Nickel-catalysed bis-allylation of internal alkynes with triallylindium

The Ni-catalysed reaction of triallylindium with internal alkynes underwent bis-allylation to afford octa-1,4,7-trienes in high yield.     

Three-dimensional susceptibility-weighted imaging at 3 T using various image analysis methods in the estimation of grading intracranial gliomas

Object

Although three-dimensional (3D), high-spatial resolution susceptibility-weighted imaging (SWI) appears to be valuable in the evaluation of central nervous system gliomas, several evaluation methods are proposed in the literature. The purpose of this study was to evaluate the use of 3D SWI for grading intracranial gliomas with various analysis methods.

Materials and Methods

Twenty-three patients suspected of having gliomas participated in this study. SWI was performed in addition to conventional MR sequences. In 15 cases, post-gadolinium enhanced SWI was also obtained. Imaging evaluation criteria were conventional grade, hypointensity ratio in the tumor-dominant structure of hypointensity on SWI (hemorrhage or vascular structure) and presence of abnormal enhancement surrounding the tumor.

Results

Mean grading scores of conventional grade showed no statistically significant difference among WHO grades. Mean grading scores of hypointensity ratios in the tumor were higher for WHO Grades 3 and 4 than for lower grade tumors (P=.05, Mann–Whitney U test). Hemorrhagic foci were more frequently seen in the higher grade tumor. Post-contrast susceptibility-weighted images of five of 11 WHO Grade 3 and 4 cases showed bright enhancement surrounding the tumor, suggesting a breakdown of the blood–brain barrier.

Conclusions

SWI at 3 T may be a useful method to analyze the structural characteristics of gliomas and to evaluate pathology in vivo. Assessment of hypointensity ratios in the glioma was the most preferable method in grading glioma. However, more studies, specifically concerning a suitable method for image analysis, are needed to establish SWI at 3 T as a useful tool in clinical routine.     

Intravoxel incoherent motion imaging of the kidney: alterations in diffusion and perfusion in patients with renal dysfunction

Purpose

To investigate the relationship between estimated glomerular filtration rate (eGFR) and parameters calculated using intravoxel incoherent motion (IVIM) imaging of the kidneys.

Materials and Methods

We studied 365 patients, divided into 4 groups based on eGFR levels (mL/min/1.73 m²): group 1, eGFR ≥ 80(n = 80); group 2, eGFR 60–80 (n = 156); group 3, eGFR 30–60 (n = 114); and group 4 ,eGFR < 30 (n = 15). IVIM imaging was used to acquire diffusion-weighted images at 12 b values. The diffusion coefficient of pure molecular diffusion (D), the diffusion coefficient of microcirculation or perfusion (D*), and perfusion fraction (f) were compared among the groups using group 1 as control.

Results

In the renal cortex, D* values were significantly lower in groups 2, 3, and 4 than in group 1. The D value of renal cortex was significantly low in only group 3. In the renal medulla, the D* and D values were significantly lower only in groups 2 and 3, respectively.

Conclusion

As renal dysfunction progresses, renal perfusion might be reduced earlier and affected more than molecular diffusion in the renal cortex. These changes are effectively detected by IVIM MR imaging.     

(Non-)Abelian discrete anomalies

We derive anomaly constraints for Abelian and non-Abelian discrete symmetries using the path integral approach. We survey anomalies of discrete symmetries in heterotic orbifolds and find a new relation between such anomalies and the so-called ‘anomalous’ U(1).     

Exhaustive search of the configurational space of heat-shock protein 90 with its inhibitor by multicanonical molecular dynamics based dynamic docking

Multicanonical molecular dynamics based dynamic docking was used to exhaustively search the configurational space of an inhibitor binding to the N-terminal domain of heat-shock protein 90 (Hsp90). The obtained structures at 300 K cover a wide structural ensemble, with the top two clusters ranked by their free energy coinciding with the native binding site. The representative structure of the most stable cluster reproduced the experimental binding configuration, but an interesting conformational change in Hsp90 could be observed. The combined effects of solvation and ligand binding shift the equilibrium from a preferred loop-in conformation in the unbound state to an α-helical one in the bound state for the flexible lid region of Hsp90. Thus, our dynamic docking method is effective at predicting the native binding site while exhaustively sampling a wide configurational space, modulating the protein structure upon binding.     

Effect of dual fullerenes on lifetimes of charge-separated States of subphthalocyanine-triphenylamine-fullerene molecular systems

Photoinduced intramolecular electron-transfer events of the newly synthesized subphthalocyanine-triphenylamine-fullerene triad (SubPc-TPA-C60) and subphthalocyanine-triphenylamine-bisfullerene tetrad (SubPc-TPA-(C(60))(2)) were studied. The geometric and electronic structures of the triad were probed by ab initio B3LYP/3-21G method, which predicts SubPc-TPA(*+)-C(60)(*-) as a stable charge-separated state. The photoinduced events via the excited singlet state of SubPc were monitored by time-resolved emission measurements as well as transient absorption techniques. Efficient charge-separations via the excited states of SubPc were observed with the rates of approximately 10(10) s(-)1. Compared with the SubPc-TPA dyad, a long-lived charge-separated state was observed for the SubPc-TPA-C(60) triad with the lifetime of the radical ion pairs (tau(RIP)) of 670 ns in benzonitrile. Interestingly, further charge stabilization was achieved in the charge-separated state of SubPc-TPA-(C(60))(2), in which the tau(RIP) was found to be 1050 ns in benzonitrile.     

Detection of N-nitroso-bile acids at 285 nm in reverse-phase HPLC

In the present study, we developed a novel, simple, and specific detection method using an RP-HPLC at UV 285 nm for the separation and quantification of N-nitroso-bile acids. First, we found that N-nitroso-bile acids have a specific spectrophotometric absorbance at 285 nm. Using this 285 nm detection system, we could especially measure N-nitroso-bile acids, even in co-existence of non-N-nitroso-bile acids. Next, we observed the decomposition of N-nitroso-glychocholate under alkaline, acidic, and neutral conditions. N-nitroso-glychocholate rapidly decomposed under alkaline conditions (pH 9) (t(1/2) = 0.96 h), but remained fairly stable under acidic (pH 2) (t(1/2) = 12.8 h) and neutral (pH 7) (t(1/2) = 7.8 h) conditions. This study is the first report, which simply and specifically analyzes N-nitroso-bile acids using an RP-HPLC system.