Multi-instrument characterization of HiPIMS and DC magnetron sputtered tungsten and copper films

In this work, copper and tungsten were sputtered onto silicon wafers by direct current magnetron sputtering (DCMS) and high-power impulse magnetron sputtering (HiPIMS). The resulting films were characterized by energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), atomic force microscopy (AFM), spectroscopic ellipsometry (SE), and X-ray diffraction (XRD). By EDX and XPS, all the sputtered films showed only the expected metal peaks. By XPS, the surfaces sputtered by DCMS were richer in oxygen than those produced by HiPIMS. By AFM, the surfaces were quite smooth. The root mean square (RMS) roughness values are as follows: 0.83 nm (W, HiPIMS), 1.10 nm (W, DCMS), 0.85 nm (Cu, HiPIMS), and 1.78 nm (Cu, DCMS). By SEM, the HiPIMS films exhibited smaller grain sizes, which was confirmed by XRD. The crystallite sizes estimated by XRD are as follows: 4 nm (W, body-centered cubic, HiPIMS), 13 nm (W, body-centered cubic, DCMS), 7 nm (W, cubic, HiPIMS), 14 nm (W, cubic, DCMS), 25 nm (Cu, HiPIMS), and 35 nm (Cu, DCMS). By SE, the HiPIMS surfaces showed higher refractive indices, which suggested that they were denser and less oxidized than the DCMS surfaces.     

The impact of P-substituents on the structures, spectroscopic properties, and reactivities of POCOP-type pincer complexes of nickel(II)

The room temperature reaction of NiBr(2)(NCCH(3))(x) with the pincer-type ligand POCHOP(Ph) gave the new pincer complex (POCOP(Ph))NiBr (1, POCOP(Ph) = κ(P), κ(C), κ(P)-2,6-{Ph(2)PO}(2)C(6)H(3)). Complex 1 reacts with AgX to give the analogous Ni-X derivatives (X = CN, 2; OSO(2)CF(3), 3; OC(O)CH(3), 4; ONO(2), 5), whereas complex 3 reacts with phenylacetylene and NEt(3) to give the Ni-CCPh derivative 6. On the other hand, reaction of 1 or 3 with RLi or RMgI did not afford the desired Ni-R derivatives, giving instead the corresponding iodo and hydroxo derivatives. Complexes 1-6 have been characterized by NMR, IR, and UV-Vis spectroscopy and X-ray crystallography. The solid state structural and IR data indicate that Ni-C(sp) interaction is dominated by ligand-to-metal σ-donation in 2 and 6. Cyclic voltammetry measurements indicate that complexes 3 and 4 display reversible redox behaviour (Ni(II)/Ni(III)); comparison of the E(0)(1/2) values for these complexes and their POCOP(i-Pr) analogues shows that both the X ligands and the P-substituent have a considerable impact on the ease of oxidation in this family of complexes.     

Energy landscape analyses of disordered histone tails reveal special organization of their conformational dynamics

Histone tails are highly flexible N- or C-terminal protrusions of histone proteins which facilitate the compaction of DNA into dense superstructures known as chromatin. On a molecular scale histone tails are polyelectrolytes with high degree of conformational disorder which allows them to function as biomolecular "switches", regulating various genetic processes. Unfortunately, their intrinsically disordered nature creates obstacles for comprehensive experimental investigation of both the structural and dynamical aspects of histone tails, because of which their conformational behaviors are still not well understood. In this work we have carried out ～3 microsecond long all atom replica exchange molecular dynamics (REMD) simulations for each of four histone tails, H4, H3, H2B, and H2A, and probed their intrinsic conformational preferences. Our subsequent free energy landscape analysis demonstrated that most tails are not fully disordered, but show distinct conformational organization, containing specific flickering secondary structural elements. In particular, H4 forms β-hairpins, H3 and H2B adopt α-helical elements, while H2A is fully disordered. We rationalized observed patterns of conformational dynamics of various histone tails using ideas from physics of polyelectrolytes and disordered systems. We also discovered an intriguing re-entrant contraction-expansion of the tails upon heating, which is caused by subtle interplay between ionic screening and chain entropy.     

Counting substructures II: Hypergraphs

For various k-uniform hypergraphs F, we give tight lower bounds on the number of copies of F in a k-uniform hypergraph with a prescribed number of vertices and edges. These are the first such results for hypergraphs, and extend earlier theorems of various authors who proved that there is one copy of F. A sample result is the following: Füredi-Simonovits [11] and independently Keevash-Sudakov [16] settled an old conjecture of Sós [29] by proving that the maximum number of triples in an n vertex triple system (for n sufficiently large) that contains no copy of the Fano plane is p(n)=( ₂ ^?n/2? )?n/2?+( ₂ ^?n/2? ?n/2?). We prove that there is an absolute constant c such that if n is sufficiently large and 1 ≤ q ≤ cn ², then every n vertex triple system with p(n)+q edges contains at least $6q\left( {\left( {_4^{\left\lfloor {n/2} \right\rfloor } } \right) + \left( {\left\lceil {n/2} \right\rceil - 3} \right)\left( {_3^{\left\lfloor {n/2} \right\rfloor } } \right)} \right)$ copies of the Fano plane. This is sharp for q≤n/2–2. Our proofs use the recently proved hypergraph removal lemma and stability results for the corresponding Turán problem.     

Automated SEM-EDS pottery classification based on minero-chemical quantitative parameters: An application on ancient Greek pottery from Adrano (NE Sicily,Italy)

A new SEM-EDS procedure for ancient ceramic classification, based on the automated acquisition and the semiautomated processing of multi-elemental X-ray maps, is described. Based on the detection of each aplastic inclusion, the procedure allows to simultaneously obtain a quantitative evaluation of both the inclusion mineral–chemical composition and the ceramic matrix chemical composition. The two data sets can individually or jointly be subjected to statistical methods. The proposed protocol was applied on a set of 22 samples of black glaze pottery from Adrano (north-eastern Sicily), Hellenistic age (4th to 2nd centuries B.C.). Two main groups emerged from the application of the procedure, mainly distinguished for their quartz–feldspars versus calcium–aluminosilicate relative abundance as the inclusion mineral–chemical composition is concerned and for their matrix SiO₂ versus CaO. The classification based on the inclusion mineral–chemical data obtained with the proposed method mirrors the results from the traditional OM observation, but when the two data sets are simultaneously considered, a subtler differentiation is observed with the separation of one of the groups in two subgroups, allowing to refine the partition.     

Efficient Co-Catalyzed Double Hydroboration of Nitriles: Application to One-Pot Conversion of Nitriles to Aldimines

The commercially available and bench-stable Co(acac)₂/dpephos system is employed as a precatalyst for selective and efficient room temperature hydroboration of organic nitriles with HBPin to produce a series of N,N-diborylamines [RN(BPin)₂], which react in situ with aldehydes to give aldimines. Formation of aldimines from N,N-diborylamines does not require a dehydrating agent, is applicable to a wide range of N,N-diborylamine and aldehyde substrates and is highly chemoselective, being unaffected by various common functional groups, such as alkenes, alkynes, secondary amines, ketones, esters, amides, carboxylic acids, pyridines, nitriles, and nitro compounds. The overall transformation represents a synthetically valuable approach to aldimines from nitriles and can be performed in a sequential one-pot manner, tolerating ester, lactone, carboxamide and unactivated alkene functionalities.     

Sharp Weighted Korn and Korn-Like Inequalities and an Application to Washers

In this paper we prove asymptotically sharp weighted “first-and-a-half” \(2D\) Korn and Korn-like inequalities with a singular weight occurring from Cartesian to cylindrical change of variables. We prove some Hardy and the so-called “harmonic function gradient separation” inequalities with the same singular weight. Then we apply the obtained \(2D\) inequalities to prove similar inequalities for washers with thickness \(h\) subject to vanishing Dirichlet boundary conditions on the inner and outer thin faces of the washer. A washer can be regarded in two ways: As the limit case of a conical shell when the slope goes to zero, or as a very short hollow cylinder. While the optimal Korn constant in the first Korn inequality for a conical shell with thickness \(h\) and with a positive slope scales like \(h^{1.5}\), e.g., (Grabovsky and Harutyunyan in arXiv:1602.03601, 2016), the optimal Korn constant in the first Korn inequality for a washer scales like \(h^{2}\) and depends only on the outer radius of the washer as we show in the present work. The Korn constant in the first and a half inequality scales like \(h\) and depends only on \(h\). The optimal Korn constant is realized by a Kirchhoff Ansatz. This results can be applied to calculate the critical buckling load of a washer under in plane loads, e.g., (Antman and Stepanov in J. Elast. 124(2):243–278, 2016).     

Korn inequalities for shells with zero Gaussian curvature

We consider shells with zero Gaussian curvature, namely shells with one principal curvature zero and the other one having a constant sign. Our particular interests are shells that are diffeomorphic to a circular cylindrical shell with zero principal longitudinal curvature and positive circumferential curvature, including, for example, cylindrical and conical shells with arbitrary convex cross sections. We prove that the best constant in the first Korn inequality scales like thickness to the power 3/2 for a wide range of boundary conditions at the thin edges of the shell. Our methodology is to prove, for each of the three mutually orthogonal two-dimensional cross-sections of the shell, a “first-and-a-half Korn inequality”—a hybrid between the classical first and second Korn inequalities. These three two-dimensional inequalities assemble into a three-dimensional one, which, in turn, implies the asymptotically sharp first Korn inequality for the shell. This work is a part of mathematically rigorous analysis of extreme sensitivity of the buckling load of axially compressed cylindrical shells to shape imperfections.     

Ion-exchange equilibria of metal ions and hydrogen ions on anilinium tin(IV) phosphate

Summary Ion-exchange equilibria of metal ions (Mn^II, Cu^II, Zn^II, Cd^II and Hg^II)/H⁺ systems have been studied at 30, 40, 50 and 60°C on anilinium tin(IV) phosphate (ATP) as a cation exchanger. The exchange isotherms were measured for both forward and reverse reactions with a solution of ionic strength 0.1 by the batch technique. The isotherms are S-shaped for each ion-exchange system. Selectivity coefficients vary linearly with the equivalent fraction of transition metal ion in the exchanger in the range from 0 to 0.6. The selectivity sequence of zero loading is: Zn^II <Mn^II<Cu^II<Cd^II<Hg^II. Overall and hypothetical (zero loading) thermodynamic data are evaluated.     

Towards Characterization of All 3 × 3 Extremal Quasiconvex Quadratic Forms

Given a d × d quasiconvex quadratic form, d ≥ 3, we prove that if the determinant of its acoustic tensor is an irreducible extremal polynomial that is not identically zero, then the form itself is an extremal quasiconvex quadratic form; i.e., it loses its quasiconvexity whenever a convex quadratic form is subtracted from it. In the special case d=3, we slightly weaken the condition; namely we prove that if the determinant of the acoustic tensor of the quadratic form is an extremal polynomial that is not a perfect square, then the form itself is an extremal quadratic form. In the case d=3 we also prove that if the determinant of the acoustic tensor of the form is identically zero, then the form is either extremal or polyconvex. Also, if the determinant of the acoustic tensor of the form is a perfect square, then the form is either extremal or polycovex, or is a sum of a rank‐1 form and an extremal whose acoustic tensor determinant is identically zero. Here we use the notion of extremality introduced by Milton in 1990. © 2017 Wiley Periodicals, Inc.