular surfactants. Recently, the application of Pickering emulsions in pharmaceutics has been attracting increasing attention but very limited practical use has been demonstrated, because most of the investigated particles possess poor biodegradability, which is inappropriate in pharmaceutics. Some reported biodegradable particles were too hydrophilic to stabilize emulsions, which needs further particle modification or additional surfactants. Fortunately, biodegradable poly(D,L-lactic-co-glycolic acid) (PLGA) with tunable hydrophilicity makes itself a promising material to prepare Pickering emulsions. However, the mechanism of emulsion stabilization still remains unknown. Moreover, fabrication of large amounts of uniform-sized and size-controlled PLGA particles by traditional methods is very difficult, which further increases the difficulty to perform the research. In the present study, we applied Shirasu Porous Glass (SPG) premix membrane emulsification to solve this problem. The stabilization mechanism of Pickering emulsions stabilized by PLGA particles was systematically studied for the first time. The factors including oil type, particle properties, concentration, molecular weight (Mw) and oil–water volume ratio were analyzed through particle wettability and interfacial influence. We found that octanol was an appropriate oil type, and its small particle size, high particle concentration and high Mw were favorable for emulsion stability. By changing the oil–water volume ratio, stable emulsions were also readily achieved. These studies proved that Pickering emulsions stabilized by PLGA particles had wide potential applications in pharmaceutics and tissue engineering.

Porous TiO2 Materials through Pickering High-Internal Phase Emulsion Templating

Abstract: We report a facile method for preparing porous structured TiO2 materials by templating from Pickering high-internal phase emulsions (HIPEs). A Pickering HIPE with an internal phase of up to 80 vol %, stabilized by poly(N-isopropylacrylamide)-based microgels and TiO2 solid nanoparticles, was first formulated and employed as a template to prepare the porous TiO2 materials with an interconnected structure. The resultant materials were characterized by scanning electron microscopy, X-ray diffraction, and mercury intrusion. Our results showed that the parent emulsion droplets promoted the formation of macropores and interconnecting throats with sizes of similar to 50 and similar to 10 mu m, respectively, while the interfacially adsorbed microgel stabilizers drove the formation of smaller pores (similar to 100 nm) throughout the macroporous walls after drying and sintering. The interconnected structured network with the bimodal pores could be well preserved after calcinations at 800 degrees C. In addition, the photocatalytic activity of the fabricated TiO2 was evaluated by measuring the photodegradation of Rhodamine B in water. Our results revealed that the fabricated TiO2 materials are good photocatalysts, showing enhanced activity and stability in photodegrading organic molecules.

Enabling multi-enzyme biocatalysis using coaxial-electrospun hollow nanofibers: redesign of artificial cells

Abstract: Highly efficient immobilization of multi-enzyme systems involving cofactor regeneration represents one of the greatest challenges in bioprocessing. Particulate artificial cells with enzymes and cofactors encapsulated within microcapsules have long been the major type of multi-enzyme biocatalysts. In the present work, a novel hollow nanofiber-based artificial cell that performs multi-step reactions involving efficient coenzyme regeneration was fabricated in situ by a facile co-axial electrospinning process. To that end, a mixture of glycerol and water containing the dissolved multi-enzyme system for the bile acid assay, which included 3α-hydroxysteroid dehydrogenase (3α-HSD), diaphorase (DP) and NADH was fed as the core phase solution, and a N,N-dimethylacetylamide solution of 30 wt% polyurethane was fed as the shell phase solution during the co-axial electrospinning. The relationship between the structures of the hollow nanofibers and the activity and stability of the encapsulated enzymes was studied. At core and shell phase electrospinning solution flow rates of 0.07 and 0.5 mL h−1, activity recoveries as high as 76% and 82% were obtained for the encapsulated 3α-HSD and DP. The hollow nanofiber-based artificial cells were successfully used for the bile acid assay, yielding good linearity for bile acid concentrations ranging from 0–200 μM. Compared with the solution-based multi-enzyme system, the hollow nanofiber-based multi-enzyme system presented a lumped activity recovery of 75%. In addition, the hollow nanofiber provided the multi-enzyme system confined inside the nano-domain of the hollow fibers with a unique stabilizing mechanism, such that more than a 170-fold increase in half-life at 25 °C was obtained for the encapsulated 3α-HSD and DP. This study is expected to greatly promote and broaden the application of multi-enzyme systems in industry, biosensor, biomedical, and many other related research fields.

Hybrid magnetic cross-linked enzyme aggregates of phenylalanine ammonia lyase from Rhodotorula glutinis.

Abstract: Novel hybrid magnetic cross-linked enzyme aggregates of phenylalanine ammonia lyase (HM-PAL-CLEAs) were developed by co-aggregation of enzyme aggregates with magnetite nanoparticles and subsequent crosslinking with glutaraldehyde. The HM-PAL-CLEAs can be easily separated from the reaction mixture by using an external magnetic field. Analysis by scanning electron microscopy (SEM) and confocal laser scanning microscopy (CLSM) indicated that PAL-CLEAs were inlayed in nanoparticle aggregates. The HM-PAL-CLEAs revealed a broader limit in optimal pH compared to free enzyme and PAL-CLEAs. Although there is no big difference in Km of enzyme in CLEAs and HM-PAL-CLEAs, Vmax of HM-PAL-CLEAs is about 1.75 times higher than that of CLEAs. Compared with free enzyme and PAL-CLEAs, the HM-PAL-CLEAs also exhibited the highest thermal stability, denaturant stability and storage stability. The HM-PAL-CLEAs retained 30% initial activity even after 11 cycles of reuse, whereas PAL-CLEAs retained 35% of its initial activity only after 7 cycles. These results indicated that hybrid magnetic CLEAs technology might be used as a feasible and efficient solution for improving properties of immobilized enzyme in industrial application.

Novel vaccine delivery system induces robust humoral and cellular immune responses based on multiple mechanisms.

Abstract: Aiming to enhance the immunogenicity of H5N1 split vaccine, the development of a novel antigen delivery system based on quaternized chitosan hydrogel microparticles (Gel MPs) with multiple mechanisms of immunity enhancement is attempted. Gel MPs based on ionic cross-linking are prepared in a simple and mild way. Gel MPs are superior as a vaccine delivery system due to their ability to: 1) enhance cellular uptake and endosomal escape of antigens in dendritic cells (DCs); 2) significantly activate DCs; 3) form an antigen depot and recruit immunity cells to improve antigen capture. Further in vivo investigation shows that Gel MPs, in comparison to aluminum salts (Alum), LPS, and covalent cross-linking quaternized chitosan MPs (GC MPs), induce higher humoral and cellular immune responses with a mixed Th1/Th2 immunity. In conclusion, these results demonstrate that Gel MPs are efficient antigen delivery vehicles based on multiple mechanisms to enhance both humoral and cellular immune responses against H5N1 split antigen.

Comparative Studies on the Influences of Primary Emulsion Preparation on Properties of Uniform-Sized Exenatide-Loaded PLGA Microspheres

Abstract: Purpose It is well known that primary emulsion (W1/O) preparation process (by ultrasonication or homogenization) plays an important role in the properties of drug-loaded microspheres, such as encapsulation efficiency, release behavior and pharmacodynamics. However, its involved mechanism has not been intensively and systematically studied, partly because that broad size distribution of the resultant particles prepared by conventional preparation can greatly disturb the analysis and reliability of the results. Here, we focused on the relevant studies.

Construction of stable chainlike Au nanostructures via silica coating and exploration for potential photothermal therapy.

Abstract: A facile one-pot approach is successfully developed to construct the stable Au nanochains with silica shell via self-assembly and classical Stober process. The resulting Au chain@SiO2 nanoparticles holds great promise for serving as a safe, reusable, and high-performance photothermal agent against cancer.

Preparation of uniform-sized colloidosomes based on chitosan-coated alginate particles and its application for oral insulin delivery

Abstract: Colloidosomes are microcapsules that consist of a hollow core coated by a shell composed of self-assembled colloidal particles. In recent years, they have attracted significant attention as potential vehicles for the controlled delivery of active ingredients. A key challenge in such applications is the production of uniform-sized colloidosomes for the encapsulation of active ingredients such that the actual delivery amount can be well controlled. Based on our previous study on an ethyl acetate-in-water emulsion stabilized by chitosan-coated alginate particles, we further prepared monodisperse colloidosomes with a high yield and low permeability by combining the premix membrane emulsification technique and polymer deposition method. The potential application of the formed colloidosomes as oral insulin delivery vehicles was investigated. Our results revealed that in comparison to conventional PLGA microspheres, the formulated colloidosomes showed high drug encapsulation efficiency (up to 96.7%) and an obvious pH sensitive release profile. Moreover, in animal testing, the colloidosomes formulation achieved a long-term hypoglycemic effect up to 6 h, which confirmed its application as an oral drug delivery system.

“Ready-to-use” hollow nanofiber membrane-based glucose testing strips

Abstract: A novel "ready-to-use" glucose test strip based on a polyurethane hollow nanofiber membrane was fabricated through facile co-axial electrospinning. By utilizing glucose oxidase and horseradish peroxidase in the core-phase solution, and a chromogenic agent either in the core solution (in which case 2,2'-azinobis-(3-ethylbenzthiazoline-6-sulphonate) (ABTS) was used) or in the shell-phase solution (in which case o-dianisidine was used) for co-axial electrospinning, in situ co-encapsulation of the two enzymes within the hollow nano-chamber and incorporation of chromogenic agents either inside the nano-chamber or in the shell of the hollow nanofibers was realized. Such unique "all-in-one" feature enabled the prepared hollow nanofiber membrane-based test strips to be applied either as colorimetric sensors in solution or as an optical biosensor operated in the "dip-and-read" mode. When used as a colorimetric biosensor in solution, the test strip with o-dianisidine as chromogenic agent shows an excellent linear response range between 0.01 mM to 20 mM and a high apparent lumped activity recovery of 62.1% as compared to the reaction rate of the free bi-enzyme system. While the activity recovery of the test strip with ABTS as chromogenic agent is only 18.0%, and the test strip is found to be unstable due to spontaneous-oxidation of the ABTS. The o-dianisidine test strip was also applied as an optical biosensor, visible rufous color was quickly developed on the surface of the membrane upon dropping 10 mu L of glucose sample, and an excellent correlation between differential diffusive reflectance of the test strip at 440 nm and glucose concentration was obtained in the range of 0.5-50 mM. The test strips also exhibited excellent long-term storage stability with a half-life at 25 degrees C as long as four months.

Comparison of PLA microparticles and alum as adjuvants for H5N1 influenza split vaccine: adjuvanticity evaluation and preliminary action mode analysis.

Abstract: To compare the adjuvanticity of polymeric particles (new-generation adjuvant) and alum (the traditional and FDA-approved adjuvant) for H5N1 influenza split vaccine, and to investigate respective action mode. Vaccine formulations were prepared by incubating lyophilized poly(lactic acid) (PLA) microparticles or alum within antigen solution. Antigen-specific immune responses in mice were evaluated using ELISA, ELISpot, and flow cytometry assay. Adjuvants’ action modes were investigated by determining antigen persistence at injection sites, local inflammation response, antigen transport into draining lymph node, and activation of DCs in secondary lymphoid organs (SLOs). Alum promoted antigen-specific humoral immune response. PLA microparticles augmented both humoral immune response and cell-mediated-immunity which might enhance cross-protection of influenza vaccine. With regard to action mode, alum adjuvant functions by improving antigen persistence at injection sites, inducing severe local inflammation, slightly improving antigen transport into draining lymph nodes, and improving the expression of MHC II on DCs in SLOs. PLA microparticles function by slightly improving antigen transport into draining lymph nodes, and promoting the expression of both MHC molecules and co-stimulatory molecules on DCs in SLOs. Considering the adjuvanticity and side effects (local inflammation) of both adjuvants, we conclude that PLA microparticles are promising alternative adjuvant for H5N1 influenza split vaccine.

Polyelectrolyte Doped Hollow Nanofibers for Positional Assembly of Bienzyme System for Cascade Reaction at O/W Interface

Abstract: Cationic polyelectrolyte doped hollow nanofibers prepared via facial coaxial electrospinning technology have been used for positional assembly of two enzymes, glucose oxidase (GOD) and Candida antactica lipase B (CALB), at two different positions, namely, in their lumen and on their surface. Therefore, the result is four combinations, including lumen (GOD+CALB), surface (GOD+CALB), surface (GOD)-lumen (CALB), and lumen (GOD)-surface (CALB). Surface attachment of enzymes was achieved by layer-by-layer (LbL) technology, which is based on the ion-exchange interactions between oppositely charged enzymes and polyelectrolyte that was doped in hollow nanofibers; whereas placing enzymes inside the lumen of hollow nanofibers was realized by in situ encapsulation during coelectrospinning. The hollow nanofibers-based biencyine systems were used for a cascade reaction in an oil-aqueous biphasic system, in which glucose was oxidized by GOD to generate H2O2, which was used as substrate and oxidant for CALB-catalyzed epoxidation of oleic acid in the second step. The bienzyme nanofibers membrane was found to float spontaneously at the O/W interface, which is advantageous to biphasic biocatalysis. Assembly strategies of the two enzymes affect their biocatalytic efficiency significantly by influencing the utilization efficiency of H2O2 in the reaction process. The highest reaction rate was attained by lumen (GOD)-surface (CALB), corresponding to 114.45 times enhancement as compared to that of the free bienzyme system.

Silicone oil emulsions: strategies to improve their stability and applications in hair care products

Abstract: Synopsis Silicone oils have wide range of applications in personal care products due to their unique properties of high lubricity, non-toxicity, excessive spreading and film formation. They are usually employed in the form of emulsions due to their inert nature. Until now, different conventional emulsification techniques have been developed and applied to prepare silicone oil emulsions. The size and uniformity of emulsions showed important influence on stability of droplets, which further affect the application performance. Therefore, various strategies were developed to improve the stability as well as application performance of silicone oil emulsions. In this review, we highlight different factors influencing the stability of silicone oil emulsions and explain various strategies to overcome the stability problems. In addition, the silicone deposition on the surface of hair substrates and different approaches to increase their deposition are also discussed in detail.

Preparation of uniform particle-stabilized emulsions using SPG membrane emulsification.

Abstract: Various aspects of particle-stabilized emulsions (or so-called Pickering emulsions) have been extensively investigated during the last two decades, but the preparation of uniform Pickering emulsion droplets via a simple and scalable method has been sparingly realized. We report the preparation of uniform Pickering emulsions by Shirasu porous glass (SPG) membrane emulsification. The size of the emulsion droplets ranging from 10-50 mu m can be precisely controlled by the size of the membrane pore. The emulsion droplets have a high monodispersity with coefficients of variation (CV) lower than 15% in all of the investigated systems. We further demonstrate the feasibility of locking the assembled particles at the interface, and emulsion droplets have been shown to be excellent templates for the preparation of monodisperse colloidosomes that are necessary in drug-delivery systems.