Two-dimensional correlation analysis study of the photo-induced molecular reorientations of photosensitive polyester film containing 1,4-phenylenediacryloyl units in the backbone.

The photochemical reaction and molecular reorientation of a novel photosensitive polyester, poly[oxy(4-n-butyl-3,5-benzoate)oxy-1,4-phenylenediacryloyl] (PPDA-C4BZ), which contains n-butyl side groups and 1,4-phenylenediacryloyl units (PDA chromophores) in the main chain, are reported in detail. We applied two-dimensional (2D) correlation analysis for the infrared (IR) and ultraviolet (UV) absorption spectra of nanoscaled films of PPDA-C4BZ to establish the sequence of the photo-induced segmental reorientations that result from UV irradiation. The photochemical reaction was found to have a greater effect on the polymer's main chains than on its side groups and to induce the reorientation of the polymer molecules.

Structural evolution in microbial polyesters.

The crystallization behavior of microbially synthesized poly(3-hydroxybutyrate) (PHB) and its copolymers [P(HB-co-HHx)] containing 2.5, 3.4, and 12 mol % 3-hydroxyhexanoate (HHx) comonomer and the melting of the resultant crystals were studied in detail using time-resolved small-angle X-ray scattering and differential scanning calorimetry.

Thermal imidization and structural evolution of thin films of poly(4,4'-oxydiphenylene p-pyromellitamic diethyl ester).

The evolution of chemical composition and structure during the thermal imidization of an ester-type polyimide precursor, poly(4,4'-oxydiphenylene p-pyromellitamic diethyl ester), in micrometer scale films were studied for a heating rate of 2.0 degrees C/min with time-resolved synchrotron X-ray diffraction, in-situ infrared spectroscopy, and modulated differential scanning calorimetry. Our analyses show that the precursor polymer undergoes imidization in a two-step process.

Recent advances in cell-penetrating, non-peptide molecular carriers.

The intracellular delivery of proteins and other bioactive molecules by employing membrane-permeable carrier peptide vectors, e.g. HIV-1 Tat, Antp-HD, and related arginine-rich peptides are well known for a number of years.

Thermal characterization of self-assembled monolayers of dialkyl disulfides containing the urea moiety.

Thermal behaviors of urea-containing dialkyl disulfides 4-(3-octadecylureido)phenyl disulfide (ODPD) and 3-(octadecylureido)ethane disulfide (ODED) and octadecyl disulfide (ODDS) self-assembled monolayers (SAMs) were investigated by infrared reflection-absorption spectroscopy (IRRAS). Among the SAMs, the alkyl chain of ODPD is thermally reversible in the temperature region between 30 and 138 degrees C, whereas alkyl chains of ODED and ODDS are irreversible. With regard to the thermal stability of alkyl chains, ODED is superior to ODPD and ODDS.

N-acyl triazenes as tunable and selective chemodosimeters toward cyanide ion.

A novel type of chemodosimeters has been developed on the basis of a displacement reaction. N-Acyl-triazenes are found to be highly selective and tunable chemodosimeters toward cyanide. When N-acetyl-triazene 1a was titrated with various anions (-CN, F-, Cl-, AcO-, H2PO4-, -SCN, ClO4-, and HSO4-) in acetonitrile, significant absorption changes (from colorless to deep purple) resulted in the cases of -CN and F-, and small changes in the cases of AcO- and H2PO4-.

Bifurcation analysis of mode-locking structure in a Hodgkin-Huxley neuron under sinusoidal current.

Nervous systems under periodic stimuli display rich dynamical states including mode-locking and chaotic responses, which have been a subject of intense studies in neurodynamics. The bifurcation structure of the Hodgkin-Huxley neuron under sinusoidal stimulus is studied in detail. The mechanisms of the firing onset and rich firing dynamics are studied with the help of the codimension-2 bifurcations, which play the role of the organizing center for myriads of saddle-node, period-doubling, and inverse-flip bifurcations forming the boundaries of the complex mode-locking structure.

Enhancement of interleukin-12 gene-based tumor immunotherapy by the reduced secretion of p40 subunit and the combination with farnesyltransferase inhibitor.

Interleukin-12 (IL-12) gene was shown to produce both IL-12 and p40 subunit. The excess production of the p40 subunit as a natural antagonist of IL-12 is a major obstacle of IL-12 gene-based cancer therapy. We previously reported that IL-12N220L gene, which selectively reduces the secretion of the p40 subunit, induces long-lasting stronger type 1 helper T cells (T(H)1) and cytotoxic T lymphocyte (CTL) immunity in hepatitis C virus (HCV) E2 DNA vaccination model and higher protection from challenge with tumor cells expressing E2 than IL-12 in a prophylactic setting.

Protective effect of DNA vaccine during chemotherapy on reactivation and reinfection of Mycobacterium tuberculosis.

Active disease of tuberculosis (TB) can be developed decades later by either a relapse of the initial infection (endogenous reactivation) or by an entrance of the secondary infection (exogenous reinfection), since the current chemotherapy cannot lead to complete elimination of tuberculosis. Although the immunotherapeutic approaches in conjunction with conventional chemotherapy were tried to prevent TB growth via boosting the immune system, their therapeutic effects are still controversial. Here, we found that TB DNA vaccination completely blocked tuberculosis reactivation and significantly prevented from the secondary infection when chemotherapy was combined simultaneously.

Anisotropic thermal expansion behavior of thin films of polymethylsilsesquioxane, a spin-on-glass dielectric for high-performance integrated circuits.

Thin films of poly(methylsilsesquioxane) (PMSSQ) are candidates for use as interdielectric layers in advanced semiconductor devices with multilayer structures. We prepared thin films of PMSSQ with thicknesses in the range 25.0-1151.

Levels and characteristic homologue patterns of polychlorinated dibenzo-p-dioxins and dibenzofurans in various incinerator emissions and in air collected near an incinerator.

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were monitored in stack gas and fly ash of various Korean incinerators and in air samples collected near the facilities. Concentrations of PCDD/Fs in emissions were investigated, and characteristic PCDD/F homologue patterns were classified using statistical analyses. The PCDD/F emission levels in stack gas and fly ash samples from small incinerators (SIs) were higher than those from municipal solid waste incinerators (MSWIs).

Mechanism of growth of colloidal silver nanoparticles stabilized by polyvinyl pyrrolidone in gamma-irradiated silver nitrate solution.

Silver nanoparticles were prepared by using polyvinyl pyrrolidone (PVP) as a stabilizer and gamma-irradiation. Transmission electron microscopy (TEM) results showed that both the amount and the molecular weight of PVP in the irradiated solution considerably affect the average size of the silver nanoparticles. The average size of the silver nanoparticles decreases with increasing the amount of PVP in the solution, but increases with increasing its molecular weight.

Sequence of Rubbing-Induced Molecular Segmental Reorientations in the Nanoscale Film Surface of a Brush Polymer Rod.

Poly(p-phenylene-3,6-bis(4-(n-butoxy)phenyloxy)pyromellitimide) (C4-PMDA-PDA PI), a well-defined model brush polymer composed of a rodlike polymer backbone with two bristles per repeat unit, was the first reported polyimide to align liquid crystals perpendicular to the rubbing direction at the rubbed film surface. In the present study, we used polarized infrared (IR) spectroscopy and 2D correlation analyses of the resulting IR spectra to study nanoscale films of C4-PMDA-PDA PI rubbed at various rubbing densities. The results of these studies allowed us to establish the nature and sequence of the rubbing-induced segmental reorientations that occur in the polymer molecules at the film surface.

Synthesis of three enantiomeric pairs of scyllo-inositol phosphate and molecular interactions between all possible regioisomers of scyllo-inositol phosphate and inositol 1,4,5-trisphosphate 3-kinase.

scyllo-Inositol phosphates, which are among the stereoisomers of myo-inositol phosphate, can have 15 possible regioisomers including three enantiomeric pairs: scyllo-I(1,2)P(2), scyllo-I(1,2,4)P(3), scyllo-I(1,2,3,4)P(4). We herein describe the facile synthetic routes to the three enantiomeric pairs of scyllo-inositol phosphate and the molecular interactions between 15 regioisomers of scyllo-inositol phosphate and inositol 1,4,5-trisphosphate 3-kinase. Geometry of the enzyme binding site is discussed.

Identification of novel target proteins of cyclic GMP signaling pathways using chemical proteomics.

For deciphering the cyclic guanosine monophosphate (cGMP) signaling pathway, we employed chemical proteomics to identify the novel target molecules of cGMP. We used cGMP that was immobilized onto agarose beads with linkers directed at three different positions of cGMP. We performed a pull-down assay using the beads as baits on tissue lysates and identified 9 proteins by MALDI-TOF (Matrix-Assisted Laser Desorption/Ionization Time-of-Flight) mass spectrometry.

Covalent crosslinking of 1-D photonic crystals of microporous Si by hydrosilylation and ring-opening metathesis polymerization.

Free-standing porous Si multilayer dielectric mirrors, prepared by electrochemical etching of crystalline Si, are treated with a ruthenium ring-opening metathesis polymerization (ROMP) catalyst followed by norbornene to produce flexible, stable composite materials in which poly(norbornene) is covalently attached to the porous Si matrix.

Divergent syntheses of all possible optically active regioisomers of myo-inositol tris- and tetrakisphosphates.

Since the discovery of D-myo-inositol 1,4,5-trisphosphate, which plays a pivotal role as a second messenger in transmembrane signaling, the scope of the phosphoinositide-based signaling processes has been continually expanding. However, the clear understanding of the molecular signal transduction mechanisms including the functions of newly found IP(n) is still lacking. As a continuing effort to our previously reported syntheses of all possible 39 optically inactive regioisomers of myo-inositol phosphates (IP(n); n = 1-6), we synthesized all possible optically active regioisomers of myo-IP(3) and myo-IP(4) using chiral IBz(3)s and IBz(2)s, respectively.

Facile syntheses of all possible diastereomers of conduritol and various derivatives of inositol stereoisomers in high enantiopurity from myo-inositol.

Phosphoinositide-based signaling processes are crucially important in intracellular signal transduction events. Inositol phosphate analogues have been useful in probing the structure-activity relationships between inositol phosphates and biomacromolecules, and in studying biological functions of newly found inositol phosphates. Thus, a systematic and ready access to inositol stereoisomers is highly desirable.

Engineering N-glycosylation mutations in IL-12 enhances sustained cytotoxic T lymphocyte responses for DNA immunization.

Interleukin-12 (IL-12), consisting of p40 and p35 subunits, produces both p70 heterodimer and free p40. p70 is essential for the induction of T-helper 1 (Th1) and cytotoxic T-cell (CTL) immunity, whereas p40 inhibits p70-mediated function. Here, we found that mutations introduced into N-glycosylation sites (N220 of murine p40 and N222 of human p40) reduced secretion of p40 but not p70.

Interactions of SV40 large T antigen and other viral proteins with retinoblastoma tumour suppressor.

Simian virus 40 large T antigen, human papilloma virus E7 and adenovirus E1A are all potent oncoproteins that can induce several types of tumours. One of the major functions of these oncoproteins is to interact with the retinoblastoma tumour suppressor protein, Rb, a master switch of the mammalian cell cycle, and to inactivate its function. Rb promotes cell-cycle arrest by recruiting and regulating proteins involved in the transcription of cell proliferation genes.

Denitrification in submerged biofilters of concentrated-nitrate wastewater.

To understand the possibilities and limitations of the treatment of concentrated nitrate in wastewater, a space-saving biofilm process was introduced to investigate how efficiently concentrated nitrate was utilized in a biofilm process. Lab-scale submerged biofilters stuffed with plastic pall-ring media were developed for the treatment of wastewater containing high nitrate concentration. Two identical biofilters were operated at 2 and 4 hr media HRT in parallel and the concentration of nitrate in the influent was increased stepwise from 50 to 3000 mg-N/L.

Design and synthesis of potential inhibitors of the ergosterol biosynthesis as antifungal agents.

A series of azolylmethyloxolane derivatives with modified sterol side-chain structures, designed as potential dual functional inhibitors of cytochrome P450 14alpha-demethylase (14DM) and delta24-sterol methyltransferase (24-SMT) based on the common characteristic features of 24-aminosterols and azole antifungal agents, were synthesized and evaluated for their antifungal activities and inhibitory activities of 14DM and 24-SMT. Among these compounds, imidazolylmethyloxolane derivatives 28a and 28b showed potent in vitro antifungal activities comparable to those of itraconazole. However, the in vitro bioactivities have not been linearly translated into in vivo protection data for some unknown reasons.

Practical synthesis of all inositol stereoisomers from myo-inositol.

Synthesis of six inositol stereoisomers was successfully carried out via conduritol intermediates prepared from myo-inositol. Dihydroxylation and epoxidation followed by ring opening of the conduritol B, C and F derivatives gave epi-, allo-, muco-, neo-, DL-chiro- and scyllo-inositol. The cis-inositol derivative, which may not be prepared by this approach, was synthesized in 5 steps via 2-O-benzoyl-myo-inositol orthoformate as the key intermediate.