The effect of growth parameters on the intrinsic properties of large-area single layer graphene grown by chemical vapor deposition on Cu

We present a comprehensive study of the parameter space for single layer graphene growth by chemical vapor deposition on Cu. The temperature is the most widely recognized control parameter in single layer graphene growth. We show that the methane-to-hydrogen ratio and the growth pressure also are critical parameters that affect the structural perfection and the cleanliness of graphene. The optimal conditions for suppressing double and multilayer graphene growth occur near 1000 °C, 1:20 methane-to-hydrogen ratio, and a total pressure in the range from 0.5 to 1 Torr. Raman mapping of a 40 × 30 μm² area shows single layer domains with 5–10 μm linear dimensions. Atomic resolution imaging of suspended graphene by aberration corrected scanning transmission electron microscopy shows that the single layer graphene consists of areas of 10–15 nm linear dimensions and smaller patches of residual contamination that was undetected by other characterization methods.     

Arsenic removal from rice by washing and cooking with water

Two Hungarian and one Chinese rice samples were selected in order to establish the extractable arsenic content by washing and cooking in water in a ratio of 6:1, water:rice (cm³:g) by inductively coupled plasma sector field mass spectrometry (ICP-SF-MS). Total arsenic concentration of the Zhenshan 97, Risabell and Ko?röstáj-333 samples were 171.3 ± 7.1 ng g⁻¹, 116.0 ± 3.7 ng g⁻¹ and 139.0 ± 6.1 ng g⁻¹, respectively, which did not exceed the toxic limits established for As in Hungary (0.3 μg g⁻¹) or in China (0.7 μg g⁻¹). The predominant chemical form of As in the raw rice samples determined by on-line high performance liquid chromatography and ICP-MS was arsenite. Moreover, enzymatic hydrolysis with α-amylase + protease and microprobe focused sonication proved that arsenite could be removed in the highest extent by washing and cooking, meanwhile the main As form remaining in the cooked rice was As(V). Thus, it is recommended to prepare rice-containing dishes in abundant water, which should be discarded after washing and cooking. The results were validated with a NIST SRM 1568a.     

Scanning thermal lithography of tailored tert-butyl ester protected carboxylic acid functionalized (meth)acrylate polymer platforms

In this paper, we report on the development of tailored polymer films for high-resolution atomic force microscopy based scanning thermal lithography (SThL). In particular, full control of surface chemical and topographical structuring was sought. Thin cross-linked films comprising poly(tert-butyl methacrylate) (MA(20)) or poly(tert-butyl acrylate) (A(20)) were prepared via UV initiated free radical polymerization. Thermogravimetric analysis (TGA) and FTIR spectroscopy showed that the heat-induced thermal decomposition of MA(20) by oxidative depolymerization is initially the primary reaction followed by tert-butyl ester thermolysis. By contrast, no significant depolymerization was observed for A(20). For A(20) and MA(20) (at higher temperatures and/or longer reaction times) the thermolysis of the tert-butyl ester liberates isobutylene and yields carboxylic acid groups, which react further intramolecularly to cyclic anhydrides. The values of the apparent activation energies (E(a)) for the thermolysis were calculated to be 125 ± 13 kJ mol(-1) and 116 ± 7 kJ mol(-1) for MA(20) and A(20), respectively. Both MA(20) and A(20) films showed improved thermomechanical stability during SThL compared to non cross-linked films. Carboxylic acid functionalized lines written by SThL in A(20) films had a typically ~10 times smaller width compared to those written in MA(20) films regardless of the tip radius of the heated probe and did not show any evidence for thermochemically or thermomechanically induced modification of film topography. These observations and the E(a) of 45 ± 3 kJ mol(-1) for groove formation in MA(20) estimated from the observed volume loss are attributed to oxidative thermal depolymerization during SThL of MA(20) films, which is considered to be the dominant reaction mechanism for MA(20). The smallest line width values obtained for MA(20) and A(20) films with SThL were 83 ± 7 nm and 21 ± 2 nm, whereas the depth of the lines was below 1 nm, respectively.     

Metabolic Adaptation as Potential Target in Papillary Renal Cell Carcinomas Based on Their In Situ Metabolic Characteristics

Metabolic characteristics of kidney cancers have mainly been obtained from the most frequent clear cell renal cell carcinoma (CCRCC) studies. Moreover, the bioenergetic perturbances that affect metabolic adaptation possibilities of papillary renal cell carcinoma (PRCC) have not yet been detailed. Therefore, our study aimed to analyze the in situ metabolic features of PRCC vs. CCRCC tissues and compared the metabolic characteristics of PRCC, CCRCC, and normal tubular epithelial cell lines. The protein and mRNA expressions of the molecular elements in mammalian target of rapamycin (mTOR) and additional metabolic pathways were analyzed in human PRCC cases compared to CCRCC. The metabolic protein expression pattern, metabolite content, mTOR, and metabolic inhibitor sensitivity of renal carcinoma cell lines were also studied and compared with tubular epithelial cells, as “normal” control. We observed higher protein expressions of the “alternative bioenergetic pathway” elements, in correlation with the possible higher glutamine and acetate consumption in PRCC cells instead of higher glycolytic and mTOR activity in CCRCCs. Increased expression of certain metabolic pathway markers correlates with the detected differences in metabolite ratios, as well. The lower lactate/pyruvate, lactate/malate, and higher pyruvate/citrate intracellular metabolite ratios in PRCC compared to CCRCC cell lines suggest that ACHN (PRCC) have lower Warburg glycolytic capacity, less pronounced pyruvate to lactate producing activity and shifted OXPHOS phenotype. However, both studied renal carcinoma cell lines showed higher mTOR activity than tubular epithelial cells cultured in vitro, the metabolite ratio, the enzyme expression profiles, and the higher mitochondrial content also suggest increased importance of mitochondrial functions, including mitochondrial OXPHOS in PRCCs. Additionally, PRCC cells showed significant mTOR inhibitor sensitivity and the used metabolic inhibitors increased the effect of rapamycin in combined treatments. Our study revealed in situ metabolic differences in mTOR and metabolic protein expression patterns of human PRCC and CCRCC tissues as well as in cell lines. These underline the importance in the development of specific new treatment strategies, new mTOR inhibitors, and other anti-metabolic drug combinations in PRCC therapy.     

Master equations for Wigner functions with spontaneous collapse and their relation to thermodynamic irreversibility

Journal of Computational Electronics - Wigner functions, allowing for a reformulation of quantum mechanics in phase space, are of central importance for the study of the quantum-classical...     

DUckCov: a Dynamic Undocking-Based Virtual Screening Protocol for Covalent Binders

Thanks to recent guidelines, the design of safe and effective covalent drugs has gained significant interest. Other than targeting non-conserved nucleophilic residues, optimizing the noncovalent binding framework is important to improve potency and selectivity of covalent binders toward the desired target. Significant efforts have been made in extending the computational toolkits to include a covalent mechanism of protein targeting, like in the development of covalent docking methods for binding mode prediction. To highlight the value of the noncovalent complex in the covalent binding process, here we describe a new protocol using tethered and constrained docking in combination with Dynamic Undocking (DUck) as a tool to privilege strong protein binders for the identification of novel covalent inhibitors. At the end of the protocol, dedicated covalent docking methods were used to rank and select the virtual hits based on the predicted binding mode. By validating the method on JAK3 and KRas, we demonstrate how this fast iterative protocol can be applied to explore a wide chemical space and identify potent targeted covalent inhibitors.     

Intermediates and isomers in the substitution of cobalt carbonyl hydride with tertiary phosphorous ligands

Mono- and disubstitution of HCo(CO)₄ with tertiary phosphines and phosphites was studied by IR and¹H-NMR spectroscopy. It was found that these substitutions proceed through phosphonium tetracarbonylcobaltate intermediates, leading to a mixture of isomers. The crystal and molecular structure of trans-HCo(CO)₃[P(O-p-C₆H₄Ph)₃] was determined by X-ray diffraction.GDR research fellow at the University of Veszprém.     

Calculation of orientation factors for crystalline polymers from X-ray pole figure intensities

Summary The characterization of polymer orientation is discussed by expanding the orientation distribution function (ODF) for the crystalline phase into a series of generalized spherical harmonics (GSH) or into a series of symmetric generalized spherical harmonics (SGSH). A transformation relation is derived between the two expansions. By means of this transformation the orientation factors (moments of the ODF) can be calculated from the SGSH series expansion coefficients. As an example, this transformation is demonstrated for crystals of hexagonal symmetry and fiber texture.     

The mechanism of orientation in cold-drawn polyoxymethylene as revealed by crystallographic pole figures

The orientation mechanism of cold-drawn, partially crystalline polyoxymethylene (ULTRAFORM) samples was studied by performing wide angle X-ray scattering (WAXS) measurements. The anisotropic samples were prepared in uniaxial tensile tests around 130°C, in a temperature range between the glass transition and the melting point. The process of the plastic deformation is discussed for different degrees of anisotropy. The orientation distribution of the crystalline lamellae was qualitatively characterized by performing pole figure intensity calculations from the measured WAXS intensities. The degree of orientation was quantitatively described by calculating the orientation factors for the [100] normal vector of the unit cell. The texture of the necked samples with high orientation degrees was a mixture of axial and uniplanar-axial textures. An explanation for the formation of this kind of orientation is proposed assuming an influence of the sample geometry on the orientation process.     

Anisotropic stick-slip friction of highly oriented thin films of poly(tetrafluoroethylene) at the molecular level

Lateral force microscopy (LFM) studies of poly(tetrafluoroethylene) (PTFE) films with molecular resolution are reported. Thin PTFE layers with a high degree of orientation were obtained by pressing and sliding a block of polymer on a clean, heated muscovite mica substrate. LFM nanographs obtained on these films by scanning at directions between ca. 40 and 90° with respect to the film orientation direction, i.e. with respect to the direction of the polymer chains, showed a stick-slip type frictional motion of the LFM probe tip at the molecular level. The friction force observed at constant load decreased with decreasing scan angles. Chain-chain packing distances obtained by LFM and contact-mode atomic force microscopy were the same to within the experimental error and had a value of 5.8 Å. Dual-mode contact AFM/LFM imaging was also performed by scanning in the chain direction. Here LFM nanographs showed no distinct stick-slip phenomenon. The contact mode AFM images, however, exhibited clear molecular resolution with the expected chain-chain periodicity. The disappearance of the stick component in LFM scans performed in the chain direction was attributed to the smooth surface of PTFE on the molecular scale.