A study of the oscillating corner meniscus in a vertical constrained vapor bubble system

A vertical constrained vapor bubble, VCVB, made of fused silica was used to study the stability and oscillations of an evaporating wetting film of HFE- 7000^® in a corner. The film thickness profile was measured as a function of time and axial position using an advanced form of image analyzing interferometry. The curvature, apparent contact angle, and pressure profiles for the evaporating film were calculated from the measured film thickness profiles. Oscillation of the liquid film was observed and profiles for both the advancing and receding films were obtained. These are the first such detailed profiles obtained for an oscillating meniscus below a thickness of 0.1 μm.The film thickness profiles demonstrated the spreading of the meniscus during advance as well as the presence of a curvature gradient near the contact line region. The maximum curvature decreased for the advancing menisci and increased with time for the receding menisci. An increase in the adsorbed film thickness was associated with the advancing stage and a decrease with the receding stage. Pressure profiles were measured as a function of position indicating the potential for driving the flow of the fluid toward or away from the contact line. As the film advances or recedes, the pressure gradients change as a function of position fueling the next oscillation cycle.     

Influence of stereochemistry and redox potentials on the single- and double-strand DNA cleavage efficiency of Cu(II) and Ni(II) Lys-Gly-His-derived ATCUN metallopeptides

The DNA cleavage chemistry of a series of metallopeptides based on the amino-terminal Cu and Ni (ATCUN) binding motif of proteins has been studied. Specifically, the impact of the positioning of charged Lys side chains and their stereochemistry on metal reduction potentials and DNA cleavage reactivity have been quantitatively evaluated. Both Cu and Ni metallopeptides show a general increase in reactivity toward DNA with an increasing number of Lys residues, while a corresponding decrease in complex reduction potential reflects the enhanced sigma-donor character of the Lys side chain relative to that of Gly. Placement of Lys at the first position in the tripeptide ligand sequence resulted in a greater increase in DNA cleavage reactivity, relative to placement at the second position, while a switch from an l-Lys to a d-Lys typically resulted in enhanced reactivity, as well as perturbations of reduction potential. In the case of Cu peptides, reactivity was enhanced with both increasing positive charge density on the peptide and stabilization of the Cu3+ state. However, for Ni peptides, while the general trends are the same, the correlation with redox behavior was less pronounced. Most likely these differences in specific trends for the Cu and Ni complexes reflect the distinct coordination preferences for Cu3+/2+ and Ni3+/2+ oxidation states, and the consequent distinct positioning of metal-associated reactive oxygen species, as well as the orientation of the DNA-associated complex. Thus, the amino acid composition and stereochemistry of ATCUN metallopeptides can tune the intrinsic reactivities of these systems (their ability to promote formation and activity of metal-associated ROS) as well as their overall structural features, and both of these aspects appear to influence their reactivity and efficiency of DNA strand scission.     

Three-dimensional visualization and characterization of morphology and internal microstructural features of primary silicon crystals in a cast Al–Si base alloy

Primary Si crystals are usually present in the cast microstructures of near-eutectic, eutectic, and hyper-eutectic Al–Si base alloys. Three-dimensional digital images of individual primary Si crystals present in a permanent mold cast unmodified Al-12 wt% Si-1 wt% Ni base alloy are reconstructed using a combination of montage serial sectioning and three-dimensional digital image processing techniques. Octahedral, prismatic, and plate-like three-dimensional morphologies of the primary Si crystals are present in the microstructure. Some of the primary Si crystals contain interior regions/islands of Al-alloy that are completely enclosed in the corresponding Si crystals indicating certain variations in the crystal growth velocities during the evolution of these crystals. The boundaries of these interior regions/islands are non-faceted smooth and curved indicating re-melting of the Al-rich islands and re-dissolution of some Si near these internal boundaries in the Al-alloy as a result of the heat generated by liquid-to-solid transformation of Si away from the islands.     

The effects of macroscopic inhomogeneities on the magnetotransport properties of the electron gas in two dimensions

In experiments on electron transport, the macroscopic inhomogeneities in the sample play a fundamental role. In this paper and a subsequent one, we introduce and develop a general formalism that captures the principal features of sample inhomogeneities (density gradients, contact misalignments) in the magnetoresistance data taken from low-mobility heterostructures. We present detailed assessments and experimental investigations of the different regimes of physical interest, notably the regime of semiclassical transport at weak magnetic fields, the plateau–plateau transitions as well as the plateau–insulator transition that generally occurs at much stronger values of the external field only.It is shown that the semiclassical regime at weak fields plays an integral role in the general understanding of the experiments on the quantum Hall regime. The results of this paper clearly indicate that the plateau–plateau transitions, unlike the plateau–insulator transition, are fundamentally affected by the presence of sample inhomogeneities. We propose a universal scaling result for the magnetoresistance parameters. This result facilitates, amongst many other things, a detailed understanding of the difficulties associated with the experimental methodology of H.P. Wei et al. in extracting the quantum critical behavior of the electron gas from the transport measurements conducted on the plateau–plateau transitions.     

A phenomenological,kinematical model of the coronal magnetic fields in terms of thin flux tubes rising from the photosphere

A kinematical model is necessary for understanding the gross structure of the coronal magnetic field and its slow evolution in consistency with the small scale structure of the photospheric fields. Here we have developed a preliminary phenomenological model in terms of flux tubes of flux amounts ≈ 10¹⁷ − 10^18.5 Mx rising across the inner corona in the form of arches and opening out in the outer corona. In contrast to Parker’s estimate, this model is consistent with the observed spans of the chromospheric fibrils and x-ray arches. It is also consistent with the number of flux tubes present above the photosphere as estimated from the observed abundance of spicules.     

Antituberculosis agent diaportheone B: synthesis, absolute configuration assignment, and anti-TB activity of its analogues

First synthesis of diaportheone B, an antituberculosis agent isolated from endophytic fungus Diaporthe sp. P133 is reported using two complementary routes, a one step and a three-step sequence. The absolute configuration of diaportheone B was determined by using X-ray crystal structure analysis of its dibromo derivative. In addition, we have prepared several close analogues of diaportheone B and determined their anti-TB potential using Alamar-blue assay (H(37)Rv).     

Tertiary DNA structure in the single-stranded hTERT promoter fragment unfolds and refolds by parallel pathways via cooperative or sequential events

The discovery of G-quadruplexes and other DNA secondary elements has increased the structural diversity of DNA well beyond the ubiquitous double helix. However, it remains to be determined whether tertiary interactions can take place in a DNA complex that contains more than one secondary structure. Using a new data analysis strategy that exploits the hysteresis region between the mechanical unfolding and refolding traces obtained by a laser-tweezers instrument, we now provide the first convincing kinetic and thermodynamic evidence that a higher order interaction takes place between a hairpin and a G-quadruplex in a single-stranded DNA fragment that is found in the promoter region of human telomerase. During the hierarchical unfolding or refolding of the DNA complex, a 15-nucleotide hairpin serves as a common species among three intermediates. Moreover, either a mutant that prevents this hairpin formation or the addition of a DNA fragment complementary to the hairpin destroys the cooperative kinetic events by removing the tertiary interaction mediated by the hairpin. The coexistence of the sequential and the cooperative refolding events provides direct evidence for a unifying kinetic partition mechanism previously observed only in large proteins and complex RNA structures. Not only does this result rationalize the current controversial observations for the long-range interaction in complex single-stranded DNA structures, but also this unexpected complexity in a promoter element provides additional justification for the biological function of these structures in cells.     

Photochemical transformations—I : Reactions of some terpene iodides

Photo-irradiation of longibornyl iodide in n-heptane containing some triethylamine as scavenger for hydrogen iodide, furnished rearranged hydrocarbons (longifolene, longicyclene and longiborn-8-ene). Citronellyl iodide, under similar conditions, led to simple elimination (to furnish 2,6-dimethylocta-2,7-diene) and π-participation (to yield trans-p-menth-8-ene) to almost equal extent. A possible mechanism for these reactions is discussed.     

Promiscuous fatty acyl CoA ligases produce acyl-CoA and acyl-SNAC precursors for polyketide biosynthesis

The study of bioactive natural products has undergone rapid advancement with the cloning and sequencing of large number of gene clusters and the concurrent progress to manipulate complex biosynthetic systems in heterologous hosts. The genetic reconstitution necessitates that the heterologous hosts possess substrate pools that could be coordinately supplied for biosynthesis. Polyketide synthases (PKS) utilize acyl-coenzyme A (CoA) precursors and synthesize polyketides by repetitive decarboxylative condensations. Here we show that acyl-CoA ligases, which belong to a large family of acyl-activating enzymes, possess potential to produce varied starter CoA precursors that could be utilized in polyketide biosynthesis. Incidentally, such protein domains have been recognized in several PKS and nonribosomal peptide synthetase gene clusters. Our studies with mycobacterial fatty acyl-CoA ligases (FACLs) show remarkable tolerance to activate a variety of fatty acids that contain modifications at alpha, beta, omega, and omega-nu positions. This substrate flexibility extends further such that these proteins also efficiently utilize N-acetyl cysteamine, the shorter acceptor terminal portion of CoASH, to produce acyl-SNACs. We show that the in situ generated acyl-CoAs and acyl-SNACs could be channeled to types I and -III PKS systems to produce new metabolites. Together, the promiscuous activity of FACL and PKSs provides new opportunities to expand the repertoire of natural products.