Calculation of quadrupole interactions in the high pressure phase of \beta {\text{ - }} gallium metal

Electric field gradient q and quadrupole interaction frequency calculated at 256.7 K in the high pressure phase (orthorhombic) of Ga metal are reported. The results are: q=+0.251 atomic units (au), =5.479 MHz. These are compared with results from experiment and previous calculation available for the monoclinic phase of Ga metal at normal pressure. The results from the previous calculation at 248 K are: q=-0.250 au and =5.318 MHz. The result from experiment extrapolated to 256.7 K is: =4.871 MHz. The sign reversal of the calculated q is attributed mainly to the change of point symmetry of the lattice from the orthorhombic to monoclinic. That the interaction frequency in high pressure phase is higher than experiment may be partly due to the increase of pressure and partly to the structural phase change.     

NMR spectra, GIAO and charge density calculations of five-membered aromatic heterocycles

The B3LYP/6-31+G(d) molecular geometry optimized structures of 17 five-membered heterocycles were employed together with the gauge including atomic orbitals (GIAO) density functional theory (DFT) method at the B3LYP/6-31+G(d,p), B3LYP/6-311++G(d,p) and B3LYP/6-311+G(2d,p) levels of theory for the calculation of proton and carbon chemicals shifts and coupling constants. The method of geometry optimization for pyrrole (1), N-methylpyrrole (2) and thiophene (7) using the larger 6-311++G(d,p) basis sets at the B3LYP/6-31+G(d,p), B3LYP/6-311++G(d,p), B3LYP/6-31+G(2d,p) and B3LYP/cc-pVTZ levels of theory gave little difference between calculated and experimental values of coupling constants. In general, the (1)H and 13C chemical shifts for all compounds are in good agreement with theoretical calculations using the smaller 6-31 basis set. The values of nJHH(n=3, 4, 5) and rmnJ(CH)(n=1, 2, 3, 4) were predicted well using the larger 6-31+G(d,p) and 6-311++G(d,p) basis sets and at the B3LYP/6-31+G(d,p), B3LYP/6-311++G(d,p), B3LYP/6-31+G(2d,2p) levels of theory. The computed atomic charges [Mülliken; Natural Bond Orbital Analysis (NBO); Merz-Kollman (MK); CHELP and CHELPG] for the B3LYP/6-311++G(d,p) geometry optimized structures of 1-17 were used to explore correlations with the experimental proton and carbon chemical shifts.     

Radiative transmission of lepton flavor hierarchies

We discuss a one loop model for neutrino masses which leads to a seesaw-like formula with the difference that the charged lepton masses replace the unknown Dirac mass matrix present in the usual seesaw case. This is a considerable reduction of parameters in the neutrino sector and predicts a strong hierarchical pattern in the right handed neutrino mass matrix that is easily derived from a U(1)_H family symmetry. The model is based on the left–right gauge group with an additional Z₄ discrete symmetry which gives vanishing neutrino Dirac masses and finite Majorana masses arising at the one loop level. Furthermore, it is one of the few models that naturally allow for large (but not necessarily maximal) mixing angles in the lepton sector. A generalization of the model to the quark sector requires three iso-spin singlet vector-like down type quarks, as in E₆. The model predicts an inert doublet type scalar dark matter.     

Characterization,luminescence and EPR investigations of Eu2+ activated strontium aluminate phosphor

Strong blue-green light emitting Eu doped SrAl₂O₄ phosphor was synthesized by a low-temperature initiated, self-propagating and gas producing combustion process in a very short time (<5 min). The prepared powder was characterized by X-ray diffraction, Fourier-transform infrared spectrometry and scanning electron microscopy. The excitation spectrum shows a peak at 397 nm. Upon excitation at 397 nm, the emission spectrum exhibits a well defined broad band with maximum at 493 nm corresponding to 4f⁶5d → 4f⁷ transition. Electron paramagnetic resonance (EPR) measurements at X-band showed low field signals due to Eu²⁺ ions in SrAl₂O₄:Eu.     

A series of trifacial Pd6 molecular barrels with porphyrin walls

Three new nanoscopic trigonal prisms, [(tmen)(6) Pd(6) (H(2)L)(3)](NO(3))(12) (1), [(Meen)(6) Pd(6)(H(2) L)(3)](NO(3))(12) (2), and [(2,2'-bipy)(6)Pd(6) (H(2)L)(3)](NO(3))(12) (3), have been synthesized in excellent yields through single-step metal-ligand-coordination-driven self-assembly using 5,10,15,20-tetrakis(3-pyridyl)porphyrin (H(2)L) as a donor and cis-blocked Pd(II) 90° acceptors. These complexes were fully characterized by spectroscopic studies and single-crystal X-ray diffraction. All of these barrels quantitatively bind Zn(II) ions in the N(4) pockets of the porphyrin walls at room temperature. Their corresponding zinc-embedded complexes, [(tmen)(6)Pd(6)(ZnL)(3)](NO(3))(12) (1?a), [(Meen)(6) Pd(6)(ZnL)(3)](NO(3))(12) (2?a), and [(2,2'-bipy)(6)Pd(6)(ZnL)(3)](NO(3))(12) (3?a), were synthesized under ambient conditions by the post-synthetic binding of Zn(II) ions into the H(2)N(4) pockets of the porphyrin walls of these complexes. These zinc-embedded complexes were characterized by electronic absorption, fluorescence emission, (1)H?NMR spectroscopy, as well as elemental analysis. Complexes 1-3 exhibited considerable microporosity in their solid state. Complex 1 was an efficient adsorbent for nitrogen gas and EtOH, MeOH, and water vapors.     

Guest-responsive reversible swelling and enhanced fluorescence in a super-absorbent, dynamic microporous polymer

A swell idea! The guest-responsive reversible swelling and fluorescence enhancement of a dynamic, microporous polymer network is presented. Guest-induced breathing of hydrophobic pores imparts multi-functional properties, such as super-absorbency, phase-selective swelling of oil from water and encapsulation of C(60) (see figure), to this soft micro-porous organic polymer.     

A highly efficient solvent system containing functionalized diglycolamides and an ionic liquid for americium recovery from radioactive wastes

Three room temperature ionic liquids (RTILs), viz. C(4)mim(+)·PF(6)(-), C(6)mim(+)·PF(6)(-) and C(8)mim(+)·PF(6)(-), were evaluated as diluents for the extraction of Am(III) by N,N,N',N'-tetraoctyl diglycolamide (TODGA). At 3 M HNO(3), the D(Am)-values by 0.01 M TODGA were found to be 102, 34 and 74 for C(4)mim(+)·PF(6)(-), C(6)mim(+)·PF(6)(-) and C(8)mim(+)·PF(6)(-), respectively. The extraction of Am(III) decreased with increasing feed acidity for all three diluents, indicating an ion exchange mechanism for the extraction. The stoichiometry of the extracted species suggested that two TODGA molecules were associated with Am(III) during the extraction for all three RTILs and the conditional extraction constants have been determined. The D(M)-values for different metal ions followed the order: 75 (Am(III)) > 30.7 (Pu(IV)) > 3.9 (Np(IV)) > 1.19 (Pu(VI)) > 0.52 (U(VI)) > 0.12 (Cs(I)) > 0.024 (Sr(II)). The distribution behaviour of Am(III) was also studied with a recently synthesized calix[4]arene-4DGA (C4DGA) extractant dissolved in C(8)mim(+)·PF(6)(-). Using this extractant diluent combination, the D(Am)-value was 194 at 3 M HNO(3) using 5 × 10(-5) M C4DGA, suggesting a very high distribution coefficient at very low extractant concentrations. The stoichiometry of the extracted species containing Am was found to be 1:2 (M:L) in C(8)mim(+)·PF(6)(-). The thermodynamics of the extraction was also studied for both extractants in C(8)mim(+)·PF(6)(-). The use of RTILs gives rise to significantly improved extraction properties than the commonly used n-dodecane and an unusual increase in separation factor values was seen for the first time which can lead to selective separation of Am from wastes containing a mixture of U, Pu and Am.     

Multifunctional magnetic calcium phosphate nanoparticles for targeted platin delivery

Magnetic mesoporous amorphous calcium phosphate nanoparticles with a size of 62 nm and abundant -COOH groups on the surface have been prepared by a simple method. The particles show excellent aqueous dispersion stability in physiological pH without any deterioration in hydrodynamic size and zetapotential. By virtue of the carboxylate groups on the surface, the platinum pharmacophore cis-diaquadiamine platinum(ii), folic acid and rhodamine isothiocyanate were conjugated on these magnetic calcium phosphate nanoparticles. The cytotoxicity and internalization efficiency of these nanocarriers have been evaluated on folate receptor overexpressed HeLa cells. These drug loaded nanoagents exhibit elevated cytotoxicity and induce apoptosis in HeLa cells.     

Simple one-step synthesis of highly luminescent carbon dots from orange juice: application as excellent bio-imaging agents

Highly photoluminescent carbon dots with a PL quantum yield of 26% have been prepared in one step by hydrothermal treatment of orange juice. Due to high photostability and low toxicity these carbon dots are demonstrated as excellent probes in cellular imaging.