Langmuir monolayers of Co nanoparticles and their patterning by microcontact printing

In this paper, we describe an easy and reliable method for the production of patterned monolayers of Co nanoparticles. A two-dimensional monolayer of Co nanoparticles is fabricated by spreading a nanoparticle solution over an air-water interface and then transferring it to a hydrophobic substrate by using the Langmuir-Blodgett (LB) method. Transmission electron microscopy (TEM) was used to show that, with increasing surface pressure, the Co nanoparticles become well-organized into a Langmuir monolayer with a hexagonal close-packed structure. By controlling the pH of the subphase, it was found that a monolayer of Co nanoparticles with long-range order could be obtained. Further, by transferring the Langmuir monolayer onto a poly(dimethoxysilane) (PDMS) mold, the selective micropatterning of the Co nanoparticles could be achieved on a patterned electronic circuit. The electronic transport properties of the Co nanoparticles showed the ohmic I-V curve.     

DFT study and Monte Carlo simulation on proton transfers of 2-amino-2-oxazoline, 2-amino-2-thiazoline, and 2-amino-2-imidazoline in the gas phase and in water

Density functional theory (DFT) and Monte Carlo (MC) simulation with free energy perturbation (FEP) techniques have been used to study the tautomeric proton transfer reaction of 2-amino-2-oxazoline, 2-amino-2-thiazoline, and 2-amino-2-imidazoline in the gas phase and in water. Two reaction pathways were considered: the direct and water-assisted transfers. The optimized structures and thermodynamic properties of stationary points for the title reaction system in the gas phase were calculated at the B3LYP/6-311+G(d, p) level of theory. The potential energy profiles along the minimum energy path in the gas phase and in water were obtained. The study of the solvent effect of water on the proton transfer of 2-amino-2-oxozoline, 2-amino-2-thiazoline, and 2-amino-2-imidazoline indicates that water as a solvent is favorable for the water-assisted process and slows down the rate of the direct transfer pathway.     

Synthesis and antitumor activity of DNA binding cationic porphyrin-platinum(II) complexes

A new series of DNA binding 5,10,15-tri(N-methyl-4-pyridiniumyl)porphyrin (TrisMPyP)-platinum(II) conjugates was synthesized, in which different spacer ligands were used for appropriate coordination to platinum(II) complexes. Compound 9b exhibited in vivo antitumor activity (T/C%, 294) superior to cisplatin (T/C%, 184) against the leukemia L1210 cell line.     

Charge transfer and electron backdonation in metallofullerenes encapsulating NSc3

Orbital interaction analysis is employed to understand the complex charge transfer mechanism operative in endohedral metallofullerenes of composition NSc₃@C_n (n = 68, 78). This phenomenon combines substantial electron transfer from the core to the cage with electron backdonation, involving the interaction between the occupied orbitals of the negatively charged cage and the unoccupied d orbitals of the positively charged core. This electron backdonation differs fundamentally from conventional orbital hybridization, which takes place primarily between the HOMO of the metal core and the LUMO of the fullerene cage. These findings imply the pronounced stability of NSc₃@C_n (n = 68, 78), especially for NSc₃ encapsulated in the non-IPR C₆₈ enclosure, as experimentally established.     

Selective Recognition of Calcium Ion through Liquid Membrane

The mole transport rate of alkaline earth metal ions through a bulk liquid membrane and a supported liquid membrane using a series of proton diionizable acyclic polyethers was measured. Among alkaline earth metal ions, the calcium ion was observed to be selectively transported in both single and competitive transport experiments. Potentiometric titration and solution calorimetric titration also gave calcium selectivity over other alkaline earth metal ions. Acyclic polyether bearing a diethylene glycol unit andn-tetradecyl lipophilic chain at the α position of carboxylic acid affords the best selectivity for the calcium ion in bulk and supported liquid membranes.     

Absorption, first-pass metabolism, and disposition of itraconazole in rats

This study examined the pharmacokinetic disposition, oral absorption and hepatic extraction of itraconazole and its active metabolite, hydroxyitraconazole, in rats. After i.v. injection, serum itraconazole concentrations decreased biexponentially, with an average terminal elimination half-life, volume of distribution and systemic clearance of 4.9 h, 6.0 l/kg and 14.2 ml/min/kg, respectively. When given orally, its absorption was low, with a mean absolute bioavailability of 16.6%. The metabolite to parent drug area under the curve (AUC) ratio was higher after oral administration compared with i.v. injection (mean ratio, 2.7 vs. 0.9). The hepatic drug extraction ratio determined after femoral and portal vein administration averaged 18.5%. When hydroxyitraconazole was injected i.v., the elimination half-life, volume of distribution and systemic clearance of itraconazole averaged 10.0 h, 2.4 l/kg and 3.4 ml/min/kg, respectively. The fraction of the systemically available itraconazole that was metabolized to hydroxyitraconazole was 21.0% and 76.0% after i.v. and oral administration, respectively. In summary, this study is the first reporting the hepatic extraction of itraconazole and the i.v. disposition characteristics of hydroxyitraconazole in rats. Itraconazole is a drug with a low hepatic extraction ratio and its systemic clearance appears to be largely accounted for by hepatic metabolism.     

Catalytic combustion of chlorobenzene over V2O5/TiO2 catalysts prepared by the precipitation-deposition method

Catalytic combustion of chlorobenzene over supported vanadium oxides has been investigated. TiO₂ was prepared by the sol-gel method from titanium isopropoxide. The supported vanadium oxide catalysts have been prepared by precipitation-deposition and impregnation method and characterized by XRD, FT-Raman and TPR. In the VO_x/TiO₂catalysts prepared using the impregnation method, when vanadium loading reaches 3 wt.%, the activity shows a maximum. However, in the VO_x/TiO₂catalysts prepared by precipitation-deposition, when vanadium loading reaches 7 wt.%, the activity shows a maximum. This result suggests that the precipitation-deposition can yield a higher metal loading on the support and a high dispersion compared to the impregnation method. This revised version was published online in August 2006 with corrections to the Cover Date.     

State-to-state reaction dynamics of CH3I photodissociation at 304 nm

The detailed reaction dynamics of CH(3)I photodissociation at 304 nm were studied by using high-resolution long time-delayed core-sampling photofragment translation spectroscopy. The vibrational state distributions of the photofragment, i.e., CH(3), are directly resolved due to the high kinetic resolution of this experiment for the first time. CH(3) radicals produced from I((3)Q(0+)), I((1)Q(1) <--( 3)Q(0+)), and I((3)Q(1)) channels are populated in different vibrational state distributions. The I((3)Q(0+)) and I((3)Q(1)) channels show only progressions in the nu2'(a2") umbrella bending mode, and the I((1)Q(1) <-- (3)Q(0+)) channel shows both progression in the nu2' umbrella bending mode and a small amount of excitation in the nu1'(a1') C-H stretching mode. The photodissociation processes from the vibrational hot band of CH(3)I (upsilon3 = 1, upsilon3 = 2) were also detected, primarily because of the absorption probability from the vibrational excited states, i.e., hot bands are relatively enhanced. Photofragments from the hot bands of CH(3)I show a cold vibrational distribution compared to that from the vibrational ground state of CH(3)I. The I* quantum yield and the curve crossing possibility were also studied for the ground vibrational state of CH(3)I. The potential energy at the curve crossing point was calculated to be 32 790 cm(-1) by using the one-dimensional Landau-Zener model.     

Ruthenium-catalyzed reductive cyclization of nitroarenes with trialkylamines leading to quinolines

Nitroarenes react with trialkylamines in the presence of a catalytic amount of a ruthenium catalyst together with tin(II) chloride dihydrate at 180 °C in an aqueous medium (toluene–H₂O) to afford the corresponding quinolines in moderate to good yields. The catalytic pathway seems to be proceeded via a sequence involving initial reduction of nitroarenes to anilines, alkyl group transfer from alkylamines to anilines to form an imine, dimerization of imine, and heterocyclization.     

Predicting the chemical reactivity of organic materials using a machine-learning approach

Stability and compatibility between chemical components are essential parameters that need to be considered in the selection of functional materials in configuring a system. In configuring devices such as batteries or solar cells, not only the functionality of individual constituting materials such as electrodes or electrolyte but also an appropriate combination of materials which do not undergo unwanted side reactions is critical in ensuring their reliable performance in long-term operation. While the universal theory that can predict the general chemical reactivity between materials is long awaited and has been the subject of studies with a rich history, traditional ways proposed to date have been mostly based on simple electronic properties of materials such as electronegativity, ionization energy, electron affinity and hardness/softness, and could be applied to only a small group of materials. Moreover, prediction has often been far from accurate and has failed to offer general implications; thus it was practically inadequate as a selection criterion from a large material database, i.e. data-driven material discovery. Herein, we propose a new model for predicting the general reactivity and chemical compatibility among a large number of organic materials, realized by a machine-learning approach. As a showcase, we demonstrate that our new implemented model successfully reproduces previous experimental results reported on side-reactions occurring in lithium–oxygen electrochemical cells. Furthermore, the mapping of chemical stability among more than 90 available electrolyte solvents and the representative redox mediators is realized by this approach, presenting an important guideline in the development of stable electrolyte/redox mediator couples for lithium–oxygen batteries.

Stability and compatibility between chemical components are essential parameters that need to be considered in the selection of functional materials in configuring a system.