Superhalogen and Superacid

A superhalogen $\rm{F@C_{20}(CN)_{20}}$ and a corresponding Br{\o}nsted superacid were designed and investigated on DFT and DLPNO-CCSD(T) levels of theory. Calculated compounds have outstanding electron affinity and deprotonation energy, respectively. We consider superacid $\rm{H[F@C_{20}(CN)_{20}]}$ to be able to protonate molecular nitrogen. The stability of these structures is discussed, while some of the previous predictions concerning Br{\o}nsted superacids of record strength are doubted.Comment: 11 pages (main paper), 32 pages (supporting information), 10 figures, 10 tables, 62 reference

Magnetic systems at criticality: different signatures of scaling

Different aspects of critical behaviour of magnetic materials are presented and discussed. The scaling ideas are shown to arise in the context of purely magnetic properties as well as in that of thermal properties as demonstrated by magnetocaloric effect or combined scaling of excess entropy and order parameter. Two non-standard approaches to scaling phenomena are described. The presented concepts are exemplified by experimental data gathered on four representatives of molecular magnets.Comment: 33 pages, 16 figure

Net Ecosystem Carbon Balance in a North Carolina, USA, Salt Marsh

Salt marshes have among the highest carbon (C) burial rates of any ecosystem and often rely on C accumulation to gain elevation and persist in locations with accelerating sea level rise. Net ecosystem carbon balance (NECB), the accumulation or loss of C resulting from vertical CO2 and CH4 gas fluxes, lateral C fluxes, and sediment C inputs, varies across salt marshes; thus, extrapolation of NECB to an entire marsh is challenging. Anthropogenic nitrogen (N) inputs to salt marshes impact NECB by influencing each component of NECB, but differences in the impacts of fertilization between edge and interior marsh must be considered when scaling up. NECB was estimated for the 0.5 km2 Spartina alterniflora marsh area of Freeman Creek, NC, under control and fertilized conditions at both interior and edge berm sites. Annual CO2 fluxes were nearly balanced at control sites, but fertilization significantly increased net CO2 emissions at edge sites. Lateral C export, modeled using respiration rates, represented a significant C loss that increased with fertilization in both edge and interior marsh. Sediment C input was a significant C source in the interior, nearly doubling with fertilization, but represented a small source on the edge. When extrapolating C exchanges to the entire marsh, including edge which comprised 17% of the marsh area, the marsh displayed net loss of C despite a net C gain in the interior. Fertilization increased net C loss fivefold. Extrapolation of NECB to whole marshes requires inclusion of C fluxes for both edge and interior marsh

X‐Ray Spectroscopy on Biological Systems

In the field of biological studies, next to the standard methods, new tools are offered by contemporary physics. X‐ray spectroscopic techniques enable probing electronic structure of occupied and unoccupied states of studied atom and distinguish the oxidation state, local geometry, and ligand type of elements that occur in biological material. Direct analysis using X‐ray spectroscopy avoids many chemical preparation steps that might modify biological samples. The information obtained gives us insight into important biochemical processes all under physiological conditions. In this chapter we focus our attention to the application of X‐ray spectroscopy to the study of biological samples, with special emphasis on mechanisms revealing interaction between DNA and different cytotoxic agents and in the determination of changes in oxidation state of different elements in pathologically altered human cells and tissue

First approach to studies of sulphur electron DOS in prostate cancer cell lines and tissues studied by XANES

Abstract Urological cancers comprise approximately one-third of all cancers diagnosed in men worldwide and out of these, prostate cancer is the most common one ( WHO World Cancer Report, 2008 ). Several risk factors such as age, hormone levels, environmental conditions and family history are suspected to play a role in the onset of this disease of otherwise obscure aetiology. It is therefore the medical need that drives multidisciplinary research in this field, carried out by means of various experimental and theoretical techniques. Out of many relevant factors, it is believed that sulphur can take an important part in cancer transformations. We have investigated the prostate cancer cell lines and tissues, along with selected organic and inorganic compounds used as references, by the X-ray absorption fine structure spectroscopy near the sulphur edge energy region. Particularly, the comparison of the experimental results collected during XANES measurements and theoretical calculations of electron density of states with use of the FEFF8 code and LAPW (linearised augmented plane-wave) method has been performed and in this work the first results of our studies are presented

EXAFS studies of prostate cancer cell lines

Sulphur plays a vital role in every human organism. It is known, that sulphur-bearing compounds, such as for example cysteine and glutathione, play critical roles in development and progression of many diseases. Any alteration in sulphur's biochemistry could become a precursor of serious pathological conditions. One of such condition is prostate cancer, the most frequently diagnosed malignancy in the western world and the second leading cause of cancer related death in men. The purpose of presented studies was to examine what changes occur in the nearest chemical environment of sulphur in prostate cancer cell lines in comparison to healthy cells. The Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy was used, followed by theoretical calculations. The results of preliminary analysis is presented

A role of OCRL in clathrin-coated pit dynamics and uncoating revealed by studies of Lowe syndrome cells

Mutations in the inositol 5-phosphatase OCRL cause Lowe syndrome and Dent's disease. Although OCRL, a direct clathrin interactor, is recruited to late-stage clathrin-coated pits, clinical manifestations have been primarily attributed to intracellular sorting defects. Here we show that OCRL loss in Lowe syndrome patient fibroblasts impacts clathrin-mediated endocytosis and results in an endocytic defect. These cells exhibit an accumulation of clathrin-coated vesicles and an increase in U-shaped clathrin-coated pits, which may result from sequestration of coat components on uncoated vesicles. Endocytic vesicles that fail to lose their coat nucleate the majority of the numerous actin comets present in patient cells. SNX9, an adaptor that couples late-stage endocytic coated pits to actin polymerization and which we found to bind OCRL directly, remains associated with such vesicles. These results indicate that OCRL acts as an uncoating factor and that defects in clathrin-mediated endocytosis likely contribute to pathology in patients with OCRL mutations

Development of a human knee joint finite element model to investigate cartilage stress during walking in obese and normal weight adults

Osteoarthritis (OA) is a degenerative condition characterized by the breakdown and loss of joint articular cartilage. While the cause of OA is not precisely known, obesity is a known risk factor [1]. Particular effort has gone towards understanding the relationship between obesity and knee OA because obesity is more strongly linked to OA at the knee than at any other lower extremity joint [2]. Although the relationship between obesity and knee OA is well established, the mechanism of pathogenesis is less understood. Excess body weight generates greater joint contact forces at the knee. However, obese individuals alter their gait, resulting in increased joint contact forces that are not proportional to body mass [3]. In this study, a partially validated knee joint finite element (FE) model was developed to predict cartilage loading during walking across individuals of varying adiposity. The model was used with kinematic and kinetic gait data to address the following hypotheses: 1) increased loading due to obesity will produce greater cartilage stress compared to the normal weight control; and 2) altered gait kinematics of obese individuals will alter the distribution of stress on the surface of the tibial cartilage