Cobalt-Catalyzed Asymmetric Alkylation of (Hetero)Arenes with Styrenes.

An efficient and general intermolecular Cobalt(II)-catalyzed asymmetric alkylation of styrenes with (hetero)arenes including indoles, thiophene and electron rich arenes has been developed, providing straightforward access to enantioenriched alkyl(hetero)arenes with high enantioselectivity. Mechanistic studies suggest that the reaction underwent a CoH-mediated hydrogen atom transfer (HAT) with alkenes, followed by a pivotal catalyst-controlled SN 2-like pathway between in situ generated organocobalt(IV) species and aromatic nucleophiles. This is the first CoH-catalyzed asymmetric hydrofunctionalization using carbon nucleophiles, providing a new strategy for asymmetric Friedel-Crafts type alkylation.

Cobalt-Catalyzed Radical Hydroamination of Alkenes with N-Fluorobenzenesulfonimides.

An efficient and general radical hydroamination of alkenes using Co(salen) as catalyst, N-fluorobenzenesulfonimide (NFSI) and its analogues as both nitrogen source and oxidant was successfully disclosed. A variety of alkenes, including aliphatic alkenes, styrenes, α, ß-unsaturated esters, amides, acids, as well as enones, were all compatible to provide desired amination products. Mechanistic experiments suggest that the reaction underwent a metal-hydride-mediated hydrogen atom transfer (HAT) with alkene, followed by a pivotal catalyst controlled SN 2-like pathway between in situ generated organocobalt(IV) species and nitrogen-based nucleophiles. Moreover, by virtue of modified chiral cobalt(II)-salen catalyst, an unprecedented asymmetric version was also achieved with good to excellent level of enantiocontrol. This novel asymmetric radical C-N bond construction opens a new door for the challenging asymmetric radical hydrofunctionalization.

A photocurable leaky dielectric for highly electrical insulating electrohydrodynamic micro-/nanopatterns.

This communication describes an innovative photocurable leaky dielectric for electrohydrodynamic patterning (EHDP). Based on the well-designed molecular structure, the material in its liquid state exhibits low viscosity, high homogeneity, and more importantly a leaky dielectric characteristic; meanwhile, UV light irradiation transforms it from a liquid leaky dielectric into a solid perfect dielectric instantaneously via an interfacial reaction. Two typical EHDP processes have confirmed that the beneficial properties of this material help to rapidly fulfill a higher aspect ratio and/or smaller feature size patterning compared to its perfect dielectric counterpart. Therefore, this material provides the potential in accessing high-performance EHDP towards fabricating electrically insulating micro-/nanostructures.

miR-139-5p suppresses cancer cell migration and invasion through targeting ZEB1 and ZEB2 in GBM.

Invasion and migration of glioblastoma multiforme (GBM) is a multistep process and an important phenotype that causes this disease to invade surrounding tissues in the brain. Recent studies have highlighted that miRNAs play a pivotal role in controlling GBM cell plasticity. In this report, we used wound healing and transwell assays to identify a novel role of miR-139-5p in inhibition of GBM cell migration and invasion. Bioinformatics coupled with luciferase and Western blot assays also revealed that miR-139-5p inhibited expression of ZEB1 and ZEB2, which are master regulators of tumor metastasis. MiR-139-5p specifically interacts with the 3'-UTR regions of ZEB1 and ZEB2, attenuating their expression in GBM cells. To corroborate this finding, we rescued ZEB1 and ZEB2 expression and found partial but significant increases in miR-139-5p-suppressed invasion of GBM cells. The biological relevance of our study was validated by analyzing levels of miR-139-5p in GBM tissue. We found that its expression significantly downregulated compared to normal tissue and shorter overall survival rates in patients with lower miR-139-5p expression. These results confirm that miR-139-5p suppresses GBM migration and invasion and highlight its potential as a biomarker and therapeutic target for treating GBM.

Pattern formation in thin polymeric films via electrohydrodynamic patterning.

The free surface of a thin polymeric film is often unstable and deforms into various micro-/nano-patterns under an externally applied electric field. This paper reviews a recent patterning technique, electrohydrodynamic patterning (EHDP), a straightforward, cost-effective and contactless bottom-up method. The theoretical and numerical studies of EHDP are shown. How the characteristic wavelength and the characteristic time depend on both the external conditions (such as voltage, film thickness, template-substrate spacing) and the initial polymer properties (such as rheological property, electrical property and surface tension) is theoretically and experimentally discussed. Various possible strategies for fabricating high-aspect-ratio or hierarchical patterns are theoretically and experimentally reviewed. Aligning and ordering of the anisotropic polymers by EHDP is emphasized. A perspective, including novelty and limitations of the methods, particularly in comparison to some conventional patterning techniques, and a possible future direction of research, is presented.

Effects of surface condition of conductive electrospun nanofiber mats on cell behavior for nerve tissue engineering.

Electrospun nanofibrous scaffold is a promising implant for peripheral nerve regeneration. Herein, to investigate the effect of surface morphological features and electrical properties of scaffolds on nerve cell behavior, we modified electrospun cellulose (EC) fibrous mats with four kind of soluble conductive polymers derivates (poly (N-(methacryl ethyl) pyrrole) (PMAEPy), poly (N-(2-hydroxyethyl) pyrrole) (PHEPy), poly (3-(Ethoxycarbonyl) thiophene) (P3ECT) and poly (3-thiophenethanol) (P3TE)) by an in-situ polymerization method. The morphological characterization showed that conductive polymers formed aggregated nanoparticles and coatings on the EC nanofibers with the increased fiber diameter further affected the surface properties. Compared with pure EC scaffold, more PC12 cells were adhered and grown on modified mats, with more integral and clearer cell morphology. The results of protein adsorption study indicated that modified EC mats could provide more protein adsorption site due to their characteristic surface morphology, which is beneficial to cell adhesion and growth. The results in this study suggested that these conductive polymers modified scaffolds with special surface morphology have potential applications in neural tissue engineering.

A Unique Strategy for Polyethylene Glycol/Hybrid Carbon Foam Phase Change Materials: Morphologies, Thermal Properties, and Energy Storage Behavior.

Polyethylene glycol (PEG)/hybrid carbon foam (CF) phase change materials (PCMs) were prepared by integrating PEG into CF via dynamic-vacuum impregnation. The hybrid CF was first synthesized by mixtures of graphene oxide (GO) and carbon nanotubes (CNTs) with different volume ratios. The morphologies, chemical structures, thermal conductivities, shape-stabilization levels, and photo-thermal energy conversion levels of these composite PCMs were characterized systematically. The prepared composite PCMs exhibited good shape-stabilization levels and showed their original shapes without any PEG leakage. It was found that the polyethylene glycol/carbon foam with multi-walled carbon nanotubes (PEG/MCF) composite PCMs had a better shape-stable performance below the temperature of 250 °C, and the thermal conductivity of the PEG/MCF composite PCMs reached as high as 1.535 W/(mK), which was obviously higher than that of polyethylene glycol/carbon foam with single-walled carbon nanotubes (PEG/SCF, 1.159 W/(mK)). The results of the photo-thermal simulation tests showed that the composite PCMs had the ability to absorb light energy and then convert it to thermal energy, and the maximum thermal energy storage efficiency of the PEG/MCF composite PCMs and the PEG/SCF composite PCMs was 92.1% and 90.6%, respectively. It was considered that a valuable technique to produce high-performance composite PCMs was developed.

High Performance Anti-Corrosion Coatings of Poly (Vinyl Butyral) Composites with Poly N-(vinyl)pyrrole and Carbon Black Nanoparticles.

Zinc is widely used in battery negative electrodes and steel coatings for automotive industries. The anti-corrosion property of zinc is the most important factor determining the performance and lifetime of the products. In this paper, both size-controlled poly N-(vinyl)pyrrole (PNVPY) nanoparticles and carbon black (CB) nanoparticles were compounded with poly (vinyl butyral) (PVB) binder developing a series of composite coatings covered on the zinc substrates using a spin-coating technique. The morphologies of the surface and cross section of the PNVPY/CB/PVB coatings indicate that the PNVPY and CB nanoparticles are uniformly distributed in the matrix. The corrosion resistance of the composite coatings was tested by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization in a 3.5% NaCl solution. It is found that the coating with 1.9 wt.% PNVPY and 2.3 wt.% CB nanoparticles shows a remarkably high resistance value (Rc) and corrosion protection efficiency (99.99%). Meanwhile, the immersion results also reveal its superior corrosion resistance. It is considered that the nanoscale dispersion of PNVPY and carbon in PVB matrix and the strong interface action between the nanoparticles and PVB result in the uniform microstructure of the composites which endues the superior corrosion properties of the coatings.

Cerebrospinal fluid from rats given hypoxic preconditioning protects neurons from oxygen-glucose deprivation-induced injury.

Hypoxic preconditioning activates endogenous mechanisms that protect against cerebral ischemic and hypoxic injury. To better understand these protective mechanisms, adult rats were housed in a hypoxic environment (8% O2/92% N2) for 3 hours, and then in a normal oxygen environment for 12 hours. Their cerebrospinal fluid was obtained to culture cortical neurons from newborn rats for 1 day, and then the neurons were exposed to oxygen-glucose deprivation for 1.5 hours. The cerebrospinal fluid from rats subjected to hypoxic preconditioning reduced oxygen-glucose deprivation-induced injury, increased survival rate, upregulated Bcl-2 expression and downregulated Bax expression in the cultured cortical neurons, compared with control. These results indicate that cerebrospinal fluid from rats given hypoxic preconditioning protects against oxygen-glucose deprivation-induced injury by affecting apoptosis-related protein expression in neurons from newborn rats.

Gabapentin Effects on PKC-ERK1/2 Signaling in the Spinal Cord of Rats with Formalin-Induced Visceral Inflammatory Pain.

Currently, the clinical management of visceral pain remains unsatisfactory for many patients suffering from this disease. While preliminary animal studies have suggested the effectiveness of gabapentin in successfully treating visceral pain, the mechanism underlying its analgesic effect remains unclear. Evidence from other studies has demonstrated the involvement of protein kinase C (PKC) and extracellular signal-regulated kinase1/2 (ERK1/2) in the pathogenesis of visceral inflammatory pain. In this study, we tested the hypothesis that gabapentin produces analgesia for visceral inflammatory pain through its inhibitory effect on the PKC-ERK1/2 signaling pathway. Intracolonic injections of formalin were performed in rats to produce colitis pain. Our results showed that visceral pain behaviors in these rats decreased after intraperitoneal injection of gabapentin. These behaviors were also reduced by intrathecal injections of the PKC inhibitor, H-7, and the ERK1/2 inhibitor, PD98059. Neuronal firing of wide dynamic range neurons in L6-S1 of the rat spinal cord dorsal horn were significantly increased after intracolonic injection of formalin. This increased firing rate was inhibited by intraperitoneal injection of gabapentin and both the individual and combined intrathecal application of H-7 and PD98059. Western blot analysis also revealed that PKC membrane translocation and ERK1/2 phosphorylation increased significantly following formalin injection, confirming the recruitment of PKC and ERK1/2 during visceral inflammatory pain. These effects were also significantly reduced by intraperitoneal injection of gabapentin. Therefore, we concluded that the analgesic effect of gabapentin on visceral inflammatory pain is mediated through suppression of PKC and ERK1/2 signaling pathways. Furthermore, we found that the PKC inhibitor, H-7, significantly diminished ERK1/2 phosphorylation levels, implicating the involvement of PKC and ERK1/2 in the same signaling pathway. Thus, our results suggest a novel mechanism of gabapentin-mediated analgesia for visceral inflammatory pain through a PKC-ERK1/2 signaling pathway that may be a future therapeutic target for the treatment of visceral inflammatory pain.

Hypoxic preconditioning stimulates angiogenesis in ischemic penumbra after acute cerebral infarction.

Previous studies have demonstrated the protective effect of hypoxic preconditioning on acute cerebral infarction, but the mechanisms underlying this protection remain unclear. To investigate the protective mechanisms of hypoxic preconditioning in relation to its effects on angiogenesis, we induced a photochemical model of cerebral infarction in an inbred line of mice (BALB/c). Mice were then exposed to hypoxic preconditioning 30 minutes prior to model establishment. Results showed significantly increased vascular endothelial growth factor and CD31 expression in the ischemic penumbra at 24 and 72 hours post infarction, mainly in neurons and vascular endothelial cells. Hy-Hypoxic preconditioning increased vascular endothelial growth factor and CD31 expression in the ischemic penumbra and the expression of vascular endothelial growth factor was positively related to that of CD31. Moreover, hypoxic preconditioning reduced the infarct volume and improved rological function in mice. These findings indicate that the protective role of hypoxic preconditioning in acute cerebral infarction may possibly be due to an increase in expression of vascular endothelial growth factor and CD31 in the ischemic penumbra, which promoted angiogenesis.