Thermal reaction of electron deficient 4‐oxo‐4H‐pyrazole 1,2‐dioxide with cycloheptatriene: the first examples of the formation of an endo‐[4π + 6π]‐cycloadduct and an intramolecular 1,3‐dipolar reaction leading to a heterocage

The reaction of 3,5‐bis(methoxycarbonyl)‐4‐oxo‐4H‐pyrazole 1,2‐dioxide (1a) with 1,3,5‐cycloheptatriene (2b) gave a mixture of the novel endo‐[4 + 6]‐cycloadduct (4ab), anti‐exo‐[4 + 2]‐cycloadduct (5ab), and the heterocage (6ab) derived from the intramolecular 1,3‐dipolar cycloaddition reaction of the syn‐endo‐[4 + 2]‐cycloadduct. Analogous endo‐[4 + 6] selectivity in 1,3‐dipolar cycloadditions has not been reported previously. The X‐ray analysis indicates that 6ab has a very long N_sp3–N_sp3 bond distance of 1.617(4) Å. The cycloaddition behaviour is discussed on the basis of transition‐state structures optimized at the B3LYP/6‐31G(d) level of theory, from which predictions of the peri‐, regio‐, and stereoselectivities agreed well with the experimental results. Copyright © 2012 John Wiley & Sons, Ltd.     

DABCO-triggered mild cascade reaction of electron-deficient cyclopentadienone: facile and efficient synthesis of condensed carbocycles

2,5-Bis(methoxycarbonyl)-3,4-diphenylcyclopentadienone (1) reacts with 4-phenylbut-3-yn-2-one (2b) in the presence of DABCO to give the bicyclic carbocycles (6b) and the tetracyclic carbocycle (7b) under extremely mild reaction conditions.     

Tandem arrays of TEMPO and nitronyl nitroxide radicals with designed arrangements on DNA

Herein we describe one-dimensional electron-spin arrays consisting of two different organic radicals with the designed arrangement based on the DNA sequence. Two mismatch-binding ligands carrying 2,2,6,6-tetramethylpiperidine N-oxide (TEMPO) and nitronyl nitroxide selectively bind to the predetermined sites on double stranded DNA. By using the two mismatch-binding ligands carrying the organic radicals as the glue for DNA, electron-spin assembly could be successfully synchronized with the hybridization. Periodically and tandemly arranged, two kinds of organic radical molecules at designed positions might be useful for an approach to build up scalable qubits of electron-spin-based quantum computing. The approach using DNA nanostructures as a scaffold to assembly functional small molecules can afford one of the promising ways for the future application of DNA nanostructures and nanotechnology.     

Photodegradation of lipopolysaccharides and the inhibition of macrophage activation by anthraquinone-boronic acid hybrids

Target-selective photodegradation of 3-deoxy-D-manno-2-octulopyranosonic acid (KDO) was achieved without additives and under neutral conditions using a designed anthraquinone-boronic acid hybrid and long wavelength UV light irradiation. The hybrid can photodegrade lipopolysaccharides (LPS) and inhibit macrophage activation induced by LPS.     

Voxel- and atlas-based analysis of diffusion tensor imaging may reveal focal axonal injuries in mild traumatic brain injury -- comparison with diffuse axonal injury

Background

The diagnosis and management of mild traumatic brain injury (MTBI) continue to be subjects of debate, with varying opinions regarding the extent to which tissue-based impairments versus the impacts of other stressors cause ongoing disability. Detecting areas of the brain with abnormalities that can explain symptoms and behavior in patients with MTBI is important in order to confirm the diagnosis of MTBI.

Methods

In this study, we calculated diffusion maps from results of diffusion tensor imaging (DTI) performed in an apparently healthy control group. We then compared these maps with those of patients with MTBI (MTBI group) or diffuse axonal injury (DAI group). All diffusion maps were normalized to the International Consortium for Brain Mapping atlas for atlas-based analysis and were segmented and normalized by the Diffeomorphic Anatomical Registration Through Exponentiated Lie tool in SPM8 to reduce misregistration.

Results

All diffusion measures in the DAI group were lower than in the control group. There were significant differences in the body and splenium of the corpus callosum, fornix and right cerebral peduncle in the DAI group compared with the control group (P<.001). The MTBI group had higher axial diffusivity than the control group in the right corticospinal tract, left medial lemniscus, left inferior cerebellar peduncle, bilateral anterior limb of the internal capsule, right anterior corona radiata, bilateral cingulum (cingulate gyrus) and left superior frontooccipital fasciculus (P<.05).

Conclusions

Voxel- and atlas-based analysis of DTI might suggest that patients with MTBI have focal axonal injury and that the pathophysiology is significantly different from that of DAI. These findings will help in the diagnosis of patients with MTBI.     

Degradation of Target Oligosaccharides by Anthraquinone–Lectin Hybrids with Light Switching

Anthraquinone–lectin hybrids were effectively synthesized using water‐soluble anthraquinone derivative 11 with concanavalin A (ConA) and hygrophorus russula lectin (HRL) to give anthraquinone–ConA ( 16 ) and anthraquinone–HRL ( 17 ) hybrids, respectively. These anthraquinone–lectin hybrids effectively and selectively degraded oligosaccharides containing a mannose residue as a non‐reducing terminal sugar, which has affinity for ConA and HRL, under photo‐irradiation with long‐wavelength UV light without additives and under neutral conditions. In addition, anthraquinone–HRL ( 17 ) selectively photo‐degraded only Man(α1,6)Man, which has a high affinity for HRL, among several mannosides by recognition of both the type and glycosidic linkage profile of the sugar in an oligosaccharide.     

2‐Phenylquinoline–Sugar Hybrids as Photoswitchable α‐Glucosidase Inhibitors

Purpose‐designed 2‐phenylquinoline (PQ)‐sugar hybrids 1 and 2 were synthesized and evaluated for their photodegradation activities against an α‐glucosidase target. The results indicated that PQ‐mannose hybrid 2 selectively and effectively photodegraded α‐glucosidase and significantly inhibited its enzymatic activity upon irradiation with long‐wavelength UV light in the absence of any additives under neutral and aqueous conditions. Furthermore, 2 selectively and effectively inhibited α‐glucosidase activity only with photo‐irradiation even in complex cell lysate.     

On Painlevé/gauge theory correspondence

We elucidate the relation between Painlevé equations and four-dimensional rank one \(\mathcal {N} = 2\) theories by identifying the connection associated with Painlevé isomonodromic problems with the oper limit of the flat connection of the Hitchin system associated with gauge theories and by studying the corresponding renormalization group flow. Based on this correspondence, we provide long-distance expansions at various canonical rays for all Painlevé \(\tau \)-functions in terms of magnetic and dyonic Nekrasov partition functions for \(\mathcal {N} = 2\) SQCD and Argyres–Douglas theories at self-dual Omega background \(\epsilon _1 + \epsilon _2 = 0\) or equivalently in terms of \(c=1\) irregular conformal blocks.