Molecular motions of tactic poly(2-hydroxyethyl methacrylate) in solutions studied by 13C-NMR relaxation measurement

The spin-lattice relaxation time and the nuclear Overhauser enhancement were measured using Bruker AM 300 spectrometer operating at 75.5 MHz for ¹³C to investigate the molecular motional characteristics and its tacticity effect for tactic poly(2-hydroxyethyl methacrylate) (PHEMA) as a function of temperature in dimethyl sulfoxide and methanol solvents. The observed relaxation data have been analyzed for both backbone motion and methyl internal rotation according to the log-χ² distribution model and the diamond-lattice model. The correlation times thus obtained for the molecular motions show that isotactic PHEMA is more flexible than syndiotactic counterpart. The syndiotactic PHEMA seems to have intramolecular hydrogen bonding which restricts the motion of C-2 carbon at temperatures below 35°C, whereas the isotactic one indicated no hydrogen bonding at all temperatures examined in this study. The methyl group of isotactic PHEMA shows a greater degree of freedom for the internal rotation than that of syndiotactic one. From the temperature dependence of correlation times, the activation energies for both backbone segmental motion and methyl internal rotation are obtained. The activation energies, 20 kJ/mol for backbone motion and 19 kJ/mol for methyl internal rotation, for isotactic PHEMA are substantially lower than the corresponding activation energies of 30 and 32 kJ/mol obtained for syndiotactic one. An examination of these energies indicates that methyl side group and backbone motions in tactic PHEMA are linked together.     

Application of129Xe NMR spectroscopy and EXAFS to probe the formation of a bimetallic cluster in zeolite Y

Palladium was supported on CaY zeolite by ion exchange of Pd(NH₃) ₄ ²⁺ into CaY zeolite, calcination in O₂ and subsequent reduction with H₂. Platinum and silver were added to this Pd/CaY zeolite by ion exchange of Pt(NH₃) ₄ ²⁺ and Ag⁺, respectively, and subsequent reduction with Hg. Extended X-ray absorption fine structure of these metals indicates that the successive metal-loading treatments lead first to the formation of a 1-nm Pd cluster inside the supercage of CaY zeolite and to the subsequent formation of bimetallic clusters through incorporation of Pt and Ag atoms into the small Pd cluster. The line width and chemical shift of¹²⁹Xe NMR spectrum of xenon gas adsorbed on the zeolite show dramatic changes during the metal clustering procedure, which indicates that¹²⁹Xe NMR spectroscopy can be used to probe the formation of bimetallic clusters.     

NF-κB-dependent miR-31/155 biogenesis is essential for TNF-α-induced impairment of endothelial progenitor cell function

Endothelial progenitor cell (EPC) dysfunction impairs vascular function and remodeling in inflammation-associated diseases, including preeclampsia. However, the underlying mechanism of this inflammation-induced dysfunction remains unclear. In the present study, we found increases in TNF-α and miR-31/155 levels and reduced numbers of circulating EPCs in patients with preeclampsia. Patient-derived mononuclear cells (MNCs) cultured in autologous serum had decreased endothelial nitric oxide synthase (eNOS) expression, nitric oxide production, and differentiation into EPCs with angiogenic potential, and these effects were inhibited by a TNF-α-neutralizing antibody and miR-31/155 inhibitors. Moreover, TNF-α treatment of normal MNCs increased miR-31/155 biogenesis, decreased eNOS expression, reduced EPC differentiation, and impaired angiogenic potential. The TNF-α-induced impairment of EPC differentiation and function was rescued by NF-κB p65 knockdown or miR-31/155 inhibitors. In addition, treatment of MNCs with synthetic miR-31/155 or an eNOS inhibitor mimicked the inhibitory effects of TNF-α on eNOS expression and EPC functions. Moreover, transplantation of EPCs that had been differentiated from TNF-α-treated MNCs decreased neovascularization and blood perfusion in ischemic mouse hindlimbs compared with those of normally differentiated EPCs. These findings suggest that NF-κB activation is required for TNF-α-induced impairment of EPC mobilization, differentiation, and function via miR-31/155 biogenesis and eNOS downregulation. Our data provide a new role for NF-κB-dependent miR-31/155 in EPC dysfunction under the pathogenic conditions of inflammation-associated vascular diseases, including preeclampsia.Subject terms: Differentiation, Cell biology     

Separation of racemic 2,4-dinitrophenyl amino acids on zirconia-immobilized quinine carbamate in reversed-phase liquid chromatography

Zirconia is known to be one of the best chromatographic support materials due to its excellent chemical, thermal, and mechanical stability. A quinine carbamate-coated zirconia was prepared as a chiral stationary phase for separation of enantiomers of DNP-amino acids in reversed-phase liquid chromatography. Retention and enantioselectivity of this phase were compared to those for quinine carbamate bonded onto silica. Most amino acids studied were separated on the quinine carbamate-zirconia CSP although retention was longer and chiral selectivity was somewhat lower than on the corresponding silica CSP. Increased retention and decreased selectivity are probably due to strong non-enantioselective Lewis acid-base interactions between the amino acid molecule and the residual Lewis acid sites on the zirconia surface.     

Synthesis of mesoporous silicas of controlled pore wall thickness and their replication to ordered nanoporous carbons with various pore diameters

A synthesis strategy for the systematic control of the pore wall thickness has been developed for the mesoporous silicas with 2-D hexagonal order using ionic and nonionic surfactant mixtures. The mesoporous silicas have been used as templates for the synthesis of 2-D hexagonally ordered mesoporous carbons with controlled pore diameters. The synthesis strategy and results are useful not only for tailoring the properties of the mesoporous materials but also for extending our insights into the synthesis mechanism.     

Synthesis of novel apio carbocyclic nucleoside analogues as selective a(3) adenosine receptor agonists

On the basis of the biological activity of neplanocin A and apio-dideoxyadenosine (apio-ddA), novel apio-neplanocin A analogues 5a-d, combining the properties of two nucleosides, were stereoselectively synthesized. The apio moiety of the target nucleosides 5a-d was stereoselectively introduced by treating lactol 10 with 37% formaldehyde in the presence of potassium carbonate. The carbasugar moiety of neplanocin A was successively built by exposing diene 12 on a Grubbs catalyst in methylene chloride. The final nucleosides 5a-d were synthesized from the condensation of the glycosyl donor 14 with nucleic bases under the standard Mitsunobu conditions. Similarly, apio-aristeromycin 6 and (N)-apio-methanocarbaadenosine 7 were derived from the common intermediate 13 using catalytic hydrogenation and Simmons-Smith cyclopropanation as key steps. All of the final nucleosides 5a-d, 6, and 7 did not show significant inhibitory activity against S-adenosylhomocysteine hydrolase (SAH) up to 100 muM, maybe due to the absence of the secondary hydroxyl group at the C3'-position, which should be oxidized by cofactor-bound NAD(+). However, apio-neplanocin A (5a) showed potent and highly selective binding affinity (K(i) = 628 +/- 69 nM) at the A(3) adenosine receptor without any binding affinity at the A(1) and A(2A) adenosine receptors. In conclusion, we have first developed novel carbocyclic nucleosides with unnatural apio-carbasugars using stereoselective hydroxymethylation and RCM reaction and also discovered a new template of human A(3) adenosine receptor agonist, which play a great role in developing new A(3) adenosine receptor agonist as well as in identifying the binding site of the receptor.     

Electron microscopy study of novel Pt nanowires synthesized in the spaces of silica mesoporous materials.

Structures of Pt-nanowires, synthesized in channels of silica mesoporous materials MCM-41, SBA-15 and MCM-48, were investigated by transmission electron microscopy. One dimensional (1D) Pt-nanowires were formed inside the channels of the MCM-41, and were single crystals with a length of several tens to several hundreds nanometers and a diameter of ca. 3 nm pt-nanowires synthesized in SBA-15 formed a new 3D-network following 3D-pore geometry of SBA-15; that is, the main 1D-channels are interconnected to each other through randomly distributed tunnels. These Pt-nanowires showed a well single crystalline. MCM-48 has two non-intersecting chiral channels, and Pt-networks were mostly formed in one of the two channels. Therefore the networks were also chiral; however, the chirality of Pt-networks remained to be determined. It was shown that all Pt-nanowires were formed following the channel geometries of silica mesoporous materials used.     

A numerical computation of the structure of the roots of q-Bernoulli polynomials

Over the years, there has been increasing interest in solving mathematical problems with the aid of computers. The main purpose of this paper is to construct new generating functions of q  -Bernoulli numbers _βn,qr${\beta }_{n,q^r}$ and q  -Bernoulli polynomials _βn,qr(x)${\beta }_{n,q^r}(x)$. We study the q  -Bernoulli polynomials _βn,qr(x)${\beta }_{n,q^r}(x)$ and investigate the roots of the q  -Bernoulli polynomials _βn,qr(x)${\beta }_{n,q^r}(x)$ for values of the index n by using computer. Finally, we consider the reflection symmetries of the q-Bernoulli polynomials.     

A new synthetic route to (North)-methanocarba nucleosides designed as A3 adenosine receptor agonists

Activation of the A3 adenosine receptor (AR) is associated with cerebroprotective, cardioprotective, and anticancer effects. Among potent and selective A3 AR agonists are novel methanocarba adenosine analogues in which the conformation of a pseudo-ribose moiety is locked in the North (N) hemisphere of the pseudorotational cycle. 5'-Uronamide (N)-methanocarba nucleosides, such as MRS1898 and MRS2346, are examples of full agonists of the human A3 AR. An improved convergent approach from easily accessible 2,3-O-isopropylidene-d-erythrose (2b), and the combination of a strategic intramolecular cyclopropanation step plus the acid-catalyzed isomerization of an isopropylidene group, provided a suitable pseudosugar precursor (23) for the synthesis of MRS1898, MRS2346, and related analogues. This new synthetic route uses readily available building blocks and opens the way for the preparation of a variety of targets on a reasonable scale.