Computational design of chemical nanosensors: Transition metal doped single-walled carbon nanotubes

We present a general approach to the computational design of nanostructured chemical sensors. The scheme is based on identification and calculation of microscopic descriptors (design parameters) which are used as input to a thermodynamic model to obtain the relevant macroscopic properties. In particular, we consider the functionalization of a (6,6) metallic armchair single-walled carbon nanotube (SWNT) by nine different 3d transition metal (TM) atoms occupying three types of vacancies. For six gas molecules (N_{2}, O_{2}, H_{2}O, CO, NH_{3}, H_{2}S) we calculate the binding energy and change in conductance due to adsorption on each of the 27 TM sites. For a given type of TM functionalization, this allows us to obtain the equilibrium coverage and change in conductance as a function of the partial pressure of the "target" molecule in a background of atmospheric air. Specifically, we show how Ni and Cu doped metallic (6,6) SWNTs may work as effective multifunctional sensors for both CO and NH_{3}. In this way, the scheme presented allows one to obtain macroscopic device characteristics and performance data for nanoscale (in this case SWNT) based devices.Comment: Chapter 7 in "Chemical Sensors: Simulation and Modeling", Ghenadii Korotcenkov (ed.), 47 pages, 22 figures, 10 table

Electronic Structure of Low-Dimensional Carbon Π-Systems

X-ray absorption spectroscopy (XAS) is combined with density functional theory (DFT) to determine the orbitals of one- and two-dimensional carbon π-systems (lycopene, beta-carotene, retinal, retinol, retinoic acid, coronene, triphenylene). Considerable fine structure is observed for the transition from the C 1s level to the lowest unoccupied molecular orbital (LUMO) and explained by DFT. The wave functions of the one-dimensional chain molecules display the node structure of a vibrating string. The XAS transition energy is decomposed into contributions from the C 1s core level, the π* final state, and the electron–hole interaction. For the latter, we develop a simple model that accurately represents a full Δ-self-consistent field (ΔSCF) calculation. The distortion of the LUMO because of its interaction with the C 1s hole is investigated. These results illustrate the electronic states of prototypical π-bonded carbon structures with low-dimensional character, such as those used in molecular complexes for solar cells, confined graphene structures, and molecular wires

A new mixed-integer programming model for irregular strip packing based on vertical slices with a reproducible survey

The irregular strip-packing problem, also known as nesting or marker making, is defined as the automatic computation of a non-overlapping placement of a set of non-convex polygons onto a rectangular strip of fixed width and unbounded length, such that the strip length is minimized. Nesting methods based on heuristics are a mature technology, and currently, the only practical solution to this problem. However, recent performance gains of the Mixed-Integer Programming (MIP) solvers, together with the known limitations of the heuristics methods, have encouraged the exploration of exact optimization models for nesting during the last decade. Despite the research effort, the current family of exact MIP models for nesting cannot efficiently solve both large problem instances and instances containing polygons with complex geometries. In order to improve the efficiency of the current MIP models, this work introduces a new family of continuous MIP models based on a novel formulation of the NoFit-Polygon Covering Model (NFP-CM), called NFP-CM based on Vertical Slices (NFP-CM-VS). Our new family of MIP models is based on a new convex decomposition of the feasible space of relative placements between pieces into vertical slices, together with a new family of valid inequalities, symmetry breakings, and variable eliminations derived from the former convex decomposition. Our experiments show that our new NFP-CM-VS models outperform the current state-of-the-art MIP models. Finally, we provide a detailed reproducibility protocol and dataset based on our Java software library as supplementary material to allow the exact replication of our models, experiments, and results

Immunohistochemical analysis of ß3 integrin (CD61): expression in pig tissues and human tumors

CD61 is a membrane glycoprotein that associates with CD41 (aIIb) to form the heterodimeric complex gpIIb/IIIa (CD41/CD61), predominantly expressed in platelets and megakariocytes. CD61 or ß3 integrin also associates with av (CD51) to form the vitronectin receptor, which is expressed in many tissues. We have used a monoclonal antibody against the porcine gpIIIa or CD61 (JM2E5) to study the distribution of this molecule in different normal pig tissues. As in humans, CD61 was broadly expressed in all tissues examined. In the kidney, strong expression of CD61 was observed in epithelial cells from renal tubules. In the testis, CD61 expression was detected in the Leydig cells. However, in liver, CD61 was weak or not detected. Many integrins are particularly involved in tumogenicity and in tumor progression mediating cellcell interaction. Immunofluorescence experiments using cultured human tumor HeLa cells showed nuclear and cytoplasmic staining of mAb JM2E5. Immunohistochemical analysis of human tumor sections from several organs showed a heterogeneus distribution in metastatic cases from colon and breast carcinoma. However, no staining was found in metastasis from melanom

Origin of Small Barriers in Jahn–Teller Systems:Quantifying the Role of 3d–4s Hybridization in the Model System NaCl:Ni⁺

Despite its relevance, the microscopic origin of the energy barrier, B, between the compressed and elongated geometries of Jahn–Teller (JT) systems is not well understood yet because of a lack of quantitative data about its various contributions. Seeking to clear up this matter, we have carried out both periodic and cluster ab initio calculations on the model system NaCl:Ni+. This system is particularly puzzling because, according to experimental data, its barrier is much smaller than that for other d9 and d7 ions in similar lattices. All calculations performed on the model system lead, in fact, to values |B| ≤ 160 cm–1, which are certainly smaller than B = 500 cm–1 derived for NaCl:M2+ (M = Ag, Rh) or B = 1024 cm–1 obtained for KCl:Ag2+. As a salient feature, analysis of calculations carried out as a function of the Qθ (3z2 – r2) coordinate unveils the microscopic origin of the barrier. It is quantitatively proven that the elongated geometry observed for NaCl:Ni+ is due to the 3d–4s vibronic admixture, which is slightly larger than the anharmonicity in the eg JT mode that favors a compressed geometry. The existence of these two competing mechanisms explains the low value of B for the model system, contrary to cases where the complex formed by d9 or d7 ions is elastically decoupled from the host lattice. Although the magnitude of B for NaCl:Ni+ is particularly small, the tunneling splitting, 3Γ, is estimated to be below 9 cm–1, thus explaining why the coherence is easily destroyed by random strains and thus a static JT effect is observed experimentally. As a main conclusion, the barrier in JT systems cannot be understood neglecting the tiny changes of the electronic density involved in small distortions. The present calculations reasonably explain the experimental g tensor of NaCl:Ni+, pointing out that the d–d transitions in NiCl65– are much smaller than those for CuCl64– and the optical electronegativity of Ni+ is only around 1.</p

UV-B radiation reduces in vitro germination of Metarhizium anisopliae s.l. but does not affect virulence in fungustreated Aedes aegypti adults and development on dead mosquitoes

Fil: Falvo, Marianel Lucía. Universidad Nacional de La Plata. Facultad de Ciencias Naturales y Museo. Centro de Estudios Parasitológicos y de Vectores; ArgentinaFil: Pereira-Junior, Ronaldo Alves. Universidade Federal de Goias. Instituto de Patologia Tropical e Saude Publica (IPTSP); BrasilFil: Rodrigues, J.. Universidade Federal de Goias. Instituto de Patologia Tropical e Saude Publica (IPTSP); BrasilFil: López Lastra, Claudia Cristina. Universidad Nacional de La Plata. Facultad de Ciencias Naturales y Museo. Centro de Estudios Parasitológicos y de Vectores; ArgentinaFil: García, Juan José. Universidad Nacional de La Plata. Facultad de Ciencias Naturales y Museo. Centro de Estudios Parasitológicos y de Vectores; ArgentinaFil: Fernandes, Everton K.K.. Fil