Grafting densely-packed poly(n-butyl methacrylate) chains from an iron substrate by aryl diazonium surface-initiated ATRP: XPS monitoring

Poly(n-butyl methacrylate), PBMA, chains were grafted by atom transfer radical polymerization (ATRP) from the surface of iron plates using electrochemically attached initiators based on diazonium salts providing an iron/polyphenylene/PBMA structure. This surface-initiated ATRP procedure was controlled by the addition of a small proportion of Cu⁺⁺ deactivator, but in the absence of any sacrificial initiator. Combined XPS, IR and AFM experiments provide a powerful means for the characterization of the obtained complex iron/polyphenylene/PBMA layered structure. It is possible to measure the thickness of the brominated aryl structure covalently attached to iron. Concerning the PBMA brushes, their presence on the surface was confirmed by IRRAS. The brominated chain end could be traced by XPS testifying for the ATRP character of the polymerization and the thickness of the polymer brushes was determined. The controlled living ATRP character of the polymerization is confirmed through a linear correlation between the thickness of the layer and the degree of polymerization. Measurement of the grafting density of PBMA chains indicates that they are compactly packed and that, approximately, one brominated aryl chain out of two efficiently initiates ATRP.     

Magnetization Slow Dynamics in Ferrocenium Complexes

The single-molecule magnet (SMM) properties of a series of ferrocenium complexes, [Fe(η⁵-C₅R₅)₂]⁺ (R=Me, Bn), are reported. In the presence of an applied dc field, the slow dynamics of the magnetization in [Fe(η⁵-C₅Me₅)₂]BAr_F are revealed. Multireference quantum mechanical calculations show a large energy difference between the ground and first excited states, excluding the commonly invoked, thermally activated (Orbach-like) mechanism of relaxation. In contrast, a detailed analysis of the relaxation time highlights that both direct and Raman processes are responsible for the SMM properties. Similarly, the bulky ferrocenium complexes, [Fe(η⁵-C₅Bn₅)₂]BF₄ and [Fe(η⁵-C₅Bn₅)₂]PF₆, also exhibit magnetization slow dynamics, however an additional relaxation process is clearly detected for these analogous systems.     

Amphiphilic water soluble cationic ring opening metathesis copolymer as an antibacterial agent

Bacterial infection is a global problem, especially resistance acquired by bacteria against to antibiotics; there is urgent need for the development of antibiotics. Here, we proposed dendron-grafted polymers via ring opening metathesis polymerization (ROMP) featuring different with tailored hydrophobicity/hydrophilicity and cationic charges. Dendritic oxanorbornene derivatives were synthesized having two and six carbon linkers and their corresponding random and block copolymers were prepared having pendant pyridinium salt moieties via ROMP. In total, 12 different water-soluble dendronized cationic polymers featuring hexyl pyridinium moieties were prepared and investigated. Six carbon linker possessing triple charge density and hexyl pyridinium functionality each repeating unit copolymers exhibited high antibacterial activity against Gram-positive bacteria (S. aureus). However, all the polymers were inactive against Gram-negative bacteria (E. coli). Most of the copolymers are non-hemolytic (>HC ₅₀ = 1,000 μg/ml). It was also observed that, there is no significant effect between block copolymers and random copolymers keeping hydrophobicity and cationic charge density constant. Zeta potential was measured to investigate the mechanism in solution via the interaction of polymers with S. aureus, while scanning electron microscope (SEM) measurements image confirms damage of the bacterial cell wall after implementation of biocidal polymer.     

Quantization of the Sphere with Coherent States

Current views link quantization with dynamics. The reason is that quantum mechanics or quantum field theories address to dynamical systems, i.e., particles or fields. Our point of view here breaks the link between quantization and dynamics: any (classical) physical system can be quantized. Only dynamical systems lead to dynamical quantum theories, which appear to result from the quantization of symplectic structures.     

Scanning electrochemical microscopy for the direct patterning of a gold surface with organic moities derived from iodonium salt

The scanning electrochemical microscope (SECM) is used in the direct mode to draw patterns of a thin passivating organic layer on a gold electrode surface and to image them. The patterning is ensured by the local electrografting of the organic moieties obtained by reduction of an aryliodonium salt, as evidenced by XPS and SECM line scans. The resolution of the writing process is controlled by the charge injected.     

Synthesis of Biologically Active 4-Oxo-4H-Chromene Derivatives Containing Sulfur-Nitrogen Heterocycles

The synthesis of 4-oxo-4H-chromenes containing sulfur-nitrogen heterocyclic rings as well as their biological activities are reviewed.     

A high efficiency 3D photovoltaic microwire with carbon nanotubes (CNT)‐quantum dot (QD) hybrid interface

An innovative hybrid QD sensitized photovoltaic carbon nanotubes microyarn has been developed using thermally‐stable and highly conductive carbon nanotubes yarns (CNYs). These CNYs are highly inter‐aligned, ultrastrong and flexible with excellent electrical conductivity, mechanical integrity and catalytic properties. The CNYs are coated with a QD‐incorporated TiO₂ microfilm and intertwined with a second set of CNYs as a counter electrode (CE). The maximum photon to current conversion efficiency (η_AM1.5) achieved with prolonged‐time stability was 5.93%. These cells are capable of efficiently harvesting incident photons regardless of direction and generating photocurrents with high efficiency and operational stability.

     

Nuclear deformation during breast cancer cell transmigration

Metastasis is the main cause of cancer mortality. During this process, cancer cells dislodge from a primary tumor, enter the circulation and form secondary tumors in distal organs. It is poorly understood how these cells manage to cross the tight syncytium of endothelial cells that lines the capillaries. Such capillary transmigration would require a drastic change in cell shape. We have therefore developed a microfluidic platform to study the transmigration of cancer cells. The device consists of an array of microchannels mimicking the confined spaces encountered. A thin glass coverslip bottom allows high resolution imaging of cell dynamics. We show that nuclear deformation is a critical and rate-limiting step for transmigration of highly metastatic human breast cancer cells. Transmigration was significantly reduced following the treatment with a protein methyltransferase inhibitor, suggesting that chromatin condensation might play an important role. Since transmigration is critical for cancer metastasis, this new platform may be useful for developing improved cancer therapies.     

Electron Ionization Mass Spectra of Organophosphorus Compounds Part I: The Mass Fragmentation Pathways of Cyclic α-Aminophosphonates Monoester Containing 1,2,4-Triazinone Moiety

Abstract

The electron impact induced fragmentation reactions of 3-(4-chlorophenyl)-3,4- dihydro-2-ethoxy-2-oxido-7-methyl-2H,6H-[1,2,4]triazino[4,3-e][1,4,5,2]thiadiazaphosphin in-6-one (1), 3,7-dimethyl-2-ethoxy-2-oxido-1,2,3,4-tetrahydro-6H-[1,2,4]triazino[4,3-b][1,2,4,5]triazaphosphinin-6-one (2), and 9-amino-3,7-dimethyl-4-ethoxy-4-oxido-2,3,4,9-tetrahydro-8H-[1,2,4]triazino[3,2-c][1,2,4,5]triazaphosphinin-8-one (3) are presented and compared. The 1,2,4-triazine rings have almost identical fragmentation routes. The 1,2,4-triazine rings are rather stable relative to the phosphorus rings. Therefore, fragmentation of the phosphorus rings is more favorable for the compounds than the stable 1,2,4-triazine rings.     

Three-dimensional numerical analysis of heat and mass transfer in heat pipes

A three-dimensional finite-element numerical model is presented for simulation of the steady-state performance characteristics of heat pipes. The mass, momentum and energy conservation equations are solved for the liquid and vapor flow in the entire heat pipe domain. The calculated outer wall temperature profiles are in good agreement with the experimental data. The estimations of the liquid and vapor pressure distributions and velocity profiles are also presented and discussed. It is shown that the vapor flow field remains nearly symmetrical about the heat pipe centerline, even under a non-uniform heat load. The analytical method used to predict the heat pipe capillary limit is found to be conservative.