Melt infiltration casting of bulk metallic-glass matrix composites

The authors describe a technique for melt infiltration casting of composites with a metallic-glass matrix. We made rods 5 cm in length and 7 mm in diameter. The samples were reinforced by continuous metal wires, tungsten powder, or silicon carbide particulate preforms. The most easily processed composites were those reinforced with tungsten and carbon steel continuous wire reinforcement. The Zr41.2Ti13.8Cu12.5Ni10.0Be22.5 matrix was quenched to a glass after infiltrating the reinforcement. We analyzed the microstructure of the composites by x-ray diffraction and scanning electron microscopy. The measured porosity was less than 3% and the matrix was about 97% amorphous material

Vibrational Enhancement of the Effective Donor - Acceptor Coupling

The paper deals with a simple three sites model for charge transfer phenomena in an one-dimensional donor (D) - bridge (B) - acceptor (A) system coupled with vibrational dynamics of the B site. It is found that in a certain range of parameters the vibrational coupling leads to an enhancement of the effective donor - acceptor electronic coupling as a result of the formation of the polaron on the B site. This enhancement of the charge transfer efficiency is maximum at the resonance, where the effective energy of the fluctuating B site coincides with the donor (acceptor) energy.Comment: 5 pages, 3 figure

Two-level system with a thermally fluctuating transfer matrix element: Application to the problem of DNA charge transfer

Charge transfer along the base-pair stack in DNA is modeled in terms of thermally-assisted tunneling between adjacent base pairs. Central to our approach is the notion that tunneling between fluctuating pairs is rate-limited by the requirement of their optimal alignment. We focus on this aspect of the process by modeling two adjacent base pairs in terms of a classical damped oscillator subject to thermal fluctuations as described by a Fokker-Planck equation. We find that the process is characterized by two time scales, a result that is in accord with experimental findings.Comment: original file is revtex4, 10 pages, three eps figure

Tight-binding parameters for charge transfer along DNA

We systematically examine all the tight-binding parameters pertinent to charge transfer along DNA. The $\pi$ molecular structure of the four DNA bases (adenine, thymine, cytosine, and guanine) is investigated by using the linear combination of atomic orbitals method with a recently introduced parametrization. The HOMO and LUMO wavefunctions and energies of DNA bases are discussed and then used for calculating the corresponding wavefunctions of the two B-DNA base-pairs (adenine-thymine and guanine-cytosine). The obtained HOMO and LUMO energies of the bases are in good agreement with available experimental values. Our results are then used for estimating the complete set of charge transfer parameters between neighboring bases and also between successive base-pairs, considering all possible combinations between them, for both electrons and holes. The calculated microscopic quantities can be used in mesoscopic theoretical models of electron or hole transfer along the DNA double helix, as they provide the necessary parameters for a tight-binding phenomenological description based on the $\pi$ molecular overlap. We find that usually the hopping parameters for holes are higher in magnitude compared to the ones for electrons, which probably indicates that hole transport along DNA is more favorable than electron transport. Our findings are also compared with existing calculations from first principles.Comment: 15 pages, 3 figures, 7 table

Hetero-cycloreversions Mediated by Photoinduced Electron Transfer

[EN] Discovered more than eight decades ago, the Diels-Alder (DA) cycloaddition (CA) remains one of the most versatile tools in synthetic organic chemistry. Hetero-DA processes are powerful methods for the synthesis of densely functionalized six-membered heterocycles, ubiquitous substructures found in natural products and bioactive compounds. These reactions frequently employ azadienes and oxadienes, but only a few groups have reported DA processes with thiadienes. The electron transfer (ET) version of the DA reaction, though less investigated, has emerged as a subject of increasing interest. In the last two decades, researchers have paid closer attention to radical ionic hetero-cycloreversions, mainly in connection with their possible involvement in the repair of pyrimidine(6-4)pyrimidone photolesions in DNA by photolyases. In biological systems, these reactions likely occur through a reductive photosensitization mechanism. In addition, photooxidation can lead to cycloreversion (CR) reactions, and researchers can exploit this strategy for DNA repair therapies. In this Account, we discuss electron-transfer (ET) mediated hetero-CR reactions. We focus on the oxidative and reductive ET splitting of oxetanes, azetidines, and thietanes. Photoinduced electron transfer facilitates the splitting of a variety of four-membered heterocycles. In this context, researchers have commonly examined oxetanes, both experimentally and theoretically. Although a few studies have reported the cycloreversion of azetidines and thietanes carried out under electron transfer conditions, the number of examples remains limited. In general, the cleavage of the ionized four-membered rings appears to occur via a nonconcerted two-step mechanism. The trapping of the intermediate 1,4-radical ions and transient absorption spectroscopy data support this hypothesis, and it explains the observed loss of stereochemistry in the products. In the initial step, either C-C or C-X bond breaking may occur, and the preferred route depends on the substitution pattern of the ring, the type of heteroatom, and various experimental conditions. To better accommodate spin and charge, C-X cleavage happens more frequently, especially in the radical anionic version of the reaction. The addition or withdrawal of a single electron provides a new complementary synthetic strategy to activate hetero-cycloreversions. Despite its potential, this strategy remains largely unexplored. However, it offers a useful method to achieve C=X/olefin metathesis or, upon ring expansion, to construct six-membered heterocyclic rings.Financial support from the Spanish Government (Grants CTQ2010-14882, SEV2012-0267, and JCI-2010-06204) and the Generalitat Valenciana (Prometeo II/2013/005) is gratefully acknowledged.Pérez Ruiz, R.; Jiménez Molero, MC.; Miranda Alonso, MÁ. (2014). Hetero-cycloreversions Mediated by Photoinduced Electron Transfer. Accounts of Chemical Research. 47(4):1359-1368. https://doi.org/10.1021/ar4003224S1359136847

Bulk metallic glass matrix composites : processing, microstructure, and application as a kinetic energy penetrator

NOTE: Text or symbols not renderable in plain ASCII are indicated by [...]. Abstract is included in .pdf document. The development of alloys with high glass forming ability allows fabrication of bulk samples of amorphous metal. This capability makes these materials available for applications which require significant material thickness in all three dimensions. Superior mechanical properties and advantages in processing make metallic glass a choice candidate as a matrix material for composites. This study reports techniques for making composites by melt-infiltration casting using the alloy [...] ([...]) as a matrix material. Composite rods 5 cm in length and 7 mm in diameter were made and found to have a nearly fully amorphous matrix; there was less than 3 volume percent crystallized matrix material. The samples were reinforced by continuous metal wires, tungsten powder, or silicon carbide particulate preforms. The most easily processed samples were made with uniaxially aligned tungsten and carbon steel continuous wire reinforcement; the majority of the analysis presented is of these samples. The measured porosity was typically less than 3%. The results also indicate necessary guidelines for developing processing techniques for large scale production, new reinforcement materials, and other metallic glass compositions. Analysis of the microstructure of the tungsten wire and steel wire reinforced composites was performed by x-ray diffraction, scanning electron microscopy, scanning Auger microscopy, transmission electron microscopy, and energy dispersive x-ray spectroscopy. The most common phase in the crystallized matrix is most likely a Laves phase with the approximate formula [...]. In tungsten-reinforced composites, a crystalline reaction layer 240 nm thick of tungsten nanocrystals in anamorphous matrix formed. In the steel reinforced composites, the reaction layer was primarily composed of a mixed metal carbide, mainly [...]. One promising application of the metallic glass mat composite is as a kinetic energy penetrator material. Ballistic tests show that a composite of 80 volume percent uniaxially aligned tungsten wires and a [...] 1 matrix has self-sharpening behavior, which is a necessary characteristic of superior penetrator materials. Small-scale tests with both aluminum and steel targets show that this composite performs better than tungsten heavy alloys typically used for penetrator applications, and comparably with depleted uranium