Phase-Selective Disordered Anatase/Ordered Rutile Interface System for Visible-Light-Driven, Metal-Free CO2 Reduction.

Visible-light-driven photocatalytic CO2 reduction using TiO2 that can absorb light of all wavelengths has been sought for over half a century. Herein, we report a phase-selective disordered anatase/ordered rutile interface system for visible-light-driven, metal-free CO2 reduction using a narrow band structure, whose conduction band position matches well with the reduction potential of CO2 to CH4 and CO. A mixed disordered anatase/ordered rutile (Ad/Ro) TiO2 was prepared from anatase and rutile phase-mixed P25 TiO2 at room temperature and under an ambient atmosphere in sodium alkyl amine solutions. The Ad/Ro TiO2 showed a narrow band structure due to multi-internal energy band gaps of Ti3+ defect sites in the disordered anatase phase, leading to high visible light absorption and simultaneously providing fast charge separation through the crystalline rutile phase, which was faster than that of pristine P25 TiO2. The band gap of Ad/Ro TiO2 is 2.62 eV with a conduction band of -0.27 eV, which matches well with the reduction potential of -0.24 VNHE of CO2/CH4, leading to effective electron transfer to CO2. As a result, the Ad/Ro TiO2 provided the highest CH4 production (3.983 µmol/(g h)), which is higher than that of even metal (W, Ru, Ag, and Pt)-doped P25, for CO2 reduction under visible light.

Chemically modulated graphene quantum dot for tuning the photoluminescence as novel sensory probe.

A band gap tuning of environmental-friendly graphene quantum dot (GQD) becomes a keen interest for novel applications such as photoluminescence (PL) sensor. Here, for tuning the band gap of GQD, a hexafluorohydroxypropanyl benzene (HFHPB) group acted as a receptor of a chemical warfare agent was chemically attached on the GQD via the diazonium coupling reaction of HFHPB diazonium salt, providing new HFHPB-GQD material. With a help of the electron withdrawing HFHPB group, the energy band gap of the HFHPB-GQD was widened and its PL decay life time decreased. As designed, after addition of dimethyl methyl phosphonate (DMMP), the PL intensity of HFHPB-GQD sensor sharply increased up to approximately 200% through a hydrogen bond with DMMP. The fast response and short recovery time was proven by quartz crystal microbalance (QCM) analysis. This HFHPB-GQD sensor shows highly sensitive to DMMP in comparison with GQD sensor without HFHPB and graphene. In addition, the HFHPB-GQD sensor showed high selectivity only to the phosphonate functional group among many other analytes and also stable enough for real device applications. Thus, the tuning of the band gap of the photoluminescent GQDs may open up new promising strategies for the molecular detection of target substrates.

Mesoporous Non-stacked Graphene-receptor Sensor for Detecting Nerve Agents.

A novel gas sensor consisting of porous, non-stacked reduced graphene oxide (NSrGO)-heaxfluorohydoroxypropanyl benzene (HFHPB) nanosheets was successfully fabricated, allowing the detection of dimethyl methyl phosphonate (DMMP), similar to sarin toxic gas. The HFHPB group was chemically grafted to the NSrGO via a diazotization reaction to produce NSrGO-HFHPB. The NSrGO-HFHPB 3D film has a mesoporous structure with a large pore volume and high surface area that can sensitively detect DMMP and concurrently selectively signal the DMMP through the chemically-attached HFHPB. The DMMP uptake of the mesoporous NSrGO-HFHPB was 240.03 Hz, 12 times greater than that of rGO-HFHPB (20.14 Hz). In addition, the response rate of NSrGO-HFHPB was faster than that of rGO-HFHPB, an approximately 3 times more rapid recovery due to the mesoporous structure of the NSrGO-HFHPB. The NSrGO-HFHPB sensor exhibited long-term stability due to the use of robust carbon and resulting high resistance to humidity.

Solar-light photocatalytic disinfection using crystalline/amorphous low energy bandgap reduced TiO2.

A generation of reactive oxygen species (ROS) from TiO2 under solar light has been long sought since the ROS can disinfect organic pollutants. We found that newly developed crystalline/amorphous reduced TiO2 (rTiO2) that has low energy bandgap can effectively generate ROS under solar light and successfully remove a bloom of algae. The preparation of rTiO2 is a one-pot and mass productive solution-process reduction using lithium-ethylene diamine (Li-EDA) at room temperature. Interestingly only the rutile phase of TiO2 crystal was reduced, while the anatase phase even in case of both anatase/rutile phased TiO2 was not reduced. Only reduced TiO2 materials can generate ROS under solar light, which was confirmed by electron spin resonance. Among the three different types of Li-EDA treated TiO2 (anatase, rutile and both phased TiO2), the both phased rTiO2 showed the best performance to produce ROS. The generated ROS effectively removed the common green algae Chlamydomonas. This is the first report on algae degradation under solar light, proving the feasibility of commercially available products for disinfection.

Inhibitory effect of dibutyryl chitin ester on nitric oxide and prostaglandin E2 production in LPS-stimulated RAW 264.7 cells.

Inflammation is a highly complex process that protects against foreign challenge or tissue injury. The ester derivative dibutyryl chitin (DBC) reportedly accelerates wound healing and exerts an anti-inflammatory effect. However, little is known regarding the inhibitory effect of DBC in anti-inflammation. In this study, we investigated the effect of DBC on the inducible nitric oxide synthetase (iNOS) and cyclooxygenage-2 (COX-2) pathways and pro-inflammatory cytokine production in lipopolysaccharide (LPS)-treated RAW 264.7 macrophages. Our results demonstrate that DBC (MW 3,772) significantly inhibits overproduction of NO and PGE(2) as well as pro-inflammatory cytokines, such as tumor necrosis factor-α and interleukin-1ß, in LPS-stimulated RAW 264.7 macrophages. Inhibition of NO and PGE(2) overproduction in LPSstimulated RAW 264.7 macrophages by DBC was mediated through the down-regulation of iNOS and COX-2 expression. These results demonstrate that DBC efficiently inhibits inflammation and has potential as an effective anti-inflammatory and wound healing agent.

Effect of electrospun non-woven mats of dibutyryl chitin/poly(lactic acid) blends on wound healing in hairless mice.

The aim of this study was to examine the proliferative ability of dibutyryl chitin (DBC) on scratch wounds in HaCaT keratinocytes and to evaluate the effect of nanoporous non-woven mat (DBCNFM) on skin wound healing in hairless mice using the advantages of DBCNFM, such as high porosity and high surface area to volume. The cell spreading activity of DBC was verified through a cell spreading assay in scratched human HaCaT keratinocytes. Scratch wound experiments showed that DBC notably accelerates the spreading rate of HaCaT keratinocytes in a dose dependent manner. The molecular aspects of the healing process were also investigated by hematoxylin & eosin staining of the healed skin, displaying the degrees of reepithelialization and immunostaining on extracellular matrix synthesis and remodeling of the skin. Topical application of DBCNFM significantly reduced skin wound rank scores and increased the skin remodeling of the wounded hairless mice in a dose dependent way. Furthermore, DBCNFM notably increased the expression of the type 1 collagen and filaggrin. These results demonstrate that DBC efficiently accelerates the proliferation of HaCaT keratinocytes and DBCNFM notably increases extracellular matrix synthesis on remodeling of the skin, and these materials are a good candidate for further evaluation as an effective wound healing agent.