Graphene/Silver Nanowires/Graphene Sandwich Composite for Stretchable Transparent Electrodes and Its Fracture Mechanism.

Polycrystalline graphene grown by chemical vapor deposition (CVD) is characterized by line defects and disruptions at the grain boundaries and nucleation sites. This adversely affects the stretchability and conductivity of graphene, which limits its applications in the field of flexible, stretchable, and transparent electrodes. We demonstrate a composite electrode comprised of a graphene/silver nanowires (AgNWs)/graphene sandwich structure on a polydimethylsiloxane substrate to overcome this limitation. The sandwich structure exhibits high transparency (>90%) and excellent conductivity improvement of the graphene layers. The use of AgNWs significantly suppresses the conductivity loss resulting from stretching. The mechanism of the suppression of the conductivity loss was investigated using scanning electron microscopy, atomic force microscopy, and lateral force microscopy. The results suggest that the high surface friction of the sandwich structure causes a sliding effect between the graphene layers would produce low crack or hole formation to maintain the conductivity. In addition to acting as conductive layers, the top and bottom graphene layers can also protect the AgNWs from oxidation, thereby enabling maintenance of the electrical performance of the electrodes over a prolonged period. We also confirmed the applicability of the sandwich structure electrode to the human body, such as on the wrist, finger, and elbow.

Flexible Transparent Electrode of Hybrid Ag-Nanowire/Reduced-Graphene-Oxide Thin Film on PET Substrate Prepared Using H2/Ar Low-Damage Plasma.

We employ H2/Ar low-damage plasma treatment (H2/Ar-LDPT) to reduce graphene oxide (GO) coating on a polymer substrate-polyethylene terephthalate (PET)-with the assistance of atomic hydrogen (Hα) at low temperature of 70 °C. Four-point probing and ultraviolet-visible (UV-Vis) spectroscopy demonstrate that the conductivity and transmittance can be controlled by varying the H2/Ar flow rate, treatment time, and radio-frequency (RF) power. Optical emission spectroscopy reveals that the Hα intensity depends on these processing parameters, which influence the removal of oxidative functional groups (confirmed via X-ray photoelectron spectroscopy) to yield reduced GO (rGO). To further improve the conductivity while maintaining high transmittance, we introduce silver nanowires (AgNWs) between rGO and a PET substrate to obtain a hybrid rGO/AgNWs/PET with a sheet resistance of ~100 Ω/sq and 81% transmittance. In addition, the hybrid rGO/AgNWs thin film also shows high flexibility and durability and is suitable for flexible and wearable electronics applications.

Sesquiterpenoids and Diterpenoids from the Wood of Cunninghamia konishii and Their Inhibitory Activities against NO Production.

Three new sesquiterpenoids, 2α-hydroxy-3,3,6α,9ß-tetramethyltricyclo[4,3,2(1,4)]undecane (1), 11-acetoxyeudesman-4ß-ol (4), and 2α,3ß-dihydroxy-4ß-methyl-6,8,10-cadinatriene (6), four known sesquiterpenoids (2, 3, 5, and 7), together with eight known diterpenoids (8-15), were isolated from the wood of Cunninghamia konishii. Their structures were determined by detailed analysis of spectroscopic data and comparison with the data of known analogues. Four sesquiterpenoids (1, 4, 5, and 6) and all the diterpenoids (8-15) were evaluated for inhibition of nitric oxide production in lipopolysaccharides (LPS)-activated RAW 264.7 macrophages and the results showed that compounds 10 and 15 exhibited moderate inhibitory activities against nitric oxide production.

Bioengineering vascularized tissue constructs using an injectable cell-laden enzymatically crosslinked collagen hydrogel derived from dermal extracellular matrix.

Tissue engineering promises to restore or replace diseased or damaged tissue by creating functional and transplantable artificial tissues. The development of artificial tissues with large dimensions that exceed the diffusion limitation will require nutrients and oxygen to be delivered via perfusion instead of diffusion alone over a short time period. One approach to perfusion is to vascularize engineered tissues, creating a de novo three-dimensional (3D) microvascular network within the tissue construct. This significantly shortens the time of in vivo anastomosis, perfusion and graft integration with the host. In this study, we aimed to develop injectable allogeneic collagen-phenolic hydroxyl (collagen-Ph) hydrogels that are capable of controlling a wide range of physicochemical properties, including stiffness, water absorption and degradability. We tested whether collagen-Ph hydrogels could support the formation of vascularized engineered tissue graft by human blood-derived endothelial colony-forming cells (ECFCs) and bone marrow-derived mesenchymal stem cells (MSC) in vivo. First, we studied the growth of adherent ECFCs and MSCs on or in the hydrogels. To examine the potential formation of functional vascular networks in vivo, a liquid pre-polymer solution of collagen-Ph containing human ECFCs and MSCs, horseradish peroxidase and hydrogen peroxide was injected into the subcutaneous space or abdominal muscle defect of an immunodeficient mouse before gelation, to form a 3D cell-laden polymerized construct. These results showed that extensive human ECFC-lined vascular networks can be generated within 7 days, the engineered vascular density inside collagen-Ph hydrogel constructs can be manipulated through refinable mechanical properties and proteolytic degradability, and these networks can form functional anastomoses with the existing vasculature to further support the survival of host muscle tissues. Finally, optimized conditions of the cell-laden collagen-Ph hydrogel resulted in not only improving the long-term differentiation of transplanted MSCs into mineralized osteoblasts, but the collagen-Ph hydrogel also improved an increased of adipocytes within the vascularized bioengineered tissue in a mouse after 1 month of implantation. STATEMENT OF SIGNIFICANCE: We reported a method for preparing autologous extracellular matrix scaffolds, murine collagen-Ph hydrogels, and demonstrated its suitability for use in supporting human progenitor cell-based formation of 3D vascular networks in vitro and in vivo. Results showed extensive human vascular networks can be generated within 7 days, engineered vascular density inside collagen-Ph constructs can be manipulated through refinable mechanical properties and proteolytic degradability, and these networks can form functional anastomoses with existing vasculature to further support the survival of host muscle tissues. Moreover, optimized conditions of cell-laden collagen-Ph hydrogel resulted in not only improving the long-term differentiation of transplanted MSCs into mineralized osteoblasts, but the collagen-Ph hydrogel also improved an increased of adipocytes within the vascularized bioengineered tissue in a mouse.

Hierarchical self-assembly of nanoparticles in polymer matrix and the nature of the interparticle interaction.

Using small angle X-ray scattering (SAXS), we elucidated the spatial organization of palladium (Pd) nanoparticles (NPs) in the polymer matrix of poly(2-vinylpyridine) (P2VP) and the nature of inter-nanoparticle interactions, where the NPs were synthesized in the presence of P2VP by the reduction of palladium acetylacetonate (Pd(acac)2). The experimental SAXS profiles were analysed on the basis of a hierarchical structure model considering the following two types of interparticle potential: (i) hard-core repulsion only (i.e., the hard-sphere interaction) and (ii) hard-core repulsion together with an attractive potential well (i.e., the sticky hard-sphere interaction). The corresponding theoretical scattering functions, which were used for analysing the experimental SAXS profiles, were obtained within the context of the Percus-Yevick closure and the Ornstein-Zernike equation in the fundamental liquid theory. The analyses revealed that existence of the attractive potential well is indispensable to account for the experimental SAXS profiles. Moreover, the morphology of the hybrids was found to be characterized by a hierarchical structure with three levels, where about six primary NPs with the diameter of ca. 1.8 nm (level one) formed local clusters (level two), and these clusters aggregated to build up a large-scale mass-fractal structure (level three) with the fractal dimension of ca. 2.3. The scattering function developed here is of general use for quantitatively characterizing the morphological structures of polymer/NP hybrids and, in particular, for exploring the interaction potential of the NPs on the basis of the fundamental liquid theory.

Enzymatic regulation of functional vascular networks using gelatin hydrogels.

To manufacture tissue engineering-based functional tissues, scaffold materials that can be sufficiently vascularized to mimic the functionality and complexity of native tissues are needed. Currently, vascular network bioengineering is largely carried out using natural hydrogels as embedding scaffolds, but most natural hydrogels have poor mechanical stability and durability, factors that critically limit their widespread use. In this study, we examined the suitability of gelatin-phenolic hydroxyl (gelatin-Ph) hydrogels that can be enzymatically crosslinked, allowing tuning of the storage modulus and the proteolytic degradation rate, for use as injectable hydrogels to support the human progenitor cell-based formation of a stable and mature vascular network. Porcine gelatin-Ph hydrogels were found to be cytocompatible with human blood-derived endothelial colony-forming cells and white adipose tissue-derived mesenchymal stem cells, resulting in >87% viability, and cell proliferation and spreading could be modulated by using hydrogels with different proteolytic degradability and stiffness. In addition, gelatin was extracted from mouse dermis and murine gelatin-Ph hydrogels were prepared. Importantly, implantation of human cell-laden porcine or murine gelatin-Ph hydrogels into immunodeficient mice resulted in the rapid formation of functional anastomoses between the bioengineered human vascular network and the mouse vasculature. Furthermore, the degree of enzymatic crosslinking of the gelatin-Ph hydrogels could be used to modulate cell behavior and the extent of vascular network formation in vivo. Our report details a technique for the synthesis of gelatin-Ph hydrogels from allogeneic or xenogeneic dermal skin and suggests that these hydrogels can be used for biomedical applications that require the formation of microvascular networks, including the development of complex engineered tissues.

Two new labdane-type diterpenes from the wood of Cunninghamia konishii.

Phytochemical investigation of the methanol extract of the wood of Cunninghamia konishii resulted in the isolation of two new acidic labdane-type diterpenoids, 12(S)-hydroxy-15,16-epoxylabda-8(17),13-dien-19-oic acid (1) and 12(S)-hydroxy-15,16-epoxylabda-8(17),13-dien-18-oic acid (2), along with one known labdane-type diterpene, 7,13E-labdadien-15-ol (3). Their structures were determined by analysis of spectroscopic data and comparison with the data of known analogues.

Diterpenoids with anti-inflammatory activity from the wood of Cunninghamia konishii.

Two new diterpenoids, konishone (1) and 3b-hydroxy-5,6-dehydrosugiol (2), along with three known diterpenoids--hinokiol (3), sugiol (4), and 12-hydroxy-6,7-secoabieta-8,11,13-triene-6,7-dial (5)--were isolated from the wood of Cunninghamia konishii. Compound 1 is a novel skeleton of the 7,20-dinorabietane-type diterpene. In addition, when RAW264.7 macrophages were treated with different concentrations of compounds 1, 3, and 5 together with LPS, a significant concentration-dependent inhibition of NO production was detected. The IC50 values for inhibition of nitrite production of compounds 1, 3, and 5 were about 9.8 ± 0.7, 7.9 ± 0.9, and 9.3 ± 1.3 µg/mL, respectively. This study presents the potential utilization of compounds 1, 3, and 5, as lead compounds for the development of anti-inflammatory drugs.

Scattering study of the conformational structure and aggregation behavior of a conjugated polymer solution.

The conformational structure and the interchain aggregation behavior of a semirigid conjugated polymer bearing a decyl side chain, poly(2,3-diphenyl-5-decyl-1,4-phenylenevinylene) (DP10-PPV), in solutions with chloroform and toluene have been investigated by means of small-angle neutron scattering (SANS), static light scattering (SLS) and dynamic light scattering (DLS). The radius of gyration, persistence length, and the second virial coefficient of the polymer in dilute solution as determined by SLS were higher in chloroform than in toluene; consequently, the polymer assumed a more extended wormlike chain conformation in the former. The difference in the strength of interaction in the two solvents gave rise to contrasting aggregation behavior of the polymer in the semidilute regime. While only a minor fraction of the polymer underwent segmental association in chloroform, a considerable fraction of it formed clusters (microgels) with several micrometers in size in toluene. These clusters were further found to consist of sheetlike nanodomains. Compared with the DP-PPV bearing a shorter hexyl side chain, DP6-PPV, the aggregates of DP10-PPV in toluene were weaker as they could be easily disrupted by moderate heating. This was attributed to a lack of strong pi-pi interaction between the DP10-PPV segments due to the greater steric hindrance imposed by the longer decyl side chains.

Silicon-induced ene-type reaction in the thermal conversion of enolates to beta-silyl enones with molecular dioxygen.

Reaction of alkyl, acetoxy, and silyl enol ethers of 3-(organosilyl)cyclohexanone with molecular dioxygen in toluene at 110 degrees C produced the corresponding conjugated enones in yields up to 88% yield. The reaction of the same type failed on replacement of the silyl group at the C-3 position with an isopropyl group. These results indicate the existence of an unprecedented silicon-induced ene-type reaction. Its reaction mechanism, generality, limitations, and exceptions are discussed.

Two-dimensional densely packed DNA nanostructure derived from DNA complexation with a low-generation poly(amidoamine) dendrimer.

One of the keys for using deoxyribonucleic acid (DNA) as a nanomaterial relies on how the individual DNA chain can be aligned and how a multitude of DNA chains can be packed into ordered nanostructures. Here we present a simple method for constructing a 2-D densely packed DNA nanostructure using the electrostatic complex of DNA with a poly(amidoamine) (PAMAM) dendrimer of generation two. Ordered DNA arrays are formed by drop-casting an aqueous solution containing positively overcharged complexes onto mica followed by a prolonged incubation. During the incubation, the complexes tend to adsorb onto the negatively charged mica surface through electrostatic attraction. The rodlike complexes organize to form ordered arrays to increase the surface density of the adsorbed complexes and hence the attractive free energy of adsorption. The densely packed nanostructure obtained here is distinguished from the previously reported spheroid or toroid structure derived from DNA complexations with the higher-generation dendrimers.

Fractal aggregates of conjugated polymer in solution state.

Semirigid conjugated polymers have received much scientific and technological interest due to their unique electrical and photonic semiconducting properties. Spectroscopic studies have indicated that these polymers underwent interchain aggregation in the solution state even at large dilution; however, the origin of this event and the structure of the resultant aggregates remained the crucial issues to be resolved. In the present study, we revealed that the interchain aggregation of a conjugated polymer, poly(2,3-diphenyl-5-hexyl-1,4-phenylenevinylene) (DP6-PPV), in solutions with chloroform and toluene generated network aggregates with the hydrodynamic radii of several micrometers. Small angle neutron scattering (SANS) demonstrated that the internal structure of these aggregates could be characterized by the mass fractal dimensions of 2.2-2.7. The networks were looser in chloroform but became highly compact in the poorer toluene solvent due to severe segmental association. Increasing the temperature alleviated the segmental association in toluene while largely retaining the mass fractal dimension of the aggregates. However, the interchain aggregation was never completely dissipated by the heating, suggesting the existence of two types of segmental association with distinct stability. The highly stable segmental association that could neither be solvated by chloroform nor be disrupted thermally in toluene was attributed to the pi-pi complex already present in the DP6-PPV powder used for the solution preparation. The chains tied firmly by this complex formed network aggregates in the solution and hence reduced the entropy of mixing of the polymer. In the poorer toluene solvent, further segmental association took place within the preexisting aggregates, making the networks more compact. This type of segmental association could be disrupted by moderate heating, and its occurrence was ascribed to the poor affinity of the aliphatic side chains of DP6-PPV for toluene.

Thermally-induced order-order transition of DNA-cationic surfactant complexes.

Polyanionic DNA interacts with cationic amphiphiles to form electrostatic complexes exhibiting rich self-assembled structures. This type of complex has been considered as a nonviral carrier in gene therapy and as a template for nanostructure construction. Here we report a thermally-induced phase transition of the complexes of DNA with the mixtures of a cationic surfactant, dodecyltrimethyl bromide (DTAB), and a neutral lipid, dioleoylphosphatidylethanolamine (DOPE), in fully hydrated state. An order-order transition between a multilamellar (L(c)alpha) phase and an inverted hexagonal (H(c)II) phase was found to occur with the transition temperature adjustable by the DTAB-to-DNA base pair molar ratio (x) and DOPE-to-DTAB molar ratio (m). The stability of the L(c)alpha phase was enhanced at lower m and x, as the L(c)alpha-to-H(c)II transition temperature increased with the decreases of these two parameters. The suppression of -to- transition at lower x was attributed to the lower entropic gain from the counterion release due to the presence of uncomplexed DNA in the bulk solution.

Large-volume sample sweeping with a high theoretical plate number using a coupled-capillary in capillary electrophoresis.

A large-volume sample injection (> 5 microL) with an extremely high theoretical plate number (N > 10(7)) was achieved when the sweeping-MEKC mode and a coupled-capillary (100 - 50 microm i.d.) were simultaneously used in a capillary electrophoresis (CE) separation. A low-cost and compact violet-LED ( approximately 2 mW) was used as the fluorescence excitation source. As a result, the theoretical plate numbers of the detected peaks (two model compounds: naphthalene-2,3-dicarboxaldehyde derivatized-dopamine and -norepinephrine) were 1.0 x 10(7) and 7.4 x 10(6), respectively. The limits of detection (at S/N = 3) of these were determined to be 2.8 x 10(-10) M (92 ppt) and 2.3 x 10(-10) M (83 ppt), respectively.

Labdane-type diterpenoids from the wood of Cunninghamia konishii.

Five new labdane-type diterpenes, 12beta,19-dihydroxymanoyl oxide (1), 8(17),13-labdadien-12,15-olid-19-oic acid (2), 12,15-epoxy-8(17),13-labdadien-18-oic acid (3), 8alpha-hydroxy-11E,13Z-labdadien-15-al (4), and (13R)-13-hydroxy-8(17), 11E,14-labdatrien-18-oic acid (5) were isolated from the wood of Cunninghamia konishii. Their structures were elucidated by two-dimensional NMR spectroscopy.