Mechanisms of Enhanced Catalysis in Enzyme–DNA Nanostructures Revealed through Molecular Simulations and Experimental Analysis

Understanding and controlling the molecular interactions between enzyme substrates and DNA nanostructures has important implications in the advancement of enzyme–DNA technologies as solutions in biocatalysis. Such hybrid nanostructures can be used to create enzyme systems with enhanced catalysis by controlling the local chemical and physical environments and the spatial organization of enzymes. Here we have used molecular simulations with corresponding experiments to describe a mechanism of enhanced catalysis due to locally increased substrate concentrations. With a series of DNA nanostructures conjugated to horseradish peroxidase, we show that binding interactions between substrates and the DNA structures can increase local substrate concentrations. Increased local substrate concentrations in HRP(DNA) nanostructures resulted in 2.9‐ and 2.4‐fold decreases in the apparent Michaelis constants of tetramethylbenzidine and 4‐aminophenol, substrates of HRP with tunable binding interactions to DNA nanostructures with dissociation constants in the micromolar range. Molecular simulations and kinetic analysis also revealed that increased local substrate concentrations enhanced the rates of substrate association. Identification of the mechanism of increased local concentration of substrates in close proximity to enzymes and their active sites adds to our understanding of nanostructured biocatalysis from which we can develop guidelines for enhancing catalysis in rationally designed systems.     

Rattle‐Structured Ag/TiO2 Nanocomposite Capsules with Bactericide and Photocatalysis Activities

A structural design featuring rattle‐type silver/titania (Ag/TiO₂) core/shell, that is, Ag@TiO₂, composite microcapsules is produced. The TiO₂ shell protects the encapsulated, movable Ag nanoparticles from breaking away under moderate loading, minimizing hence adverse environmental and biological exposure due to the metal loss, whereas the mesoporous shell serves as conduits for Ag ions released from the caged Ag nanoparticles to kill Escherichia coli in aqueous solutions under dark condition. The anatase TiO₂ shell imparts an additional, synergistic photocatalysis activity under ultraviolet irradiation. A pronouncedly enhanced photocatalysis activity results when the Ag@TiO₂ composite capsules were thermally annealed under vacuum. This “rattle‐in‐ball” hybrid architecture enables bifunctional bactericide and photocatalysis capability under both light and dark conditions, as well as mitigated environmental and biological impact in practical use.     

Fabrication and Thermal Dissipation Properties of Carbon Nanofibers Derived from Electrospun Poly(Amic Acid) Carboxylate Salt Nanofibers

Polyimides (PIs) possess excellent mechanical properties, thermal stability, and chemical resistance and can be converted to carbon materials by thermal carbonization. The preparation of carbon nanomaterials by carbonizing PI‐based nanomaterials, however, has been less studied. In this work, the fabrication of PI nanofibers is investigated using electrospinning and their transformation to carbon nanofibers. Poly(amic acid) carboxylate salts (PAASs) solutions are first electrospun to form PAAS nanofibers. After the imidization and carbonization processes, PI and carbon nanofibers can then be obtained, respectively. The Raman spectra reveal that the carbon nanofibers are partially graphitized by the carbonization process. The diameters of the PI nanofibers are observed to be smaller than those of the PAAS nanofibers because of the formation of the more densely packed structures after the imidization processes; the diameters of the carbon nanofibers remain similar to those of the PI nanofibers after the carbonization process. The thermal dissipation behaviors of the PI and carbon nanofibers are also examined. The infrared images indicate that the transfer rates of thermal energy for the carbon nanofibers are higher than those for the PI nanofibers, due to the better thermal conductivity of carbon caused by the covalent sp² bonding between carbon atoms.     

Making reusable reaction-bonded silicon nitride crucibles for silicon casting from kerf-loss silicon waste

Silicon kerf loss during wafer slicing and the broken quartz crucibles after silicon casting are two major solid wastes from photovoltaic (PV) industry. Especially, the recycle of kerf-loss silicon has become an urgent issue because near 100 000 t of solid wastes are generated every year. One of the most meaningful recycle routes of the kerf-loss silicon is to make silicon nitride crucibles to replace the quartz crucibles. In this study, we demonstrated how this is feasible through acid leaching refining, slip casting, and nitridation. The reaction-bonded silicon nitride (RBSN) crucibles after oxidation were found pure enough for silicon ingot growth. More importantly, they could be reused after ingot growth. With the present examples, the potential of using the kerf-loss silicon for fine ceramics is prominent.     

Two‐dimensional electrolyte nature of exfoliated montmorillonite nanoplatelets fabricated by soap‐free emulsion polymerization and their affinity for cations

Montmorillonite (MMT) nanoplatelets, fabricated by the exfoliation of MMT during participating in the soap‐free emulsion polymerization of methyl methacrylate, were well‐dispersed in water and performed like a two‐dimensional electrolyte. Their ionic conductivity roughly follows the Manning's limiting law for the conduction of a polyelectrolyte. The dissociated MMT nanoplatelets that carry negative charges in water were able to rapidly adsorb cations, such as tris(2,2′‐bipyridyl)ruthenium(II) (Ru(bpy)) and methylene blue (MB⁺), and recover into a smectic configuration floating as a separating phase. By using the Langmuir equation, we were able to estimate the occupied surface areas of MMT nanoplatelets by each Ru(bpy) and MB⁺ cations as 4.708 and 1.806 nm²/ion, respectively. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Theoretical analysis of the effects of asymmetric membrane structure on fouling during microfiltration

There is a growing interest in the use of both asymmetric and composite membranes for microfiltration and ultrafiltration processes. This includes particle removal applications in the semiconductor industry and virus clearance in biopharmaceutical applications. Filter fouling plays an important role in these processes. Although flux decline models have been developed for homogeneous membranes, the effects of asymmetric membrane structure on flux decline behavior remain poorly understood on a fundamental level. Here, we develop a theoretical model to describe the effects of asymmetric membrane structure on flux decline. The asymmetric structure was described by the spatial variation in Darcy permeability in the directions normal to and parallel to the membrane surface. The velocity profile and flux decline because of pore blockage were described using Darcy's law and a pore blockage and cake filtration model. Flux decline data were obtained using pseudocomposite membranes with highly interconnected polyvinylidene fluoride membranes (PVDF) and straight through pore polycarbonate track‐etched membranes (PCTE). Model composite membranes were formed by layering PCTE or PVDF membranes with different pore sizes on top of each other. Flux decline data for the composite membrane were in good agreement with model calculations. The results provide important insights into the effects of asymmetric membrane pore structures on flux decline. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Resveratrol inhibits migration and invasion of human breast‐cancer cells

Metastasis is the primary cause of death from breast cancer. Cell migration and invasion play important roles in neoplastic metastasis. The insulin‐like growth factor (IGF‐1) stimulates cell migration through activation of PI‐3K/Akt signaling pathway. IGF‐1 induces the tumorigenicity of many types of cancer cells and is critical for metastatic cell spread in estrogen receptor (ER)‐negative breast‐cancer cells. Matrix metalloproteinase‐2 (MMP‐2) is a key enzyme in the degradation of extracellular matrices and its expression has been dysregulated in breast cancer invasion and metastasis. Resveratrol exhibited potential anticarcinogenic activities in several studies. However, the inhibitory effects of resveratrol on the expression of MMP‐2, migration and invasion of breast‐cancer cell have not been demonstrated yet. In the present study, we investigated the anti‐invasive mechanism of resveratrol in human breast cancer MDA‐MB 435cells. Here, we showed that IGF‐1 is a potent stimulant of the migration of ER‐negative human breast‐cancer cells. Resveratrol could inhibit IGF‐1‐mediated cell migration of MDA‐MB 435 in vitro. The inhibitory effect of resveratrol was mediated in part through the suppression of the activation of PI‐3K/Akt signaling pathway. Furthermore, IGF‐1‐mediated expression of MMP‐2 was significantly inhibited by resveratrol in concomitance with alteration of cell invasion.     

Biotransformation of ginsenoside Rd in the ginseng extraction residue by fermentation with lingzhi (Ganoderma lucidum)

Ginseng and lingzhi (Ganoderma lucidum) both are valuable traditional Chinese medicines and have been extensively utilised in functional foods and traditional medicines in many Asian countries. However, massive quantity of ginseng residue is produced after extraction of ginseng which still contains a lot of bioactive compounds such as ginsenosides. The goal of this study was to reuse the American ginseng extraction residue as the fermentation medium of G. lucidum to produce bioactive ginsenoside enriched biotransformation products. The changes of ginsenosides in the fermentation products were analysed during fermentation. Our results showed that after 30 days of fermentation, ginsenoside Rg1, Rd, and compound K (CK) significantly increased, especially Rd, while other ginsenosides (Re, Rb1 and Rc) decreased during fermentation. Ginsenoside Rd is the major ginsenoside in the final fermentation product. Furthermore, the biotransformation of ginsenosides was the major reaction in this fermentation process.     

中国沉积盆地结构类型与成油期规律

中国沉积盆地可分为单层结构箕状断陷型，双层结构断拗型，多层结构，台，断，拗，型实践证明，不论单层，双层，多层结构含油气盆地，一般说来，箕状断陷发育的中期为主要的成油期，多层结构的含油气盆地，台型构造层发育期为最佳成气期。     

MMSE‐based transceiver design for distributed MIMO amplify‐and‐forward cooperative networks in correlated channels

In this paper, the source‐precoder, multiple‐relay amplifying matrices, and destination‐equalizer joint optimization is investigated in distributed MIMO amplify‐and‐forward multiple‐relay networks with direct source–destination transmission in correlated fading channels. With the use of taking both the direct link and spatial correlation between antenna elements into account, the cooperative transceiver joint design is developed based on the minimum mean‐squared error criterion under individual power constraints at the source and multiple‐relay nodes. Simulation results demonstrate that the cooperative transceiver joint design architecture for an amplify‐and‐forward MIMO multiple‐relay system outperforms substantially the noncooperative transceiver design techniques on the BER performance under the spatial‐correlation channels.Copyright © 2012 John Wiley & Sons, Ltd.