Novel efficient routes to heparin monosaccharides and disaccharides achieved via regio- and stereoselective glycosidation

A new methodology for the synthesis of heparin building blocks has been developed. We describe novel efficient routes to both L-iduronic acid and D-glucuronic acid acceptors. Glycosylation with thioglycosides donors gave corresponding disaccharides in a regio- and stereoselective fashion. An improved approach to synthesizing azido-glucose thioglycoside donor to render azido-sugar from mannose via nucleophilic substitution is described. [reaction: see text]     

Reliability of mean transit time obtained using perfusion-weighted MR imaging; comparison with positron emission tomography

The purpose of this project was to assess the reliability of the cerebral mean transit time (MTT) obtained using perfusion-weighted MR imaging by comparing it with the MTT obtained when performing positron emission tomography (PET). Ten patients with chronic occlusive cerebrovascular disease were investigated. They had either unilateral internal carotid artery occlusion or middle cerebral artery occlusion. The regions-of-interest were placed in non-infarcted areas within the territory of the middle cerebral artery on the affected side. Control regions-of-interest were placed in mirrored regions of the contralateral side. Linear regression analyses were performed using the parameters of the MTT obtained with perfusion-weighted MR imaging and the MTT, cerebral blood flow, vascular reactivity, and oxygen extraction fraction obtained with PET. The respective MTTs of the affected and non-affected sides obtained with perfusion-weighted MR imaging versus those with PET were 7.3 +/- 2.2 s and 6.0 +/- 1.2 s versus 8.2 +/- 3.0 s and 6.4 +/- 1.7 s. The MTT obtained using perfusion-weighted MR imaging and PET demonstrated statistically significant correlation (r = 0.87, p < 0.0001). The MTT obtained with perfusion-weighted MR imaging correlated statistically with cerebral blood flow (r = -0.74, p < 0.001), vascular reactivity (r = -0.73, p < 0.001) and oxygen extraction fraction (r = 0.61, p < 0.01). Similarly, the MTT obtained using PET statistically correlated with cerebral blood flow (r = -0.78, p < 0.0001), vascular reactivity (r = -0.51, p < 0.05) and oxygen extraction fraction (r = 0.68, p < 0.01). The reliability of the MTT obtained using perfusion-weighted MR imaging appears to be approximately equal to that obtained with positron emission tomography.     

Noise-driven switching and chaotic itinerancy among dynamic states in a three-mode intracavity second-harmonic generation laser operating on a Lambda transition

We studied the antiphase self-pulsation in a globally coupled three-mode laser operating in different optical spectrum configurations. We observed locking of modal pulsation frequencies, quasiperiodicity, clustering behaviors, and chaos, resulting from the nonlinear interaction among modes. The robustness of [p:q:r] three-frequency locking states and quasiperiodic oscillations against residual noise has been examined by using joint time-frequency analysis of long-term experimental time series. Two sharply antithetical types of switching behaviors among different dynamic states were observed during temporal evolutions; noise-driven switching and self-induced switching, which manifests itself in chaotic itinerancy. The modal interplay behind observed behaviors was studied by using the statistical dynamic quantity of the information circulation. Well-organized information flows among modes, which correspond to the number of degeneracies of modal pulsation frequencies, were found to be established in accordance with the inherent antiphase dynamics. Observed locking behaviors, quasiperiodic motions, and chaotic itinerancy were reproduced by numerical simulation of the model equations.     

Krafft temperature and enthalpy of solution of<Emphasis Type="Italic"> N</Emphasis>-acyl amino acid surfactants and their racemic modifications: effect of the counter ion

The Krafft temperatures and enthalpies of solution of N-hexadecanoyl alaninate and valinate, and N-tetradecanoyl phenylalaninate were obtained from differential scanning calorimetry. The Krafft temperature of N-acyl amino acid surfactant increased with decreasing size of the counter ion, with some exceptions. The enthalpy of solution was endothermic and increased with decreasing size of the counter ion except for the cases of lithium salt. The results showed that the L-L interaction in the solid state of N-hexadecanoyl amino acid surfactant salt was superior to the D-L interaction for both the alanine and valine systems when the counter ion size increased. However, the D-L interaction was still advantageous for the phenylalanine system with Cs⁺ as a counter ion. Both Fourier transform infrared spectroscopy studies and theoretical calculations suggested that the difference in magnitudes of the interactions between peptide and counter ion was a dominant factor for the chiral effect.     

The first example of alpha-thiomagnesiums generated from dithioacetal monoxides with Grignard reagent; their properties and some synthetic applications

Dithioacetal monoxides were synthesized from aldehydes and cyclohexanone, and reaction of the dithioacetal monoxides with Grignard reagents was investigated. The dithioacetal monoxide synthesized from alkylaldehyde and 4-chlorobenzenethiol reacted with i-PrMgCl to afford the desired alpha-thiomagnesium in high yield. The generated alpha-thiomagnesium was found to be stable at room temperature and to be useful in organic synthesis. In contrast to this, the dithioacetal monoxides derived from benzaldehyde and cyclohexanone did not give satisfactory results.     

Electrolytic synthesis of ammonia in molten salts under atmospheric pressure

Ammonia was successfully synthesized by using a new electrochemical reaction with high current efficiency at atmospheric pressure and at lower temperatures than the Haber-Bosch process. In this method, nitride ion (N3-), which is produced by the reduction from nitrogen gas at the cathode, is anodically oxidized and reacts with hydrogen to produce ammonia at the anode.     

Oxidation of sec‐alcohols with Ru(II)‐bearing microgel star polymer catalysts via hydrogen transfer reaction: Unique microgel‐core catalysis

Oxidation of sec‐alcohols was investigated with ruthenium‐bearing microgel core star polymer catalysts [Ru(II)‐Star]. The star polymer catalysts were directly prepared via RuCl₂(PPh₃)₃‐catalyzed living radical polymerization of methyl methacrylate (MMA), followed by the arm‐linking reaction with ethylene glycol dimethacrylate ( 1 ) in the presence of diphenylphosphinostyrene ( 2 ). The Ru(II)‐Star efficiently and homogeneously catalyzed the oxidation of 1‐phenylethanol ( S1 ) to give a corresponding ketone (acetophenone) in higher yield (92%) than the analogs of polymer‐supported ruthenium complexes. Importantly, the star catalyst afforded high recycling efficiency in the oxidation. They held catalytic activity against three times catalysis even though they were recovered under air‐exposure, whereas the conventional RuCl₂(PPh₃)₃ lost the activity for same recycling procedure due to the deactivation by oxygen. The stability of the star catalysts during the recycle experiment was confirmed by detailed spectroscopic characterization. The star polymers also catalyzed oxidation for a wide range of sec‐alcohols with aromatic and aliphatic groups. The substrate affinity was different from that with RuCl₂(PPh₃)₃, suggesting the unique selectivity caused by the specific structure. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.