High-Yield Gold Nanohydrangeas on Three-Dimensional Carbon Nanotube Foams for Surface-Enhanced Raman Scattering Sensors.

Recently, carbon nanomaterial-supported plasmonic nanocrystals used as high-performance surface-enhanced Raman scattering (SERS) substrates have attracted increasing attention due to their ultra-high sensitivity of detection. However, most of the work focuses on the design of 2-D planar substrates with traditional plasmonic structures, such as nanoparticles, nanorods, nanowires, and so forth. Here, we report a novel strategy for the preparation of high-yield Au nanohydrangeas on three-dimensional porous polydopamine (PDA)/polyvinyl alcohol (PVA)/carbon nanotube (CNT) foams. The structures and growth mechanisms of these specific Au nanocrystals are systematically investigated. PDA plays the role of both a reducing agent as well as an anchoring site for Au nanohydrangeas' growth. We also show that the ratio of surfactant KBr to the gold precursor (HAuCl4) is key to obtain these structures in a manner of high production. Moreover, the substrate of the CNT foam-Au nanohydrangea hybrid can be employed as SERS sensors and can detect the analytes down to 10-9 M.

Fabrication and Characterization of Solid Composite Yarns from Carbon Nanotubes and Poly(dicyclopentadiene).

In this report, networks of carbon nanotubes (CNTs) are transformed into composite yarns by infusion, mechanical consolidation and polymerization of dicyclopentadiene (DCPD). The microstructures of the CNT yarn and its composite are characterized by scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), and a focused ion beam used for cross-sectioning. Pristine yarns have tensile strength, modulus and elongation at failure of 0.8 GPa, 14 GPa and 14.0%, respectively. In the composite yarn, these values are significantly enhanced to 1.2 GPa, 68 GPa and 3.4%, respectively. Owing to the consolidation and alignment improvement, its electrical conductivity was increased from 1.0 × 105 S/m (raw yarn) to 5.0 × 105 S/m and 5.3 × 105 S/m for twisted yarn and composite yarn, respectively. The strengthening mechanism is attributed to the binding of the DCPD polymer, which acts as a capstan and increases frictional forces within the nanotube bundles, making it more difficult to pull them apart.

One-Pot Self-Templated Growth of Gold Nanoframes for Enhanced Surface-Enhanced Raman Scattering Performance.

As one of the representative metallic hollow nanostructures, Au nanoframes have shown fascinating properties such as strong localized surface plasmon resonance associated with emerging applications such as surface-enhanced Raman scattering (SERS) sensors. In this study, for the first time, a facile one-pot synthetic approach for hollow Au nanoframes is demonstrated by directly etching Au nanoplates, that is, the so-called self-templates. A novel growth mechanism has been revealed that involves a synergistic function of Ag and Br ions. The presence of Ag+ leads to the observation of self-limiting Au film thickness, whereas Au{111} facets are preferentially attacked by the presence of Br- in the reaction ambient. More importantly, graphene is introduced to prevent/minimize aggregation during the formation of Au nanoframes. The combined simulation and experimental studies show that the hybrid platform made of graphene/Au nanoframes is capable of detecting analytes at concentration levels down to 10-9 M by using the SERS technique.

Synthesis and characterization of a new organic-inorganic hybrid ferroelectric: (C4H10N)6[InBr6][InBr4]3·H2O.

Organic-inorganic hybrid ferroelectric materials have attracted attention from researchers as promising candidates for functional materials, because they combine high performance and low cost. Herein, a new organic-inorganic hybrid ferroelectric material (C4H10N)6[InBr6][InBr4]3·H2O (1) was synthesized and characterized. The compound undergoes a paraelectric-ferroelectric phase transition at TC = 232 K, which is investigated by differential scanning calorimetry (DSC), dielectric measurements and variable-temperature structural analyses. Crystal structure analyses indicated that the disorder-order transition of Br atoms in [InBr4]- anions depending on temperature was the main factor driving the phase transition from Pbcn to Pna21. This finding will open up a new direction to probe the organic-inorganic hybrid molecular ferroelectric phase transition materials.

Ultrasonication-assisted synthesis of high aspect ratio gold nanowires on a graphene template and investigation of their growth mechanism.

We report a facile synthesis of Au nanowires (AuNWs) with a high aspect ratio (l/D) of up to 5000 on a plasma activated graphene template with ultrasound assistance. We demonstrate that the ultrasonication induced symmetry breaking of Au clusters facilitates the growth of AuNWs from the embryonic stages. Furthermore, the growth mechanism of AuNWs is systematically investigated using high resolution electron transmission microscopy (HRTEM), which reveals the unique role of the defective graphene template in directing the growth of AuNWs.

One-Step Synthesis of Tunable-Size Gold Nanoplates on Graphene Multilayers.

Au nanoplates (quasi-two-dimensional single crystals) are most commonly synthesized using a mixture of Au precursors via approaches involving multiple processing steps and the use of seed crystals. Here, we report the synthesis of truncated-hexagonal {111}-oriented micrometer-scale Au nanoplates on graphene multilayers using only potassium tetrabromoaurate (KAuBr4) as the precursor. We demonstrate that the nanoplate sizes can be controllably varied from tens of nanometers up to a few micrometers by introducing desired concentrations of chloroauric acid (HAuCl4) to KAuBr4 and their thicknesses from ∼13 to ∼46 nm with the synthesis time. Through a series of experiments carried out as a function of synthesis time and precursor composition [mixtures of HAuCl4 and KAuBr4, KBr, or ionic liquid 1-butyl-3-methylimidazolium bromide ([Bmim]Br)], we identify the optimal HAuCl4 and KAuBr4 concentrations and synthesis times that yield the largest and the thinnest size nanoplates. We show that the nanoplates are kinetically limited morphologies resulting from preferential growth of {111} facets facilitated by bromide ions in KAuBr4 solutions; we suggest that the presence of chloride ions enhances the rate of Au deposition and the relative concentration of chloride and bromide ions determines the shape anisotropy of resulting crystals. Our results provide new insights into the kinetics of nanoplate formation and show that a single precursor containing both Au and Br is sufficient to crystallize nanoplates on graphitic layers, which serve as reducing agent while enabling the nucleation and growth of Au nanoplates. We suggest that a similar approach may be used for the synthesis of nanoplates of other metals on weakly interacting van der Waals layers for, potentially, a variety of new applications.

Graphene template-induced growth of single-crystalline gold nanobelts with high structural tunability.

Assembling Au nanocrystals with tunable dimensions and shapes on graphene templates has attracted increasing attention recently. However, directly growing anisotropic Au nanobelts on a graphene support has been rarely reported. Here, a facile, one-pot, and surfactant-free route is demonstrated to synthesize well-defined Au nanobelts with the induction of a multilayer graphene (mlG) template. The obtained Au nanobelts are single-crystalline with a preferable (111) orientation. More importantly, their structural evolution starting from Au clusters is systematically investigated using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results confirm that mlG consistently induces the growth of Au nanobelts from nucleation to the growth completion. The interfacial interaction between Au atoms and the graphene lattice is a predominant factor to direct the shapes and structures of Au nanocrystals, which makes the structures of Au nanobelts highly tunable with the surface modification of the mlG template. The assembly of mlG-Au nanobelts also presents extraordinary detection sensitivity when employed as a flexible surface-enhanced Raman scattering (SERS) substrate, suggesting their great potential application in high-performance sensors. This report strengthens the fundamental understanding of the interactions between noble metals and carbon interfaces, which paves the way to construct and manipulate the complex structures of metals on graphitic substrates.

Novel Strategy for One-Pot Synthesis of Gold Nanoplates on Carbon Nanotube Sheet As an Effective Flexible SERS Substrate.

In this work, we demonstrate a novel route for one-pot synthesis of two-dimensional gold nanoplates (2-D AuNPLs) on carbon nanotube (CNT) sheet. Well-defined AuNPLs are grafted onto CNT sheet via a facile hydrothermal reduction process, during which bromine ions are employed as the surfactant for gold anisotropic growth. Scanning electron microscopy (SEM) shows large-scale AuNPLs with micrometer-scaled length and sub-100 nm thickness are deposited uniformly on the CNT sheet. Transmission electron microscopy (TEM) and X-ray diffraction (XRD) results confirm the synthesized AuNPLs are single-crystalline with preferential {111} orientation. Based on the CNT sheet/AuNPLs hybrid, we have fabricated a flexible surface-enhanced Raman scattering (SERS) substrate, which can effectively detect the analyte Rhodamine 6G (Rh6G) at the concentration as low as 1 × 10-7 M. The excellent SERS performance of this novel flexible substrate is mainly attributed to nanoscaled gaps between the neighbors, large surface area with roughness, and their sharp edges and corners.

Prenylated phloroglucinol derivatives from Hypericum sampsonii.

Six new acylphloroglucinol derivatives, sampsonols A-F (1-6), were isolated from the petroleum ether extract of the aerial parts of Hypericum sampsonii. The structures and relative configurations of sampsonols A-F were elucidated by extensive spectroscopic analyses. All these compounds were tested for their in vitro cytotoxic and anti-inflammatory activities. Sampsonols A and B (1 and 2) showed significant cytotoxicity against four human tumor cell lines with IC(50) values in the range of 13-28µM, whereas sampsonols C and F (3 and 6) showed potent inhibitory activities against LPS-induced NO production in RAW 264.7 macrophages with IC(50) values of 27.3 and 29.3µM, respectively.

Triterpenoid saponins from the seeds of Caragana microphylla.

Two new triterpenoid saponins, namely caraganoside C (1) and caraganoside D (2), were isolated from the seeds of Caragana microphylla. Their structures were elucidated on the basis of spectroscopic analyses, including homo- and hetero-nuclear correlation NMR experiments (COSY, HSQC and HMBC). Both 1 and 2 exhibited moderate inhibitory activity against NO production in LPS-stimulated RAW264.7 cells with IC(50) values of 26.4 µM and 32.2 µM, respectively. In addition, 1 showed weak cytotoxicity against MCF-7, HL-60, HCT116, and A549 cell lines.

Isolation and characterization of two flavonoids, engeletin and astilbin, from the leaves of Engelhardia roxburghiana and their potential anti-inflammatory properties.

Engeletin, a flavonoid compound, was isolated from the leaves of Engelhardia roxburghiana for the first time, along with astilbin, another flavonoid. The chemical structures of engeletin and astilbin were confirmed by (1)H and (13)C nuclear magnetic resonance (NMR) and mass spectrometry (MS) spectra, and their anti-inflammatory activities were studied in lipopolysaccharide (LPS)-stimulated mouse J774A.1 macrophage cells. LPS induced the inflammatory state in macrophage cells and increased mRNA expressions of pro-inflammatory cytokines. Engeletin and astilbin exhibited remarkable inhibitory effects on interleukin (IL)-1ß and IL-6 mRNA expression. Significant inhibition of LPS-mediated mRNA expressions were also seen in LPS binding toll-like receptor (TLR)-4, pro-inflammatory cytokine tumor necrosis factor (TNF)-α, IL-10, chemoattractant monocyte chemotactic protein (MCP)-1, and cyclooxygenase (COX)-2 genes. The reduced expression of these cytokines may alleviate immune response and reduce inflammatory activation, indicating that engeletin and astilbin may serve as potential anti-inflammatory agents.

Two new xanthones from Hypericum sampsonii and biological activity of the isolated compounds.

Phytochemical investigation of the CH(2) Cl(2) extract of the aerial part of Hypericum sampsonii yielded two new prenylated xanthones, hypericumxanthone A and B, together with three known xanthones. Their structures were elucidated by analysis of physical and spectral (UV, IR, mass and NMR) data and comparison of spectroscopic data with those reported previously. All these compounds were evaluated for in vitro antibacterial activity against methicillin-resistant Staphylococcus aureus (MRSA). Two new compounds were also tested for their cytotoxicity against human breast (MCF-7), hepatoma (HepG2), colon (HT-29) and lung (A549) tumour cell lines. Two new compounds showed moderate antibacterial activities at minimum inhibitory concentrations (MIC) of 16 and 32 µg/mL, respectively, whereas the positive standard antibacterial drug, vancomycin, showed an MIC of 8 µg/mL. The other compounds were inactive against MRSA. In addition, hypericumxanthone B showed weak inhibitory activities against four human tumour cell lines.

Rosin-derived imide-diacids as epoxy curing agents for enhanced performance.

Two rosin-based imide-diacids were synthesized and studied as epoxy curing agents. In comparison, a similar imide-diacid based on trimellitic anhydride was also prepared. The chemical structures were confirmed by (1)H NMR and FT-IR. The curing of a commercial epoxy with these imide-containing diacids was studied by differential scanning calorimetry (DSC). Thermal stability, tensile and dynamic mechanical properties of the cured epoxies were investigated. The results indicate that rosin-based imide-diacids used as curing agents resulted in significantly higher glass transition temperature, tensile and dynamic mechanical properties than the imide-diacid derived from trimellitic anhydride. Rosin acids have a great potential to replace some of current petroleum-based compounds in the synthesis of epoxy curing agents.

[Studies on alkalodial constituents in leaves of Uncaria hirsuta].

OBJECTIVE: To study the alkaloidial constituents of the leaves of uncaria hirsuta. METHOD: Some chromatographic methods were applied to isolate pure compounds and their structures were elucidated by spectroscopic methods. RESULT: Eleven compounds were isolated and identified as 19-epi-3-iso-ajmalicine (1), 3-isoajmalicine (2), harman (3), mitraphylline (4), isomitraphylline (5), isorhynchophylline (6), corynoxine (7), rhynchophylline (8), isomitraphyllic acid (9), uncarine A (10) and uncarine B (11). CONCLUSION: Compounds 1-9 were firstly isolated from this plant.