The basis set superposition error in multilevel methods: a test on the H2O and HF dimer

The basis set superposition error (BSSE) is often very important in the accurate calculation of dimerization energies. Accurate prediction of thermochemical properties requires appropriate consideration of the basis set incompleteness error. Multilevel methods introduce adjustable parameters to reproduce experimental data, that is, the higher level correction (HLC) in G3 and adjustable coefficients in the MCCM. However, the HLC term is cancelled out and the adjustable coefficients in the MCCM do not remove the BSSE completely. We have calculated the BSSE involved in the multilevel methods. The H₂O and HF dimer systems were used as a test case. This study shows that empirical coefficients do reduce the BSSE in some cases and an MCCM with good parameters can be used to reproduce dimerization energies within chemical accuracy without the BSSE correction.     

Zinc selective chemosensor based on pyridyl-amide fluorescence

Chemosensors are developed to image zinc ions. Fluorescence enhancement due to Zn²⁺ binding is an excellent way to detect its presence. A chemosensor for Zn²⁺ based on dipicolylamine (DPA) groups connected by a pyridyl amide backbone has been synthesized. Addition of 2-chloroacetyl chloride to 2,6-diaminopyridine affords 2,6-bis(chloroethylamido)pyridine, which is converted to the sensor BADPA-P by 2,2′-dipicolylamine displacement of chlorine. This compound along with two others, the mono-DPA, ADPA-P and the benzyl in place of pyridyl, BADPA-B, present three potential Zn²⁺ sensors. It was found that BADPA-P in the presence of Zn²⁺ shows a large increase in fluorescence, whether in polar organic or aqueous environments. Its fluorescence in the presence of Cd²⁺, unlike with Zn²⁺, is not enhanced when excited at longer wavelengths. Proton NMR measurements, indicate two Zn²⁺ ions bind to BADPA-P. Also, Zn²⁺ enhances fluorescence even when other metal ions are present.     

Cost‐Effective,High‐Performance Porous‐Organic‐Polymer Conductors Functionalized with Sulfonic Acid Groups by Direct Postsynthetic Substitution

We demonstrate the facile microwave‐assisted synthesis of a porous organic framework 1 and the sulfonated solid ( 1S ) through postsubstitution. Remarkably, the conductivity of 1S showed an approximately 300‐fold enhancement at 30 °C as compared to that of 1 , and reached 7.72×10^?2 S cm^?1 at 80 °C and 90 % relative humidity. The superprotonic conductivity exceeds that observed for any conductive porous organic polymer reported to date. This material, which is cost‐effective and scalable for mass production, also revealed long‐term performance over more than 3 months without conductivity decay.     

Contralaterally transplanted human embryonic stem cell-derived neural precursor cells (ENStem-A) migrate and improve brain functions in stroke-damaged rats

The transplantation of neural precursor cells (NPCs) is known to be a promising approach to ameliorating behavioral deficits after stroke in a rodent model of middle cerebral artery occlusion (MCAo). Previous studies have shown that transplanted NPCs migrate toward the infarct region, survive and differentiate into mature neurons to some extent. However, the spatiotemporal dynamics of NPC migration following transplantation into stroke animals have yet to be elucidated. In this study, we investigated the fates of human embryonic stem cell (hESC)-derived NPCs (ENStem-A) for 8 weeks following transplantation into the side contralateral to the infarct region using 7.0T animal magnetic resonance imaging (MRI). T2- and T2*-weighted MRI analyses indicated that the migrating cells were clearly detectable at the infarct boundary zone by 1 week, and the intensity of the MRI signals robustly increased within 4 weeks after transplantation. Afterwards, the signals were slightly increased or unchanged. At 8 weeks, we performed Prussian blue staining and immunohistochemical staining using human-specific markers, and found that high percentages of transplanted cells migrated to the infarct boundary. Most of these cells were CXCR4-positive. We also observed that the migrating cells expressed markers for various stages of neural differentiation, including Nestin, Tuj1, NeuN, TH, DARPP-32 and SV38, indicating that the transplanted cells may partially contribute to the reconstruction of the damaged neural tissues after stroke. Interestingly, we found that the extent of gliosis (glial fibrillary acidic protein-positive cells) and apoptosis (TUNEL-positive cells) were significantly decreased in the cell-transplanted group, suggesting that hESC-NPCs have a positive role in reducing glia scar formation and cell death after stroke. No tumors formed in our study. We also performed various behavioral tests, including rotarod, stepping and modified neurological severity score tests, and found that the transplanted animals exhibited significant improvements in sensorimotor functions during the 8 weeks after transplantation. Taken together, these results strongly suggest that hESC-NPCs have the capacity to migrate to the infarct region, form neural tissues efficiently and contribute to behavioral recovery in a rodent model of ischemic stroke.     

Characterization of Nitro-Substituted Polybenzimidazole Synthesized by the Reaction with Nitric Acid

Abstract

Nitro-substituted poly[2,2′-(m-phenylene)-5,5′-bibenzimidazole]s (PBIs) were synthesized by the reaction of PBI with nitric acid in sulfuric acid under various conditions. The number of nitro groups substituted on the aromatic ring of PBI per polymeric unit varied from 1.44 to 3.55 according to the reaction conditions. An increase in reaction temperature and concentration of the nitric acid increased the degree of substitution. The inherent viscosity of the substituted polymer increased as the reaction temperature decreased. When the reaction temperature was 30°C, the inherent viscosity of the polymer increased as the concentration of nitric acid increased. The nitro-substituted PBI exhibited polyelectrolyte behavior in formic acid. The nitro groups substituted on PBI were dissociated when the polymer was heated to 450°C, displaying exothermic behavior, and the decomposition of polymer was proportional to its nitro group content. All nitro-substituted PBIs showed better solubilities in polar aprotic and acidic solvents, such as dimethylacetamide, dimethylsulfoxide, dimethylformamide, N-methylpyrrolidone, formic acid, sulfuric acid, and trifluoromethanesulfonic acid.     

Glucose Oxidase/Cellulose–Carbon Nanotube Composite Paper as a Biocompatible Bioelectrode for Biofuel Cells

Biofuel cells are devices for generating electrical energy directly from chemical energy of renewable biomass using biocatalysts such as enzymes. Efficient electrical communication between redox enzymes and electrodes is essential for enzymatic biofuel cells. Carbon nanotubes (CNTs) have been recognized as ideal electrode materials because of their high electrical conductivity, large surface area, and inertness. Electrodes consisting entirely of CNTs, which are known as CNT paper, have high surface areas but are typically weak in mechanical strength. In this study, cellulose (CL)–CNT composite paper was fabricated as electrodes for enzymatic biofuel cells. This composite electrode was prepared by vacuum filtration of CNTs followed by reconstitution of cellulose dissolved in ionic liquid, 1-ethyl-3-methylimidazolium acetate. Glucose oxidase (GOx), which is a redox enzyme capable of oxidizing glucose as a renewable fuel using oxygen, was immobilized on the CL–CNT composite paper. Cyclic voltammograms revealed that the GOx/CL–CNT paper electrode showed a pair of well-defined peaks, which agreed well with that of FAD/FADH_2, the redox center of GOx. This result clearly shows that the direct electron transfer (DET) between the GOx and the composite electrode was achieved. However, this DET was dependent on the type of CNTs. It was also found that the GOx immobilized on the composite electrode retained catalytic activity for the oxidation of glucose.     

The Reaction of Ninhydrin with Trimethylbenzenes under Friedel-Crafts Reaction Conditions

The reaction of ninhydrin with 1,2,3- and 1,2,4-trimethylbenzene in the presence of H₂SO₄ or AlCl₃ afforded 2-monoaryl and 2,2-diaryl-1,3-indanedione derivatives as the major products. With 1,3,5-trimethylbenzene as the arene nucleophile, either a reduction product or an indenoindanone derivative was obtained depending upon the catalyst employed in the reaction.     

New regioisomeric naphthol–thiazole based ‘turn-on’ fluorescent chemosensor for Al

Two new reactive and highly selective turn-on fluorescent chemosensors based on the position of ring annulation of the naphthalene–thiazole moiety for aluminum ions in ethanol, were synthesized and investigated. It was found that sensors 2 and 4 exhibited a remarkable enhancement of emission upon complexation with Al³⁺. A TD-B3LYP/6-31G(d,p) calculation was performed to characterize the nature of the fluorescence behavior of sensors 2 and 4 upon Al³⁺ complexation. The mechanism of fluorescence was based on the cation promoted hydrolysis of ester and subsequent complexation. The combination of experimental and computational analyses provides a more complete understanding of the molecular level origin of these types of unique photophysical properties.     

Electro-optic applications of soluble polypyrrole

The optical transmittance of the film spin-cast from the polypyrrole(PPy) solution in chloroform depended on the thickness of the film. The film with 80% transmittance showed a surface resistivity of 23kΩ/□. A TN-LCD cell with rubbed PPy films as the LC alignment layers responded properly to an applied potential of 3.0V. Reflective mode cholesteric LCD cells made with black PPy film electrodes responded to AC fields to switch between the planar and focal conic states. PPy with imine structures introduced by deprotonation of doped PPy with NaOH solution was used as a diode material to exhibit a photo-current on exposing to light.     

Serum exosomal microRNAs as novel biomarkers for hepatocellular carcinoma

Recent studies have shown that circulating microRNAs are a potential biomarker in various types of malignancies. The aim of this study was to investigate the feasibility of using serum exosomal microRNAs as novel serological biomarkers for hepatocellular carcinoma (HCC) in patients with chronic hepatitis B (CHB). We measured the serum exosomal microRNAs and serum circulating microRNAs in patients with CHB (n=20), liver cirrhosis (LC) (n=20) and HCC (n=20). Serum exosomal microRNA was extracted from 500 μl of serum using an Exosome RNA Isolation kit. The expression levels of microRNAs were quantified by real-time PCR. The expression levels of selected microRNAs were normalized to Caenorhabditis elegans microRNA (Cel-miR-39). The serum levels of exosomal miR-18a, miR-221, miR-222 and miR-224 were significantly higher in patients with HCC than those with CHB or LC (P<0.05). Further, the serum levels of exosomal miR-101, miR-106b, miR-122 and miR-195 were lower in patients with HCC than in patients with CHB (P=0.014, P<0.001, P<0.001 and P<0.001, respectively). There was no significant difference in the levels of miR-21 and miR-93 among the three groups. Additionally, the serum levels of circulating microRNAs showed a smaller difference between HCC and either CHB or LC. This study suggests that serum exosomal microRNAs may be used as novel serological biomarkers for HCC.