Structural scaffold of 18-crown-6 tetracarboxylic Acid for optical resolution of chiral amino acid: x-ray crystal analyses of complexes of D- and L-isomers of serine and glutamic acid

(+)-18-crown-6 tetracarboxylic acid (18C6H4) has been used as a chiral selector for D/L-amino acids in HPLC, where L-isomer is usually eluted prior to D-isomer, except for the case of serine. To clarify why serine exhibits the reverse order for the elusion, the chiral interactions of D- and L-serines with (+)-18C6H4 were investigated by the X-ray single crystal analyses, together with the case of D- and L-glutamic acids, which exhibit the usual elution order in HPLC. The backbone structures (amino, Calpha-H and carboxyl groups) of these four amino acids showed the nearly same interaction with (+)-18C6H4 despite their different chirality. In contrast, the hydroxyl group of L-serine side chain formed a hydrogen bond with the carboxyl group of (+)-18C6H4, whereas such a interaction was not formed for the side chain of D-serine and D- and L-glutamic acids. Thus, it was shown that the exception of D/L-serine from the first elution rule of L-isomer in HPLC is due to the presence and absence of a hydrogen bond formation of its side chain OH group.     

DNA functionalization of carbon nanotubes for ultrathin atomic layer deposition of high kappa dielectrics for nanotube transistors with 60 mV/decade switching

For single-walled carbon nanotube (SWNT) field effect transistors, vertical scaling of high kappa dielectrics by atomic layer deposition (ALD) currently stands at approximately 8 nm with a subthreshold swing S approximately 70-90 mV/decade at room temperature. ALD on as-grown pristine SWNTs is incapable of producing a uniform and conformal dielectric layer due to the lack of functional groups on nanotubes and because nucleation of an oxide dielectric layer in the ALD process hinges upon covalent chemisorption on reactive groups on surfaces. Here, we show that by noncovalent functionalization of SWNTs with poly-T DNA molecules (dT40-DNA), one can impart functional groups of sufficient density and stability for uniform and conformal ALD of high kappa dielectrics on SWNTs with thickness down to 2-3 nm. This enables approaching the ultimate vertical scaling limit of nanotube FETs and reliably achieving S approximately 60 mV/decade at room temperature, and S approximately 50 mV/decade in the band-to-band tunneling regime of ambipolar transport. We have also carried out microscopy investigations to understand ALD processes on SWNTs with and without DNA functionalization.     

Comparison of bifurcation and imperfection analyses of localized necking in rate-independent polycrystalline sheets

Plastic flow localization into a narrow band is investigated for a rate-independent polycrystalline sheet. Strain localization is considered to initiate at a point of bifurcation from the homogeneous deformation state or to result from the growth of a preexisting imperfection. Bifurcation analysis based on the rate-independent crystal plasticity model is found to give limit strains at a realistic strain level in the biaxial-stretching range. Limit strains predicted by the imperfection analysis are lower than those for bifurcation analysis and tend to approach those strain levels with decreasing amount of initial imperfection. Then, the bifurcation analysis is applied to the simulation of the forming limit for strongly textured sheets. The bifurcation analysis reveals the same trend of a texture dependence of limit strains as that for the imperfection analysis employing a rate-dependent model reported in the literature.     

Power extraction using flow-induced vibration of a circular cylinder placed near another fixed cylinder

We conducted an experiment in a towing tank to investigate the performance of an energy extraction system using the flow-induced vibration of a circular cylinder. This experiment tested three different cases involving the following arrangements of cylinder(s) of identical diameter: the upstream fixed–downstream movable arrangement (case F); the upstream movable–downstream fixed arrangement (case R); and a movable isolated cylinder (case I). In cases F and R, the separation distance (ratio of the distance between the centers of the two cylinders to their diameters) is fixed at 1.30. Measurement results show that while cases F and I generate vortex-induced vibration (VIV) resonance responses, case R yields wake-induced vibration (WIV) at reduced velocity over 9.0, which is significantly larger than that of the VIV response, leading to the induction of higher electronic power in a generator. Accordingly, primary energy conversion efficiency is higher in the case involving WIV.     

Novel plasma biomarker surrogating cerebral amyloid deposition

Alzheimer’s disease (AD) is the most common and devastating dementia. Simple and practical biomarkers for AD are urgently required for accurate diagnosis and to facilitate the development of disease-modifying interventions. The subjects for the study were selected on the basis of PiB amyloid imaging by PET. Forty PiB-positive (PiB+) individuals, including cognitively healthy controls (HC), and mild cognitive impairment and AD individuals, and 22 PiB-negative (PiB−) HC participated. Employing our novel highly sensitive immunoprecipitation-mass spectrometry, we measured plasma amyloid β-proteins (Aβs; Aβ1-40 and Aβ1-42) and Aβ-approximate peptides (AβAPs), which were cleaved from amyloid precursor protein (APP). Among the AβAPs, APP669-711 appeared to be a good reference for deciphering pathological change of Aβ1-42. We evaluated the performance of the ratio of APP669-711 to Aβ1-42 (APP669-711/Aβ1-42) as a biomarker. APP669-711/Aβ1-42 significantly increased in the PiB+ groups. The sensitivity and specificity to discriminate PiB+ individuals from PiB− individuals were 0.925 and 0.955, respectively. Our plasma biomarker precisely surrogates cerebral amyloid deposition.     

Phosphopeptide-dependent labeling of 14-3-3 ζ proteins by fusicoccin-based fluorescent probes

Fluorescent combination: Cell-penetrating probes derived from the diterpene fusicoccin can form ternary complexes with 14-3-3 proteins and phosphopeptide ligands, whereupon the probes site-specifically attach a fluorescent tag onto the surface of the 14-3-3 proteins.     

An Iron(III)-Monoamidate Complex Catalyst for Selective Hydroxylation of Alkane CH Bonds with Hydrogen Peroxide

Selective oxidation: The success of the title reaction is caused by the strong electron donation from the amidate moiety of the dpaq ligand to the iron center (dpaq=2-[bis(pyridin-2-ylmethyl)]amino-N-quinolin-8-yl-acetamidate). This process facilitates the O?O bond heterolysis of the intermediate Fe(III) OOH species to generate a selective oxidant without forming highly reactive hydroxyl radicals.     

Group chase and escape with conversion from targets to chasers

We study the effect of converting caught targets into new chasers in the context of the recently proposed ‘group chase and escape’ problem. Numerical simulations have shown that this conversion can substantially reduce the lifetimes of the targets when a large number of them are initially present. At the same time, it also leads to a non-monotonic dependence on the initial number of targets, resulting in the existence of a maximum lifetime. As a counter-effect for this conversion, we further introduce self-multiplying abilities to the targets. We found that the longest lifetime exists when a suitable combination of these two effects is created.     

Magnetic resonance differentiation between T2 and T1 gallbladder carcinoma: significance of subserosal enhancement on the delayed phase dynamic study

Purpose

The aim of this study is to investigate whether subserosal enhancement on the delayed-phase dynamic magnetic resonance (MR) study (SED) can differentiate T2 from T1 gallbladder carcinoma (GBC).

Methods

The institutional research board approved this retrospective study. Between 1997 and 2006, there were surgically proven 11 T1 and 21 T2 GBC in 30 patients, all of whom had undergone preoperative contrast enhanced dynamic MR study, either with a 2D sequence (n=17) or 3D sequences (n=15). All images were reviewed by two radiologists for the presence of SED, and receiver operating characteristic (ROC) curve analysis was performed. Sensitivity, specificity, positive and negative predictive values were calculated by consensus.

Results

The areas under the ROC curves of the two readers were 0.91 and 0.86, and the kappa value was 0.78. Of the 21 T2 GBC, 18 and 3 showed positive and negative SED, respectively. Of the 11 T1 GBC, 1 and 10 showed positive and negative SED, respectively. The sensitivity, specificity, positive and negative predictive values of SED for diagnosing T2 lesions were 86%, 88%, 91% and 77%, respectively.

Conclusions

In conclusion, SED may be a useful sign to differentiate T2 from T1 GBC, which would affect the preoperative surgical planning of the patients.