Regioselective synthesis of pyrimido[1,2-a][1,3,5]triazin-6-ones via reaction of 1-(6-oxo-1,6-dihydropyrimidin-2-yl)guanidines with triethylorthoacetate: observation of an unexpected rearrangement

A novel thermal rearrangement, involving pyrimidine ring opening and subsequent ring closure leading to recyclization of the system, was identified in the reaction of (6-oxo-1,6-dihydropyrimidin-2-yl)guanidines 3 (where NR(1)R(2) = NH(2), NH alkyl, NH aralkyl, NHCH(2)Ph(R)) with triethyl orthoacetate, affording 4-substituted-2-methyl-6H-pyrimido[1,2-a][1,3,5]triazin-6-ones 6 and their ring opened products. However, no such rearrangement was observed with (6-oxo-1,6-dihydropyrimidin-2-yl)guanidines 3 bearing a tertiary amino or anilino substituent (i.e. where NR(1)R(2) = N(CH(3))(2), indoline, morpholino, NHAr). As expected, 2-substituted-4-methyl-6H-pyrimido[1,2-a][1,3,5]triazin-6-ones 4 were obtained as the final products. Experimental structural determination and theoretical studies were carried out to get an understanding of the observed thermal rearrangement. In addition, an attempt to obtain similar pyrimido[1,2-a][1,3,5]triazin-6-ones using N,N-dimethylacetamide dimethyl acetal (DMA-DMA) as one carbon inserting synthon had furnished triazine ring annulated product 14 bearing N,N-dimethyl enamino substituent at position 4 as a result of further reaction with a second molecule of DMA-DMA.     

Signals of leptophilic dark matter at the ILC

Adopting a model independent approach, we constrain the various effective interactions of leptophilic DM particles with the visible world from the WMAP and Planck data. The thermally averaged indirect DM annihilation cross section and the DM–electron direct-detection cross section for such a DM candidate are observed to be consistent with the respective experimental data. We study the production of cosmologically allowed leptophilic DM in association with \(Z\, (Z\rightarrow f\bar{f})\), \(f\equiv q,\,e^-,\, \mu ^-\) at the ILC. We perform the \(\chi ^2\) analysis and compute the 99% C.L. acceptance contours in the \(m_\chi \) and \(\varLambda \) plane from the two-dimensional differential distributions of various kinematic observables obtained after employing parton showering and hadronisation to the simulated data. We observe that the dominant hadronic channel provides the best kinematic reach of 2.62 TeV (\(m_\chi \) = 25 GeV), which further improves to \(\sim \)3 TeV for polarised beams at \(\sqrt{s} = 1\) TeV and an integrated luminosity of 1 ab\(^{-1}\).     

A note on the dispersion of Love waves in layered monoclinic elastic media

The dispersion equation for Love waves in a monoclinic elastic layer of uniform thickness overlying a monoclinic elastic half-space is derived by applying the traction-free boundary condition at the surface and continuity conditions at the interface. The dispersion curves showing the effect of anisotropy on the calculated phase velocity are presented. The special cases of orthotropic and transversely isotropic media are also considered. It is shown that the well-known dispersion equation for Love waves in an isotropic layer overlying an isotropic half-space follows as a particular case.     

Structural effects on encapsulation as probed in redox-active core dendrimer isomers

Three pairs of isomeric, iron-sulfur core dendrimers were prepared. Each isomer pair was distinguished by a 3,5-aromatic substitution pattern (extended) versus 2,6-aromatic substitution pattern (backfolded). Several observations were made that supported the hypothesis that the iron-sulfur cluster cores were encapsulated more effectively in the backfolded isomers as compared to their extended isomeric counterparts. The backfolded isomers were more difficult to reduce electrochemically, consistent with encapsulation in a more hydrophobic microenvironment. Furthermore, heterogeneous electron-transfer rates for the backfolded molecules were attenuated compared to the extended molecules. From diffusion measurements obtained by pulsed field gradient spin-echo NMR and chronoamperometry, the backfolded dendrimers were found to be smaller than the extended dendrimers. Comparison of longitudinal proton relaxation (T(1)) values also indicated a smaller, more compact dendrimer conformation for the backfolded architectures. These findings indicated that the dendrimer size was not the major factor in determining electron-transfer rate attenuation. Instead, the effective electron-transfer distance, as determined by the relative core position and mobility in a dendrimer, is most relevant for encapsulation.     

Positron annihilation spectroscopic studies on Nd-doped ceria

We report a new result on the characterization of Nd-doped ceria, Ce_1−xNd_xO_2−x/2 (x=0.075-0.675) using positron lifetime spectroscopy (LTS) and coincidence Doppler broadening (CDB) measurements. A systematic increase in lifetime that is attributed to formation of Nd-oxygen vacancy associates is seen from x=0.075-0.4 followed by a sharper increase up to x=0.5. The change in profile of lifetime around x=0.4 suggests drastic increase in the concentration of these associates. Discontinuity in lifetime around x=0.5 is ascribed to ordering of oxygen vacancies. Coincidence Doppler broadening measurements indicate reduction in the overlap of positron wavefunction with oxygen core electrons due to trapping of positrons. Low-temperature (50-300 K) lifetime measurements indicate the presence of Rydberg-like positron states associated with Nd³⁺ sites.     

A novel content-based active contour model for brain tumor segmentation

Brain tumor segmentation is a crucial step in surgical and treatment planning. Intensity-based active contour models such as gradient vector flow (GVF), magneto static active contour (MAC) and fluid vector flow (FVF) have been proposed to segment homogeneous objects/tumors in medical images. In this study, extensive experiments are done to analyze the performance of intensity-based techniques for homogeneous tumors on brain magnetic resonance (MR) images. The analysis shows that the state-of-art methods fail to segment homogeneous tumors against similar background or when these tumors show partial diversity toward the background. They also have preconvergence problem in case of false edges/saddle points. However, the presence of weak edges and diffused edges (due to edema around the tumor) leads to oversegmentation by intensity-based techniques. Therefore, the proposed method content-based active contour (CBAC) uses both intensity and texture information present within the active contour to overcome above-stated problems capturing large range in an image. It also proposes a novel use of Gray-Level Co-occurrence Matrix to define texture space for tumor segmentation. The effectiveness of this method is tested on two different real data sets (55 patients - more than 600 images) containing five different types of homogeneous, heterogeneous, diffused tumors and synthetic images (non-MR benchmark images). Remarkable results are obtained in segmenting homogeneous tumors of uniform intensity, complex content heterogeneous, diffused tumors on MR images (T1-weighted, postcontrast T1-weighted and T2-weighted) and synthetic images (non-MR benchmark images of varying intensity, texture, noise content and false edges). Further, tumor volume is efficiently extracted from 2-dimensional slices and is named as 2.5-dimensional segmentation.     

Electrical properties and diffusion behavior of hafnium in single crystal silicon

Electrical properties and diffusivity of Hf in single crystal Si have been studied. Several deep level defects were found for Hf in both the upper and lower half of the silicon band gap, and their parameters were measured. Energy levels, concentrations, and capture cross sections were determined for all Hf defects. The DLTS spectra depend on the cooling rate. Analysis of electrical properties yielded a dominant deep level defect at E_C -0.27 eV, which showed field enhanced emission due to Poole–Frenkel effect, confirming its donor nature. This agreed with results obtained using CV and TSCAP. In the lower half of the bandgap, a defect level at E_V +0.24 eV was found to have a capture barrier of 0.04 eV. Diffusivity of Hf was studied using two methods for Hf incorporation in Si – ion implantation and sputtering. Analysis of broadening of the Hf profile in implanted samples, which were annealed for 168 h, allowed us to estimate the diffusivity of Hf as 1.7×10^-15 cm²/s at 1250 °C: the spreading of implanted profiles at lower temperatures was too small. Analysis of Hf depth profiles in the sputtered and annealed samples reveals that Hf appears to have a fast and slow component to its diffusivity whose migration energy was determined to be 3.5±0.3 eV and 4.1±0.3 eV respectively. The fast and slow component are ascribed to interstitial and substitutional Hf with an energy level of E_C -0.27 eV and E_V +0.43 eV respectively. The mechanism for the fast component seems to indicate a direct interstitial diffusion mechanism whereas the diffusion of the substitutional Hf seems most consistent with the concerted exchange diffusion mechanism. In addition, estimates of solubility for both, interstitial and substitutional Hf, are included. PACS 61.72.Tt; 66.30.Jt; 71.55.Cn     

Shape control of piezolaminated thin-walled structures using nonlinear piezoelectric actuators

In the present paper a 2D-shell finite element model is proposed to carry out static analysis of piezolaminated composite shells by incorporating nonlinear constitutive relations in order to describe the electromechanical coupling under strong electric fields. The present shell element has 5 mechanical DOFs and 3 electrical DOFs per node. The developed composite piezolaminated shell element is employed to study the static behavior and shaping of spherical antenna reflector laminated with piezo-patches under both weak and strong electric fields. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and modeling of composite poly (styrene-co-acrylonitrile) membrane for the separation of chromic acid

In this work, we have prepared a composite styrene acrylonitrile (SAN) membrane on a ceramic clay plate by coating a prepolymer solution prepared using a dual initiator system. This membrane is chemically modified by gas phase nitration followed by amination and quaternization to make it charged and has been characterized by FTIR, SEM, contact angle measurements, AFM, water content, water permeability measurements and molecular weight cut-off experiments. The membrane has been further characterized using chromic acid rejection (real and observed) at different pressures, feed concentrations and pH. The modified membrane is found to possess a real rejection of above 90% with high water flux at low pressure drop.     

DNA‐Catalyzed Lysine Side Chain Modification

Catalyzing the covalent modification of aliphatic amino groups, such as the lysine (Lys) side chain, by nucleic acids has been challenging to achieve. Such catalysis will be valuable, for example, for the practical preparation of Lys‐modified proteins. We previously reported the DNA‐catalyzed modification of the tyrosine and serine hydroxy side chains, but Lys modification has been elusive. Herein, we show that increasing the reactivity of the electrophilic reaction partner by using 5′‐phosphorimidazolide (5′‐Imp) rather than 5′‐triphosphate (5′‐ppp) enables the DNA‐catalyzed modification of Lys in a DNA‐anchored peptide substrate. The DNA‐catalyzed reaction of Lys with 5′‐Imp is observed in an architecture in which the nucleophile and electrophile are not preorganized. In contrast, previous efforts showed that catalysis was not observed when Lys and 5′‐ppp were used in a preorganized arrangement. Therefore, substrate reactivity is more important than preorganization in this context. These findings will assist ongoing efforts to identify DNA catalysts for reactions of protein substrates at lysine side chains.