Influence of formic acid on electrochemical properties of high‐porosity Pt/TiN nanoparticle aggregates

Platinum‐deposited titanium nitride (Pt/TiN) nanoparticle aggregates with high porosities were successfully prepared via a self‐assembly‐assisted spray pyrolysis method. The addition of formic acid (HCOOH) had a significant influence on the process, promoting the simultaneous formation of metallic Pt and reduction on the surface of the TiN support material. Complete reduction of the Pt/TiN nanoparticle aggregates improved the catalytic activity. The electrochemical surface area (ECSA) of Pt/TiN with HCOOH (Pt/TiN_w/HCOOH) was 87.15 m²/g‐Pt, which was higher than that of Pt/TiN without HCOOH (Pt/TiN_w/o‐HCOOH). The catalytic durability of Pt/TiN_w/HCOOH was twice that of Pt/TiN_w/o‐HCOOH. An effective strategy for obtaining carbon‐free catalysts with high activities and durabilities was identified. © 2013 American Institute of Chemical Engineers AIChE J, 59: 2753–2760, 2013     

Perspectives on biodiesel as a sustainable fuel

The present global economy downturn affects every corner of the world including the vehicular fuel industry. This paper highlights some of the perspectives for the biodiesel industry to thrive as an alternative fuel, while discussing benefits and limitations of biodiesel. This includes the improvement of the conversion technology to achieve a sustainable process at cheaper cost, environmentally benign and cleaner emissions, diversification of products derived from glycerol, and policy and government incentives. More specifically, an overview is given on making the production process more economical by developing high conversion and low cost catalysts from renewable sources, and utilizing waste oil as feedstock. Further emphasis is given on the need for public education and awareness for the use and benefits of biodiesel, while promoting policies that will not only endorse the industry, but also promote effective land management.     

生物油中提取热解木质素的性质分析(英文)

Bio-oil is a new liquid fuel produced by fast pyrolysis, which is a promising technology to convert biomass into liquid. Pyrolytic lignin extracted from bio-oil, a fine powder, contributes to the instability of bio-oil. The paper presents the structural features of three kinds of pyrolytic lignin extracted from bio-oil with different methods (WIF, HMM, and LMM). The pyrolytic lignin samples are characterized by Fourier transform infrared spectrometer (FTIR) and X-ray photoelectron spectroscopy (XPS). FTIR data indicate that the three pyrolytic lignin samples have similar functional groups, while the absorption intensity is different, and show characteristic vibrations of typical lignocellulosic material groups O H (3340-3380 cm1), C H (2912-2929 cm1) and C O (1652-1725 cm1). Comparison in the region (3340-3380 cm1) indicates that WIF has more O H stretch groups than HMM and LMM. The carbon spectra are fitted to four peaks: C1, C C or C H, BE 283.5 eV; C2, C OR or C OH, BE 284.5-285.8 eV; C3, C O or HO C OR, BE 286.10-287.10 eV; C4, O C O, BE 287.5-287.7 eV. The absence of C1, C C or C H indicates the dominant polymerization structure of aromatic carbon in pyrolytic lignin samples. For HMM and WIF, C2a and C2b can not be separated, so there is no free hydroxyl group in the samples. The oxygen peaks are also fitted to four peaks: O1, OH, BE = 530.3 eV; O2, RC O, BE 531.45-531.72 eV; O3, O C O, BE = 532.73-533.74 eV; O4, H2O, BE 535 eV. The absence of O1 and O4 indicates that little hydroxyl groups and adsorbed water are present in the samples.     

Impact of Oncogenic Targets by Tumor-Suppressive miR-139-5p and miR-139-3p Regulation in Head and Neck Squamous Cell Carcinoma

We newly generated an RNA-sequencing-based microRNA (miRNA) expression signature of head and neck squamous cell carcinoma (HNSCC). Analysis of the signature revealed that both strands of some miRNAs, including miR-139-5p (the guide strand) and miR-139-3p (the passenger strand) of miR-139, were downregulated in HNSCC tissues. Analysis of The Cancer Genome Atlas confirmed the low expression levels of miR-139 in HNSCC. Ectopic expression of these miRNAs attenuated the characteristics of cancer cell aggressiveness (e.g., cell proliferation, migration, and invasion). Our in silico analyses revealed a total of 28 putative targets regulated by pre-miR-139 (miR-139-5p and miR-139-3p) in HNSCC cells. Of these, the GNA12 (guanine nucleotide-binding protein subunit alpha-12) and OLR1 (oxidized low-density lipoprotein receptor 1) expression levels were identified as independent factors that predicted patient survival according to multivariate Cox regression analyses (p = 0.0018 and p = 0.0104, respectively). Direct regulation of GNA12 and OLR1 by miR-139-3p in HNSCC cells was confirmed through luciferase reporter assays. Moreover, overexpression of GNA12 and OLR1 was detected in clinical specimens of HNSCC through immunostaining. The involvement of miR-139-3p (the passenger strand) in the oncogenesis of HNSCC is a new concept in cancer biology. Our miRNA-based strategy will increase knowledge on the molecular pathogenesis of HNSCC.     

Sulfated Hyaluronan Binds to Heparanase and Blocks Its Enzymatic and Cellular Actions in Carcinoma Cells

We examined whether sulfated hyaluronan exerts inhibitory effects on enzymatic and biological actions of heparanase, a sole endo-beta-glucuronidase implicated in cancer malignancy and inflammation. Degradation of heparan sulfate by human and mouse heparanase was inhibited by sulfated hyaluronan. In particular, high-sulfated hyaluronan modified with approximately 2.5 sulfate groups per disaccharide unit effectively inhibited the enzymatic activity at a lower concentration than heparin. Human and mouse heparanase bound to immobilized sulfated hyaluronan. Invasion of heparanase-positive colon-26 cells and 4T1 cells under 3D culture conditions was significantly suppressed in the presence of high-sulfated hyaluronan. Heparanase-induced release of CCL2 from colon-26 cells was suppressed in the presence of sulfated hyaluronan via blocking of cell surface binding and subsequent intracellular NF-κB-dependent signaling. The inhibitory effect of sulfated hyaluronan is likely due to competitive binding to the heparanase molecule, which antagonizes the heparanase-substrate interaction. Fragment molecular orbital calculation revealed a strong binding of sulfated hyaluronan tetrasaccharide to the heparanase molecule based on electrostatic interactions, particularly characterized by interactions of (−1)- and (−2)-positioned sulfated sugar residues with basic amino acid residues composing the heparin-binding domain-1 of heparanase. These results propose a relevance for sulfated hyaluronan in the blocking of heparanase-mediated enzymatic and cellular actions.     

Mutated KIT Tyrosine Kinase as a Novel Molecular Target in Acute Myeloid Leukemia

KIT is a type-III receptor tyrosine kinase that contributes to cell signaling in various cells. Since KIT is activated by overexpression or mutation and plays an important role in the development of some cancers, such as gastrointestinal stromal tumors and mast cell disease, molecular therapies targeting KIT mutations are being developed. In acute myeloid leukemia (AML), genome profiling via next-generation sequencing has shown that several genes that are mutated in patients with AML impact patients’ prognosis. Moreover, it was suggested that precision-medicine-based treatment using genomic data will improve treatment outcomes for AML patients. This paper presents (1) previous studies regarding the role of KIT mutations in AML, (2) the data in AML with KIT mutations from the HM-SCREEN-Japan-01 study, a genome profiling study for patients newly diagnosed with AML who are unsuitable for the standard first-line treatment (unfit) or have relapsed/refractory AML, and (3) new therapies targeting KIT mutations, such as tyrosine kinase inhibitors and heat shock protein 90 inhibitors. In this era when genome profiling via next-generation sequencing is becoming more common, KIT mutations are attractive novel molecular targets in AML.     

Antisense Oligonucleotide Modified with Disulfide Units Induces Efficient Exon Skipping in mdx Myotubes through Enhanced Membrane Permeability and Nucleus Internalization

We have found that antisense oligonucleotides and siRNA molecules modified with repeat structures of disulfide units can be directly introduced into the cytoplasm and exhibit a suppressive effect on gene expression. In this study, we analyzed the mechanism of cellular uptake of these membrane-permeable oligonucleotides (MPONs). Time-course analysis by confocal microscopy showed that the uptake of MPONs from the plasma membrane to the cytoplasm reached 50 % of the total uptake in about 5 min. In addition, analysis of the plasma membrane proteins to which MPONs bind, identified several proteins, including voltage-dependent anion channel. Next, we analyzed the behavior of MPONs in the cell and found them to be abundant in the nucleus as early as 24 h after addition with the amount increasing further after 48 and 72 h. The amount of MPONs was 2.5-fold higher than that of unmodified oligonucleotides in the nucleus after 72 h. We also designed antisense oligonucleotides and evaluated the effect of MPONs on mRNA exon skipping using DMD model cells; MPONs caused exon skipping with 69 % efficiency after 72 h, which was three times higher than the rate of the control. In summary, the high capacity for intracytoplasmic and nuclear translocation of MPONs is expected to be useful for therapeutic strategies targeting exon skipping.     

Completely Chemically Synthesized Long DNA Can be Transcribed in Human Cells

Chemical ligation reaction of DNA is useful for the construction of long functional DNA using oligonucleotide fragments that are prepared by solid phase chemical synthesis. However, the unnatural linkage structure formed by the ligation reaction generally impairs the biological function of the resulting ligated DNA. We achieved the complete chemical synthesis of 78 and 258 bp synthetic DNAs via multiple chemical ligation reactions with phosphorothioate and haloacyl-modified DNA fragments. The latter synthetic DNA, coding shRNA for luciferase genes with a designed truncated SV promoter sequence, successfully induced the expected gene silencing effect in HeLa cells.     

Absolute Stereochemistry of TXIB,a Bioactive Plasticizer That Inhibits Oviposition of the Peach Fruit Moth,Carposina sasakii (Lepidoptera: Carposinidae)

Journal of Chemical Ecology - TXIB (2,2,4-trimethyl-1,3-pentanediol diisobutyrate), a common plasticizer, inhibits the peach fruit moth, Carposina sasakii from ovipositing on young apple fruits....