[M(CO)4PPh3] radicals (M = Cr, Mo, W): DFT and single crystal EPR investigations

[M(CO)₄PPh₃]⁻ (M = Mo, W) were trapped at 77 K in X-irradiated single crystals of M(CO)₅PPh₃ and studied by EPR. Structures of [M(CO)₄PPh₃]⁻ (M = Cr, Mo, W) were optimized by DFT; predicted g and ³¹P-hyperfine tensors agree with experiments for M = Mo, W. The anions adopt a slightly distorted pyramidal structure with PPh₃ in basal position and the spin mostly delocalized in a metal-d_z² orbital and carbon-p_z orbitals of carbonyls. The EPR tensors are slightly modified by annealing, they suggest that new constraints in the matrix distort the structure of [M(CO)₄PPh₃]⁻ (M = Cr, Mo, W).     

Tunable interplay between superconductivity and correlations in nanoscopic heterostructures

Artificial heterostructures consisting of the superconducting electrode(s) and the free electron reservoir(s) interconnected through various nanoscopic objects, like: quantum dots, nanowires or molecules enable a fully controllable confrontation of the correlation effects with electron pairing. Discrete energy spectrum of the nanoscopic objects (due to the quantum size effect) strongly depends on the many-body effects. Via the proximity effect, these nanoscopic objects are converted into the superconducting grains. Since the coupling to external electrodes can be varied experimentally, this enables a fully controllable investigation of an interplay between the electron correlations and superconductivity. In this work, we explore the subgap (Shiba) states arising from the induced pairing and analyse their influence on the Kondo-type correlations. This issue is currently widely explored using various nanoscopic devices.     

Regularly varying tails in a queue with discrete autoregressive arrivals of order p

We consider a discrete time single server queueing system where the service time of a customer is one slot, and the arrival process is governed by a discrete autoregressive process of order p (DAR(p)). For this queueing system, we investigate the tail behavior of the queue size and the waiting time distributions. Specifically, we show that if the stationary distribution of DAR(p) input has a tail of regular variation with index −β−1, then the stationary distributions of the queue size and the waiting time have tails of regular variation with index −β. This research was supported by the MIC (Ministry of Information and Communication), Korea, under the ITRC (Information Technology Research Center) support program supervised by the IITA (Institute of Information Technology Assessment).     

The analysis of a multiserver queue fed by a discrete autoregressive process of order 1

Based on matrix analytic methods and the theory of Markov regenerative processes, we obtain the stationary distributions of the system size and the waiting time in a multiserver queue into which packets arrive according to a discrete autoregressive process of order 1.     

On Matrix-Geometric Solution of Nested QBD Chains

In this paper, a generalization of the level dependent Quasi-Birth-and-Death (QBD) chains is presented. We analyze nested level dependent QBD chains and provide the complete characterization of their fundamental matrices in terms of minimal non-negative solutions of a number of matrix quadratic equations. Our results provide mixed matrix-geometric solution for the stationary distribution of nested QBD chains. Applications in overload control in communication networks are also discussed.     

Radiological measurement of phosphate rock and phosphogypsum from fertilizer industries in India

Phosphate deposits are generally characterized by high levels of natural radionuclide concentrations. Natural radionuclides from the uranium and thorium series were measured, using high-resolution gamma-spectrometry in phosphate rock and phosphogypsum samples from the phosphate fertilizer industry in India. Equilibrium was found to be disrupted during the chemical processing of phosphate rock with 83 % of the ²²⁶Ra and only 5 % of ²³⁸U fractionating to phosphogypsum. Activity concentrations of ²³⁸U and ²²⁶Ra in phosphogypsum produced from various fertilizer industries of India showed levels < 1,000 Bq kg^?1 and pose no restriction for use in building/construction material.     

CRISPR/Cas9-mediated Knockout of SIRT6 Imparts Remarkable Antiproliferative Response in Human Melanoma Cells in vitro and in vivo

Melanoma is one of the most aggressive, potentially fatal forms of skin cancer and has been shown to be associated with solar ultraviolet radiation-dependent initiation and progression. Despite remarkable recent advances with targeted and immune therapeutics, lasting and recurrence-free survival remain significant concerns. Therefore, additional novel mechanism-based approaches are needed for effective melanoma management. The sirtuin SIRT6 appears to have a pro-proliferative function in melanocytic cells. In this study, we determined the effects of genetic manipulation of SIRT6 in human melanoma cells, in vitro and in vivo. Our data demonstrated that CRISPR/Cas9-mediated knockout (KO) of SIRT6 in A375 melanoma cells resulted in a significant (1) decrease in growth, viability and clonogenic survival and (2) induction of G1-phase cell cycle arrest. Further, employing a RT² Profiler PCR array containing 84 key transformation and tumorigenesis genes, we found that SIRT6 KO resulted in modulation of genes involved in angiogenesis, apoptosis, cellular senescence, epithelial-to-mesenchymal transition, hypoxia signaling and telomere maintenance. Finally, we found significantly decreased tumorigenicity of SIRT6 KO A375 cells in athymic nude mice. Our data provide strong evidence that SIRT6 promotes melanoma cell survival, both in vitro and in vivo, and could be exploited as a target for melanoma management.     

The prospect of the dalton in the new SI: an educator’s point of view

If the definitions of the kilogram and the mole, based on exact values of the Planck and Avogadro constants, respectively, are accepted within the framework of the new SI, then the current definition of the dalton cannot be retained. Acceptance implies redefinition of the dalton exactly in terms of the kilogram. The redefined, exact dalton is useless in mass spectrometry, and hence, a new quantity for the carbon-12 reference mass would have to be established—against the principle of Ockham’s razor. In order to remove the roots of this awkward concept, the kilogram based on the Planck constant, and the mole, consisting of a particular number of entities equal to the inexactly determined numerical value of gram-to-dalton mass ratio, should be included in the new SI system. Some controversies related to the concept of mole have been also briefly outlined.     

Assessment of 226Ra and 228Ra activity concentration in west coast of India

An investigation on the distribution of ²²⁶Ra and ²²⁸Ra activity concentration in coastal surface sea water from Okha in Gujarat to Ratnagiri in Maharashtra state along the west coast of India was carried out. In-situ pre-concentration technique was used to measure radium isotopes by passing 1,000 L of seawater through MnO₂ impregnated polypropylene filter cartridges at all the locations. ²²⁶Ra was estimated using gamma ray peak of its daughter radionuclides ²¹⁴Bi and ²¹⁴Pb. ²²⁸Ra was estimated from its daughter ²²⁸Ac. In the coastal waters, ²²⁶Ra and ²²⁸Ra activity concentration were observed to be in the range of 1.5–2.9 and 2.5–8.6 Bq m^?3 with a mean of 2.2 and 4.9 Bq m^?3 respectively. The activity of ²²⁸Ra was observed to be more than ²²⁶Ra in all the locations. The variation in spatial distribution of the radium isotopes activity concentration and its ratio with respect to location is discussed in the paper. The radioactive database obtained represents reference values for coastal environment of India.