Photocatalytic and antibacterial activities of silver and iron doped titania nanoparticles in solution and polyaspartic coatings.

Visible region active photocatalytic coatings are of interest for antimicrobial activity in low light applications or those employing LED lights with limited UV content. This work examined Ag and Fe doped titania nanoparticles (nTiO2) with varying dopant ranges in polyaspartic polymer coatings for potential light and dark activity. First, the Ag and Fe doped nTiO2 were synthesized by sol-gel chemistry with varying dopant concentrations, then characterized with respect to their size and aggregate size distribution, crystallinity, and surface and band gap features. The photocatalytic activity was then tested with methylene blue under both AM 1.5 G and visible light. From both sample sets (Ag and Fe doped nTiO2), the best photo catalytically active sample materials were chosen for antibacterial tests with gram-negative Escherichia coli (E. coli) and gram-positive Bacillus subtilis (B. subtilis) in (a) solution and (b) polyaspartic nanocomposites under UV and visible irradiation. The results showed that Ag doped nTiO2 samples delivered the best and excellent antibacterial action, even in the dark, attributed to both an enhanced band gap and surface area, as well as a combination of photocatalytic activity and Ag being present at the nanoparticle's surface. No leaching of Ag at room temperature was observed from the nTiO2 structure, giving potential for next generation coatings that are both light and dark active.

Impact of the chemical nature and position of spacers on controlling the optical properties of silicon quantum dots.

The unique properties of silicon quantum dots (SQDs), including intriguing optical properties, biocompatibility, and ease of surface modification have made them excellent candidates for a variety of optoelectronic and biomedical applications. Unfortunately, the low quantum efficiency (QE), unstable photoluminescence, and poor colloidal stability of SQDs have hindered their wide applicability. Herein, we report the synthesis of four assemblies of SQDs (1.6-1.8 nm average diameter) functionalized with fluorescein dye through isothiocyanate (-NCS) and carboxylate (COO-) spacers in the benzene ring of the fluorescein to produce the dyads Am-SQD-Fl, DiAm-SQD-Fl, urea-SQD-Fl, and SQD-Fl. The photophysical measurements showed that the spacer played a key role in directing and controlling the optical properties of SQDs dyads, with the isothiocyanate spacer leading to a significant improvement in the QE of the dyad systems up to 65% and extending their photostability for at least one year. The interactions between the SQDs and fluorescein in the dyads Am-SQD-Fl, DiAm-SQD-Fl, and SQD-Fl were found to mainly proceed through photoinduced electron transfer at different rates, while energy transfer was confirmed to be the predominant process in the dyad urea-SQD-Fl. To demonstrate the suitability of the functionalized SQDs for bioimaging applications, the water-soluble dyads were examined for fluorescence imaging of human bone cancerous U2OS cells.

The effect of silica thickness on nano TiO2 particles for functional polyurethane nanocomposites.

In order to help reduce the agglomeration of TiO2 nanoparticles in polyurethane coatings while enhancing their photoactivity and mechanical/physical properties, this work examined encapsulating TiO2 nanoparticles in a thin layer of SiO2, prior to their nanocomposite polymerization. By applying a Stöber process, varying thicknesses of SiO2 were successfully coated onto the surface of anatase and rutile TiO2 nanoparticles. The methylene blue results showed that different loadings of SiO2 onto the TiO2 surface significantly influenced their photocatalytic activity. When the loading weight of SiO2 was lower than 3.25 wt%, the photocatalytic activity was enhanced, while with higher loadings, it gave lower photocatalytic activity. When the rutile phase TiO2 surface was fully covered with SiO2, an enhanced photocatalytic activity was observed. When these silica coated nanoparticles were applied in polyurethane coatings, increasing the amount of SiO2 on the titania surface increased the coatings contact angle from 75° to 87° for anatase phase and 70°-78° for rutile phase. The Young's modulus was also increased from 1.06 GPa to 2.77 GMPa for anatase phase and 1.06-2.17 GPa for rutile phase, attributed to the silica layer giving better integration. The thermal conductivity of the polyurethane coatings was also successfully decreased by encapsulating SiO2 on the titania surface for next generation high performance coatings.

Nanostructural adsorption of vanadium oxide on functionalized graphene: a DFT study.

Rutile-monoclinic phase transitions of vanadium oxide (VO2) nanocrystals adsorbed on graphene-based substrates are of current scientific interest, although their adsorption and growth mechanisms have not been investigated theoretically. In this study, we use density functional theory (DFT) calculations for determining the binding energies and predicting the corresponding directions of growth of VO2 nanostructures (rutile and M1-monoclinic) interacting with both pure graphene and functionalized graphene nanoribbons. Several adsorption sites of pure graphene including the top, bridge, and hollow sites are considered, while additional adsorption sites of functionalized graphene nanoribbons, epoxy, alcohol and carboxylate are investigated. Vanadium oxide nanostructures are found to favor physical adsorption on the hollow sites of pure graphene, while chemical adsorption is favored on the carboxylate sites of functionalized graphene nanoribbons (FGNRs). Charge density maps showed the electron distribution originating from the interaction between VO2 and graphene substrates, helping to understand the mechanism of charge transfer. Electronic local potentials showed vertical growth tendencies for rutile VO2, while M1-monoclinic VO2 showed horizontal growth tendencies. Partial density of states (PDOS) helped examine the electronic structure of metallic rutile VO2 binding to hollow and carboxylate sites of functionalized graphene. These results provide an improved understanding of the controlled and oriented growth of VO2 nanocrystals on graphene-based substrates which can enable various properties such as the metal-insulator transition (MIT) of VO2 in light regulation applications.

Stimulation and suppression of innate immune function by American ginseng polysaccharides: biological relevance and identification of bioactives.

BACKGROUND: Polysaccharides constituting about 10% by weight of ginseng root are known to stimulate the immune system but have recently been shown to also suppress induced proinflammatory responses. Our study aims to determine whether American ginseng root polysaccharides (AGRPS) stimulates basal innate immune function and at the same time can suppress response to lipopolysaccharide (LPS) induced proinflammatory response. An in vitro mechanistic study was used to identify the bioactive fraction(s) responsible for AGRPS immunomodulatory effects. METHODS: The ex vivo and in vivo immunomodulatory effects after oral administration of AGRPS extract was studied in adult rats by measuring cultured alveolar macrophage production of NO and changes of plasma cytokine level, modification of LPS proinflammatory immune response by AGRPS extract was also examined. To identify the bioactive fraction(s) responsible for AGRPS extract immunomodulatory effects, the immunobioactivities of the extract fractions (isolated by ion exchange and size exclusion chromatography) was investigated in an in vitro mechanistic study. RESULTS: Culture of alveolar macrophages obtained from AGRPS extract treated rats resulted in an increase of ex vivo production of NO and also reduced alveolar macrophage responsiveness to ex vivo LPS challenge. Oral treatment with AGRPS extract elevated plasma TNF-α concentration in vivo. This treatment also suppressed LPS induced elevation of plasma TNF-α in vivo. AGRPS extract immunostimulatory and immunosuppressive effects were mediated primarily by acid PS and its species with molecular weights ≥ 100 kDa and 50-100 kDa. CONCLUSION: AGRPS extract exerted immunostimulation and suppressed LPS immune response under basal and LPS induced proinflammatory conditions respectively.

Quantum dots/silica/polymer nanocomposite films with high visible light transmission and UV shielding properties.

The dispersion of light-absorbing inorganic nanomaterials in transparent plastics such as poly(ethylene-co-vinyl acetate) (PEVA) is of enormous current interest in emerging solar materials, including photovoltaic (PV) modules and commercial greenhouse films. Nanocrystalline semiconductor or quantum dots (QDs) have the potential to absorb UV light and selectively emit visible light, which can control plant growth in greenhouses or enhance PV panel efficiencies. This work provides a new and simple approach for loading mesoporous silica-encapsulated QDs into PEVA. Highly luminescent CdS and CdS-ZnS core-shell QDs with 5 nm size were synthesized using a modified facile approach based on pyrolysis of the single-molecule precursors and capping the CdS QDs with a thin layer of ZnS. To make both the bare and core-shell structure QDs more resistant against photochemical reactions, a mesoporous silica layer was grown on the QDs through a reverse microemulsion technique based on hydrophobic interactions. By careful experimental tuning, this encapsulation technique enhanced the quantum yield (∼65%) and photostability compared to the bare QDs. Both the encapsulated bare and core-shell QDs were then melt-mixed with EVA pellets using a mini twin-screw extruder and pressed into thin films with controlled thickness. The results demonstrated for the first time that mesoporous silica not only enhanced the quantum yield and photostability of the QDs but also improved the compatibility and dispersibility of QDs throughout the PEVA films. The novel light selective films show high visible light transmission (∼90%) and decreased UV transmission (∼75%).

Fe doped TiO2-graphene nanostructures: synthesis, DFT modeling and photocatalysis.

In this work, Fe-doped TiO(2) nanoparticles ranging from a 0.2 to 1 weight % were grown from the surface of graphene sheet templates containing -COOH functionalities using sol-gel chemistry in a green solvent, a mixture of water/ethanol. The assemblies were characterized by a variety of analytical techniques, with the coordination mechanism examined theoretically using the density functional theory (DFT). Scanning electron microscopy and transmission electron microscopy images showed excellent decoration of the Fe-doped TiO(2) nanoparticles on the surface of the graphene sheets >5 nm in diameter. The surface area and optical properties of the Fe-doped photocatalysts were measured by BET, UV and PL spectrometry and compared to non-graphene and pure TiO(2) analogs, showing a plateau at 0.6% Fe. Interactions between graphene and Fe-doped anatase TiO(2) were also studied theoretically using the Vienna ab initio Simulation Package based on DFT. Our first-principles theoretical investigations validated the experimental findings, showing the strength in the physical and chemical adsorption between the graphene and Fe-doped TiO(2). The resulting assemblies were tested for photodegradation under visible light using 17ß-estradiol (E2) as a model compound, with all investigated catalysts showing significant enhancements in photocatalytic activity in the degradation of E2.

Isolation and immunosuppressive effects of 6″-O-acetylginsenoside Rb1 extracted from North American ginseng.

Extraction of medicinally active components from natural health products has become an emerging source for drug discovery. Of particular interest for this work was the finding and testing of a new ginsenoside from North American ginseng (Panax quinquefolius). In the present study, a large amount of 6″-O-acetylginsenoside Rb1, compound 7, was found using ultrasonic extraction of North American ginseng with DMSO aqueous solution. This new ginsenoside was well identified with MS, FTIR, and 1D (1H and 13C) and 2D (gCOSY, gHSQC, and gHMBC) NMR. Subsequent bioassay experiments confirmed that compound 7 demonstrated an additional immunosuppressive activity towards inhibiting the production of nitric oxide and tumor necrosis factor alpha in lipopolysaccharide-induced macrophage cells in a dose-dependent manner using murine macrophages. This new ginsenoside is encouraging for the further exploration and development of novel drugs.

Enhanced Photocatalytic Properties of All-Organic IDT-COOH/O-CN S-Scheme Heterojunctions Through π-π Interaction and Internal Electric Field.

Herein, we present a distinct methodology for the in situ electrostatic assembly method for synthesizing a conjugated (IDT-COOH)/oxygen-doped g-C3N4 (O-CN) S-scheme heterojunction. The electron delocalization effect due to π-π interactions between O-CN and self-assembled IDT-COOH favors interfacial charge separation. The self-assembled IDT-COOH/O-CN exhibits a broadened visible absorption to generate more charge carriers. The internal electric field between the IDT-COOH and the O-CN interface provides a directional charge-transfer channel to increase the utilization of photoinduced charge carriers. Moreover, the active species (•O2-, h+, and 1O2) produced by IDT-COOH/O-CN under visible light play important roles in photocatalytic disinfection. The optimum 40% IDT-COOH/O-CN can kill 7-log of methicillin-resistant Staphylococcus aureus (MRSA) cells in 2 h and remove 88% tetracycline (TC) in 5 h, while O-CN only inactivates 1-log of MRSA cells and degrades 40% TC. This work contributes to a promising method to fabricate all-organic g-C3N4-based S-scheme heterojunction photocatalysts with a wide range of optical responses and enhanced exciton dissociation.

Growing TiO2 nanowires on the surface of graphene sheets in supercritical CO2: characterization and photoefficiency.

Tremendous interest exists towards synthesizing nanoassemblies for dye-sensitized solar cells (DSSCs) using earth-abundant and -friendly materials with green synthetic approaches. In this work, high surface area TiO(2) nanowire arrays were grown on the surface of functionalized graphene sheets (FGSs) containing -COOH functionalities acting as a template by using a sol-gel method in the green solvent, supercritical carbon dioxide (scCO(2)). The effect of scCO(2) pressure (1500, 3000 and 5000 psi), temperature (40, 60 and 80 °C), acetic acid/titanium isopropoxide monomer ratios (HAc/TIP = 2, 4 and 6), functionalized graphene sheets (FGSs)/TIP weight ratios (1:20, 1:40 and 1:60 w/w) and solvents (EtOH, hexane) were investigated. Increasing the HAc/TIPweight ratio from 4 to 6 in scCO(2) resulted in increasing the TiO(2) nanowire diameter from 10 to 40 nm. Raman and high resolution XPS showed the interaction of TiO(2) with the -COOH groups on the surface of the graphene sheets, indicating that graphene acted as a template for polycondensation growth. UV-vis diffuse reflectance and photoluminescence spectroscopy showed a reduction in titania's bandgap and also a significant reduction in electron-hole recombination compared to bare TiO(2) nanowires. Photocurrent measurements showed that the TiO(2)nanowire/graphene composites prepared in scCO(2) gave a 5× enhancement in photoefficiency compared to bare TiO(2) nanowires.

CdS and CdTeS quantum dot decorated TiO2 nanowires. Synthesis and photoefficiency.

An easy process was developed to synthesize TiO(2) nanowires sensitized with CdS and CdTeS quantum dots (QDs) requiring no pretreatment of the TiO(2) nanowires prior to nanoparticle generation. CdS and CdTeS nanoparticles were firstly grown by an in situ colloidal method directly onto the TiO(2) surface, hence not requiring subsequent functionalization of the QDs. The resulting nanostructure assembly and composition was confirmed by transmission electron microscopy (TEM), x-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. Successful decoration of the TiO(2) nanowires by the QDs was observed by TEM, while XPS spectra provided clear evidence for the coexistence of CdS and CdTeS QDs and TiO(2) nanowires. The electronic structure of the TiO(2) nanowires was preserved as indicated by Raman spectroscopy. Preliminary photocurrent measurements showed that inclusion of Te in CdS QDs improved the photocurrent efficiency. Compared to bare TiO(2) nanowires, CdS/TiO(2) nanoassemblies showed an enhancement in photocurrent efficiency of 300% while CdTeS/TiO(2) presented an improvement of 350%. This study indicates that the generation of strongly anchored CdS and CdTeS QDs on a TiO(2) nanowire surface is achievable without introduction of a linker molecule, whose presence is known to decrease the electron injection efficiency.

2-[(Meth-oxy-carbonothio-yl)sulfan-yl]acetic acid.

The title compound, C(4)H(6)O(3)S(2), features a characteristic xanthate group; the C=S double bond is shorter than the C-S single bond, and the methyl group is coplanar with the xanthate group. In the crystal pairs of mol-ecules form dimers through inter-molecular O-H⋯O hydrogen bonding.

2-[(Dodecylsulfanyl)carbonothioyl-sulfanyl]-propanoic acid.

In the title compound, C(16)H(30)O(2)S(3), the decyl chain adopts an extended zigzag conformation. Two mol-ecules are disposed about a center of inversion, forming an O-H⋯O hydrogen-bonded dimer.

2-[(Eth-oxy-carbonothio-yl)sulfan-yl]acetic acid.

In the title compound, C(5)H(8)O(3)S(2), the C-S and C-O bonds in the xanthate unit are shorter than those linked to it. In the crystal, inversion dimers linked by pairs of O-H⋯O hydrogen bonds occur.

Metal Oxide-Related Dendritic Structures: Self-Assembly and Applications for Sensor, Catalysis, Energy Conversion and Beyond.

In the past two decades, we have learned a great deal about self-assembly of dendritic metal oxide structures, partially inspired by the nanostructures mimicking the aesthetic hierarchical structures of ferns and corals. The self-assembly process involves either anisotropic polycondensation or molecular recognition mechanisms. The major driving force for research in this field is due to the wide variety of applications in addition to the unique structures and properties of these dendritic nanostructures. Our purpose of this minireview is twofold: (1) to showcase what we have learned so far about how the self-assembly process occurs; and (2) to encourage people to use this type of material for drug delivery, renewable energy conversion and storage, biomaterials, and electronic noses.

Transdermal nanotherapeutics: Panax quinquefolium polysaccharide nanoparticles attenuate UVB-induced skin cancer.

Ultraviolet (UV) radiation is known to cause an imbalance of the endogenous antioxidant system leading to an increase in skin cancer. Panax quinquefolium (American ginseng) polysaccharides (GPS) can inhibit such an imbalance due to its anti-oxidative and anti-inflammatory properties. The aim of this study was to investigate the therapeutic effects of topical formulations containing GPS nanoparticles (NPs) to inhibit UVB induced oxidative damage and skin cancer. Photoaging was conducted under UVB irradiation with a dose of 300 mJ/cm2 on SKH1 hairless mice. The treatment groups (n = 5) were as follows: sham control, native GPS, GPS NPs and fluorescent labeled GPS NPs. To compare the photoprotective performance, the topical formulations were applied before and after UVB induction (pre-treatment and post-treatment), followed by sacrificing the animals. Then, skin and blood samples were collected, and inflammatory cytokines production was measured using ELISA. Compared to the sham control, GPS NPs pre-treated mice skin and blood samples exhibited a significant lowering in all cytokine production. In addition, skin histology analysis showed that pre-treatment of GPS NPs prevented epidermal damage and proliferation. The results support that topical formulation containing GPS NPs can inhibit UVB induced oxidative damage and skin cancer.

Zr doping on one-dimensional titania nanomaterials synthesized in supercritical carbon dioxide.

The growth mechanism of one-dimensional metal oxide nanotubular structures is of tremendous current interest to tailor materials using "green" synthetic procedures for emerging industries in alternative energy and biomaterials. In this study, ZrO(2)-modified TiO(2) nanorods and tubular structures were successfully synthesized via a surfactant-free sol-gel route using supercritical carbon dioxide (scCO(2)) as the solvent/drying agent. The effect of metal alkoxide concentration (0.35-1.4 mol/L), acid/metal alkoxide ratio (R = 3-7), and Zr ratio (0-20%) was examined on the morphology and crystallinity of the resulting nanostructures as measured by electron microscopy (SEM and TEM), EDX, XPS, and XRD. The electron microscopy results showed that the crystal growth of the synthesized binary Ti-Zr nanomaterials could be tailored by changing the operating variables with nanotubular structure formed at metal alkoxide concentration of 1.2 mol/L, R = 5-6, and Zr ratio between 4% and 20%. Gelation kinetics for this new system was also studied and revealed that increasing alkoxide concentration and R value enhanced the gelation kinetics. In situ and powder FTIR results revealed that this Ti-Zr binary system follows a similar reaction scheme to that of either single-component system, showing the flexibility of this approach for tailoring nanotubular production.

One-pot procedure to synthesize high surface area alumina nanofibers using supercritical carbon dioxide.

For the first time, high surface area nanofibers were synthesized using aluminum isopropoxide monomer with acetic acid as the polycondensation agent in the green solvent, supercritical carbon dioxide (scCO(2)). It was found that the synthesis temperature, pressure, concentration, and acid/alkoxide ratio had a large effect on fiber formation. By optimizing the experimental conditions at 80 degrees C and 6000 psi of scCO(2) using aluminum isopropoxide at a concentration of 0.3 mmol/mL and acid/alkoxide ratio of 10, alumina nanofibers were formed ranging from 11 to 22 nm in diameter and 500 to 1000 nm in length, and with surface areas up to 580 m(2)/g. Lower temperatures gave irregular shaped nanoparticles, while a lower acid/alkoxide ratio (5:1) resulted in the formation of low surface area alumina bars. Increasing pressure led to better separation of the nanofibers and higher surface areas. In addition to the synthesis conditions, the influence of calcination temperature on the structural, textural, and morphological properties of the materials was examined using various physicochemical techniques including electron microscopy, TGA/DTA, powder XRD, FTIR, XPS, and nitrogen adsorption/desorption analysis. The long fibers with high aspect ratios were found to be thermally stable even after calcining at up to 1050 degrees C. The mechanism of fiber formation in scCO(2) is proposed based on a [Al(OH)(CH(3)CO(2))(2)](n) polycondensate backbone.

Preparing titania aerogel monolithic chromatography columns using supercritical carbon dioxide.

The search for a method to fabricate monolithic inorganic columns has attracted significant recent attention due to their unique ability in separation applications of various biomolecules. Silica and polymer based monolithic columns have been prepared, but titania and other metal oxide monoliths have been elusive, primarily due to their fragility. This article describes a new approach for preparing nanostructured titania based columns, which offer better performance over conventional particle packed columns for separating a wide variety of biomolecules including phosphopeptides. TiO(2) monolithic aerogels were synthesized in separation columns using in situ sol-gel reactions in supercritical carbon dioxide (scCO(2)) followed by calcination, and compared to those prepared in heptanes. The characterization results show that scCO(2) is a better solvent for the sol-gel reactions, providing lower shrinkage with the anatase TiO(2) monolith composed of nanofibers with very high surface areas. The monolithic columns show the ability to isolate phosphopeptides with little flow resistance compared to conventional titania particle based microcolumns.

2-[(Isopropoxycarbonothio-yl)sulfanyl]-acetic acid.

The title compound, C(6)H(10)O(3)S(2), features a planar C atom connected to one O and two S atoms, the C-S single bond being distinctly longer than the C-S double bond. Two mol-ecules are linked by an O-H⋯O hydrogen bond about a center of inversion, generating a dimer.