Quantum-chemical calculations and IR spectra of the (F2)MF2 molecules (M = B, Al, Ga, In, Tl) in solid matrices: a new class of very high electron affinity neutral molecules

Electron-deficient group 13 metals react with F(2) to give the compounds MF(2) (M = B, Al, Ga, In, Tl), which combine with F(2) to form a new class of very high electron affinity neutral molecules, (F(2))MF(2), in solid argon and neon. These (F(2))MF(2) fluorine metal difluoride molecules were identified through matrix IR spectra containing new antisymmetric and symmetric M-F stretching modes. The assignments were confirmed through close comparisons with frequency calculations using DFT methods, which were calibrated against the MF(3) molecules observed in all of the spectra. Electron affinities calculated at the CCSD(T) level fall between 7.0 and 7.8 eV, which are in the range of the highest known electron affinities.     

Quantum chemical study of trivalent group 12 fluorides

In view of the recent experimental observation of the existence of tetravalent Hg (IV) in HgF 4, a quantum chemical study of various trivalent group 12 M(III) fluoride complexes has been carried out. The M-F bonds in neutral MF 3 are relatively weak, making these species unlikely targets. Some additional stability can be obtained by dimerizing HgF3 to Hg2F6, which has a doubly fluorine-bridged triplet ground state. Anionic [MF4]- and [MF5]2- species are found to be more stable toward F2 elimination and M-F bond breaking than neutral MF 3.     

Group 4 transition metal CH2=MF2, CHF=MF2, and HC/MF3 complexes formed by C-F activation and alpha-fluorine transfer

Group 4 transition metal methylidene difluoride complexes (CH2=MF2) are formed by the reaction of methylene fluoride with laser-ablated metal atoms and are isolated in an argon matrix. Isotopic substitution of the CH2F2 precursor and theoretical computations (B3LYP and CCSD) confirm product identifications and assignments. Our calculations indicate that the CH2=MF2 complexes have near C2v symmetry and are considerably more stable than other possible products (CH2(mu-F)MF and CHF=MHF). The primary reaction exothermicity provides more than enough energy to activate the initial bridge-bonded CH2(mu-F)MF products on the triplet potential energy surface to complete an alpha-F transfer to form the very stable CH2=MF2 products. Analogous experiments with CHF3 produce CHF=TiF2, which is not distorted at the C-H bond, whereas the heavier group 4 metals form lower-energy triplet HC/MF3 complexes, which contain weak degenerate C(p)-M(d) pi-bonding interactions. Comparisons are made with the CH2=MHF methylidene species, which showed considerable agostic distortions.     

The role of microfilaments in early meiotic maturation of mouse oocytes.

Mouse oocyte microfilaments (MF) were perturbed by depolymerization (cytochalasin B) or stabilization (jasplakinolide) and correlated meiotic defects examined by confocal microscopy. MF, microtubules, and mitochondria were vitally stained; centrosomes (gamma-tubulin), after fixation. MF depolymerization by cytochalasin in culture medium did not affect central migration of centrosomes, mitochondria, or nuclear breakdown (GVBD); some MF signal was localized around the germinal vesicle (GV). In maturation-blocking medium (containing IBMX), central movement was curtailed and cortical MF aggregations made the plasma membrane wavy. Occasional long MF suggested that not all MF were depolymerized. MF stabilization by jasplakinolide led to MF aggregations throughout the cytoplasm. GVBD occurred (unless IBMX was present) but no spindle formed. Over time, most oocytes constricted creating a dumbbell shape with MF concentrated under one-half of the oocyte cortex and on either side of the constriction. In IBMX medium, the MF-containing half of the dumbbell over time sequestered the GV, MF, mitochondria, and one to two large cortical centrosomes; the non-MF half appeared empty. Cumulus processes contacted the oocyte surface (detected by microtubule content) and mirrored MF distribution. Results demonstrated that MF play an essential role in meiosis, primarily through cortically mediated events, including centrosome localization, spindle (or GV) movement to the periphery, activation of (polar body) constriction, and establishment of oocyte polarity. The presence of a cortical "organizing pole" is hypothesized.     

M-F interatomic distances and effective volumes of second and third transition series MF6- and MF6(2-) anions

Synchrotron X-ray powder diffraction data (SPDD) for representative LiMF6 and Li2MF6 salts of the second and third transition series have provided unit-cell parameters and, from Rietveld analysis, M-F interatomic distances. M-F distances have also been obtained from X-ray single-crystal structural analyses of LiOsF6, Li2PtF6, and KRhF6. The LiMF6 all have the LiSbF6 structure type (space group R3). For M = Ta to Au the primitive unit cell volume decreases with increasing nuclear charge (Z), the volumes (sigma = 0.01 A3) being as follows: Ta, 111.26; Os, 102.42; Ir, 100.77; Pt, 99.62; and Au, 99.12 A3. A similar contraction, with increase in Z, occurs from Nb to Rh, the primitive cell volume (sigma = 0.01 A3) being: Nb, 110.92; Ru, 100.51; and Rh, 98.64 A3. For the TaF6- to AuF6- the M-F distances are not significantly different across the series, at approximately 1.87(1) A; also, Nb-F, Ru-F, and Rh-F = 1.86(1) A. In each series, the a and c values of the hexagonal-cell representation for the LiMF6 structure (separate layers of MF6- and Li+ stacked along c) change smoothly. As Z increases, a decreases and c increases. The variation in a, like the volume change, indicates that the size of MF6- is decreasing with Z. The variation in c suggests that the charge on the F-ligand is decreasing with Z. In the trirutile Li2MF6 series, M = Mo to Pd, the formula-unit volume decreases with Z(Mo, 100.92(6); Ru, 98.21(1); Rh, 97.43(1); Pd, 96.83(1) A3) and a shortening in M-F occurs (Mo-F = 1.936(4); Ru-F = 1.921(7); Rh-F = 1.910(7); Pd-F = 1.899(4) A). The less abundant data for MF6(2-) salts of the third transition series indicate similar trends. For both series, M-F distances of MF6(2-) are longer by 0.03-0.09 A than in MF6-.     

Production of methyl-oxonium ion and its complexes in the core-excited (HC(O)OCH3)n clusters: H/H+ transfer from the alpha carbonyl

Dissociation of free methyl-formate (MF), HC(O)OCH3, and its clusters (MF)n, (HC(O)OCH3)n, induced by core-level excitation was studied near the oxygen K edge by time-of-flight fragment-mass spectroscopy. Besides the protonated clusters, (MF)nH+ with n < or = 15, we identified the production for another series of (MF)mCH3OH2+ with m < or = 14 as well as methyl-oxonium ion, CH3OH2+, characteristic of hydrogen transfer reactions in the cationic clusters. Here; specifically labeled methyl-formate-d (MFD), DC(O)OCH3 was also used to examine the core-excited dissociation mechanisms. Deuterium-labeled experiments indicated that MFD+ with low internal energies, partially generated after the core excitation, produces CH3OD+ via a site-specific deuterium transfer from the alpha carbonyl in the molecular cation and that CH3OD2+ can be formed via the successive transfer of another deuterium from the neighbor molecule in the clusters. The deuteron (proton) transfer was also found to take place preferentially from the alpha carbonyl of the neighbor molecule for the production of deuteronated (MFD)nD+, (protonated (MF)nH+), clusters. The minimal energy requirement paths were examined for dimer (MF)2+ cation to support the present dissociation mechanisms of core-excited (MF)n clusters using ab initio molecular-orbital calculations.     

Fluorimetric investigation of supramolecular system by modified β-cyclodextrin and its analytical application

The supramolecular interaction of MAH-β-cyclodextrin (MAH-β-CD, a modified β-cyclodextrin carrying seven vinyl carboxylic acid groups) and meferamic acid (MF) has been studied by spectrofluorimetry. The results showed that MAH-β-CD reacted with MF to form a host-guest complex (MAH-β-CD-MF) with stoichiometry (1:1) and the inclusion constant (K=7.15×10(2) L/mol) was ascertained by the typical double reciprocal plots. From the phase-solubility diagram, an increase in the water solubility of the drug was observed and the apparent stability constant (K(1:1)) was calculated to be 8.62×10(2) L/mol. Furthermore, the thermodynamic parameters (ΔG°, ΔH° and ΔS°) of MAH-β-CD-MF were obtained and the inclusion mechanism was also preliminarily discussed. In order to further confirm the experimental results, investigation on the molecular modeling was performed. On the basis of the significant enhancement of the fluorescence intensity of MF, a spectrofluorimetric method for MF determination in bulk aqueous solution in the presence of MAH-β-CD was developed. The linear range was 2.00×10(-8)-9.00×10(-5) mol/L and the detection limit was 3.36×10(-9) mol/L. The proposed method was successfully applied to determine MF in tablets, serum and urine with the satisfactory result.     

Developing imprinted polymer nanoparticles for the selective separation of antidiabetic drugs

In this study, new molecularly imprinted polymer (MIP) nanoparticles are designed for selective recognition of different drugs used for the treatment of type 2 diabetes mellitus, i.e. sitagliptin (SG) and metformin (MF). The SG‐ and MF‐imprinted polymer nanoparticles are synthesized by free‐radical initiated polymerization of the functional monomers: methacrylic acid and methyl methacrylate; and the crosslinker: ethylene glycol dimethacrylate. The surface morphology of resultant MIP nanoparticles is studied by atomic force microscopy. Fourier transform infrared spectra of MIP nanoparticles suggest the presence of reversible, non‐covalent interactions between the template and the polymer. The effect of pH on the rebinding of antidiabetic drugs with SG‐ and MF‐imprinted polymers is investigated to determine the optimal experimental conditions. The molecular recognition characteristics of SG‐ and MF‐imprinted polymers for the respective drug targets are determined at low concentrations of SG (50–150 ppm) and MF (5–100 ppm). In both cases, the MIP nanoparticles exhibit higher binding response compared to non‐imprinted polymers. Furthermore, the MIPs demonstrate high selectivity with four fold higher responses toward imprinted drugs targets, respectively. Recycled MIP nanoparticles retain 90% of their drug‐binding efficiency, which makes them suitable for successive analyses with significantly preserved recognition features.     

Preparation of Organotrifluoroborate Salts: Precipitation-Driven Equilibrium under Non-Etching Conditions

Simple, rapid, and scaleable: In contrast to current procedures using corrosive HF/MF or MHF(2) reagents (M=e.g. K), a wide range of trifluoroborates can be rapidly, simply, and safely prepared from MF (M=K, Cs), RCO(2) H, and a boronic acid/ester in regular glassware (see figure; left versus right). The use of L-(+)-tartaric acid as an alkali-metal sponge is key and allows isolation of RBF(3) M by a simple stir/filter/evaporate sequence.     

Spectroscopic investigation of interaction of 6-methoxyflavanone and its β-cyclodextrin inclusion complex with calf thymus DNA

The interaction of 6-methoxyflavanone (6MF, 6-methoxy-2-phenyl-4H-1-benzopyran-4-one) with calf thymus DNA (ctDNA) was investigated by absorption spectroscopy, fluorescence spectroscopy, and cyclic voltammetry in the presence and absence of ??-cyclodextrin (??-CD) acting as capping agent. Molecular modelling was used to optimise the study of 6MF-??-CD and 6MF-DNA interactions. Enhancement in the fluorescence intensity of 6MF was observed due to the formation of 1 : 1 complex with ??-CD. In the presence and absence of DNA, 6MF showed different characteristics such as hyperchromic effect, red shift of absorption spectra and fluorescence quenching of 6MF due to binding between 6MF and ctDNA. The nature of the binding group was found to be different for the 6MF-ctDNA and 6MF-ctDNA-??-CD systems. An increase in fluorescence intensity was observed for the 6MF-ctDNA system while varying the concentration of ??-CD due to encapsulation of a part of 6MF in cyclodextrin. The results are compatible with the possibility of the interaction of dihydrobenzopyran-4-one moiety of 6MF with ctDNA as well as with ??-CD. Cyclic voltammetric studies confirmed the binding interaction between 6MF and ctDNA in the absence and presence of ??-CD and molecular modelling explains the site of the interaction of 6MF with cyclodextrin and ctDNA.     

Tuning the Halogen/Hydrogen Bond Competition: A Spectroscopic and Conceptual DFT Study of Some Model Complexes Involving CHF2I

Insight into the key factors driving the competition of halogen and hydrogen bonds is obtained by studying the affinity of the Lewis bases trimethylamine (TMA), dimethyl ether (DME), and methyl fluoride (MF) towards difluoroiodomethane (CHF₂I). Analysis of the infrared and Raman spectra of solutions in liquid krypton containing mixtures of TMA and CHF₂I and of DME and CHF₂I reveals that for these Lewis bases hydrogen and halogen‐bonded complexes appear simultaneously. In contrast, only a hydrogen‐bonded complex is formed for the mixtures of CHF₂I and MF. The complexation enthalpies for the C?H ??? Y hydrogen‐bonded complexes with TMA, DME, and MF are determined to be ?14.7(2), ?10.5(5) and ?5.1(6) kJ mol^?1, respectively. The values for the C?I ??? Y halogen‐bonded isomers are ?19.0(3) kJ mol^?1 for TMA and ?9.9(8) kJ mol^?1 for DME. Generalization of the observed trends suggests that, at least for the bases studied here, softer Lewis bases such as TMA favor halogen bonding, whereas harder bases such as MF show a substantial preference for hydrogen bonding.     

External magnetic field-induced mesoscopic organization of Fe3O4 pyramids and carbon sheets

The current investigation is centered on the thermal decomposition of iron(II) acetyl acetonate, Fe(C5H7O2)2, in a closed cell at 700 degrees C, which is conducted under a magnetic field (MF) of 10 T. The product is compared with a similar reaction that was carried out without a MF. This article shows how the reaction without a MF produces spherical Fe3O4 particles coated with carbon. The same reaction in the presence of a 10 T MF causes the rejection of the carbon from the surface of pyramid-shaped Fe3O4 particles, increases the Fe3O4 particle diameter, forms separate carbon particles, and leads to the formation of an anisotropic (long cigarlike) orientation of Fe3O4 pyramids and C sheets. The macroscopic orientation of Fe3O4 pyramids+C sheets is stable even after the removal of an external MF. The suggested process can be used to fabricate large arrays of uniform wires comprised of some magnetic nanoparticles, and to improve the magnetic properties of nanoscale magnetic materials. The probable mechanism is developed for the growth and assembly behavior of magnetic Fe3O4 pyramids+C sheets under an external MF. The effect of an applied MF to synthesize morphologically different, but structurally the same, products with mesoscopic organization is the key theme of the present paper.     

The Effect of Magnetic Field on Corrosion Inhibitor of Copper in 0.5 M HCl Solution

Corrosion of metals within magnetic field (MF) had been actively studied for better understanding of the corrosion mechanism when the magnetic sources are presented. However, findings regarding the effect of MF on metals are inconclusive, and there is a lack of studies of MF interaction with various corrosion control techniques, such as corrosion inhibitor. In this paper, the effect of MF on the corrosion of copper in 0.5 M hydrochloric acid (HCl) solution, with or without corrosion inhibitor were studied. Benzotriazole (BTA), a common copper inhibitor, was chosen as the inhibitor for this study. To determine the effect of MF, a MF of 13 mT, generated using a pair of permanent neodymium magnet, was applied during weight loss and electrochemical tests. The results showed that corrosion inhibition efficiency of BTA decreased when it is under an applied MF. A decrease from 47% to 60% in inhibition efficiency had been observed for all samples in an applied MF. By using Tafel extrapolation technique on the polarization curves, it revealed that MF had increased the corrosion current of copper in HCl, causing a decrease in the inhibition efficiency.     

Increased electroactive species concentration in anodic biofilm of <Emphasis Type="Italic">Geobacter</Emphasis>-inoculated microbial fuel cells under static magnetic field

The effects of a static magnetic field (MF) on the electricity production and anodic bioelectrochemical activity in Geobacter sulfurreducens-inoculated microbial fuel cells (MFCs) were investigated. The results showed that application of a MF of 100, 200, and 400 mT improved the electricity generation considerably, with an increase in the maximum power density by 27–100 %. The maximum power density of 0.030 mW cm^?2 was obtained at field strength of 100 mT, representing the best MFC performance with the lowest internal resistance of 453.6 Ω. Electrochemical impedance spectroscopy results showed that the MFC activation resistance was decreased under a MF. The impact of a MF on the bioelectrochemical activity of Geobacter-based biofilm was analyzed by cyclic voltammetry (CV). The redox peak currents of the voltammetric behavior increased in the presence of a MF, indicating enhanced bioelectrochemical catalyzed activity. In addition, evidence from CV revealed higher density of electroactive species in the anodic biofilm with MF than without, leading to a more efficient direct electron transfer process by G. sulfurreducens.     

Ni(OH)2修饰的三聚氰胺泡沫用于可压缩超级电容器电极

通过化学镀和电化学镀的方法制备了一种Ni(OH)₂电化学活性材料修饰三聚氰胺泡沫(MF)可压缩骨架的超级电容器电极材料MF/Ni(OH)₂。MF/Ni(OH)₂可压缩电极材料表现出最佳的电容性能,例如循环稳定性(即使在40 mA/cm^-3的电流密度下经过2000次充放电循环后,可压缩电极仍能保持90.63%的初始电容)和可压缩稳定性(即使在压缩率为50%时,仍具有97.88%的电容保持率)。层状可压缩超级电容器由MF/Ni(OH)₂弹性材料作为阳极,镍/碳(Ni/C)为阴极以及实验室中常用的滤纸作隔膜材料组成。这种超级电容器装置在不同的压缩下表现出良好的电化学性能和优异的压缩稳定性。最后,使用可压缩的超级电容器来点亮LED灯,以展示其在柔性电子设备中的应用。这些优化的电化学和机械性能表明MF/Ni(OH)₂可作为可压缩超级电容器的应用中的候选电极。     

Effects of extremely low frequency magnetic field on the antioxidant defense system in mouse brain: a chemiluminescence study

Among the putative mechanisms, by which extremely low frequency (ELF) magnetic field (MF) may affect biological systems is that of increasing free radical life span in organisms. To test this hypothesis, we investigated whether ELF (60 Hz) MF can modulate antioxidant system in mouse brain by detecting chemiluminescence and measuring superoxide dismutase (SOD) activity in homogenates of the organ. Compared to sham exposed control group, lucigenin-initiated chemiluminescence in exposed group was not significantly increased. However, lucigenin-amplified t-butyl hydroperoxide (TBHP)-initiated brain homogenates chemiluminescence, was significantly increased in mouse exposed to 60 Hz, MF, 12 G for 3 h compared to sham exposed group. We also measured SOD activity, that plays a critical role of the antioxidant defensive system in brain. In the group exposed to 60 Hz, MF, 12 G for 3 h, brain SOD activity was significantly increased. These results suggest that 60 Hz, MF could deteriorate antioxidant defensive system by reactive oxygen species (ROS), other than superoxide radicals. Further studies are needed to identify the kind of ROS generated by the exposure to 60 Hz, MF and elucidate how MF can affect biological system in connection with oxidative stress.     

Determination of Heavy Metals in Waters by Atomic Absorption Spectrophotometry Coupled with Membrane Filtration/Concentration

Ultra trace amounts of heavy metals, such as Cu, Pb, were determined by graphite furnace-atomic absorption spectrophotometry (GF-AAS) after miniature membrane filer (MF) concentration/dissolution. Heavy metals were concentrated as pyrrolidine-dithiocarbamate (APDC) chelates on a miniature MF of which diameter was 5 mm, effec-tive filtering diameter was 2 mm and pore size was 2 μm.     

Synthesis and Photoluminescence Properties of Uniform Y2O3:Eu3+ Hollow Spheres with Tunable Shell Thickness

Y2O3:Eu3+ hollow spheres were successfully prepared with melamine formaldehyde(MF) spheres as template. The MF spheres played a significant role in directing the formation of the hollow shells which are composed of numerous primary nanoparticles. Furthermore, the shell thickness of these hollow spheres could be readily tailored by adjusting the dosage of MF template. Based on the photoluminescence(PL) investigation, the red emission intensities(613 nm) of these Y2O3:Eu3+ hollow spheres are greatly influenced by their shell thickness and it was found that hollow spheres with thin shell thickness and intact hollow structures permit a better PL performance.     

Temperature-controlled 'breathing' of carbon dioxide bubbles

We report a microfluidic (MF) approach to studies of temperature mediated carbon dioxide (CO(2)) transfer between the gas and the liquid phases. Micrometre-diameter CO(2) bubbles with a narrow size distribution were generated in an aqueous or organic liquid and subsequently were subjected to temperature changes in the downstream channel. In response to the cooling-heating-cooling cycle the bubbles underwent corresponding contraction-expansion-contraction transitions, which we term 'bubble breathing'. We examined temperature-controlled dissolution of CO(2) in four exemplary liquid systems: deionized water, a 0.7 M aqueous solution of NaCl, ocean water extracted from Bermuda coastal waters, and dimethyl ether of poly(ethylene glycol), a solvent used in industry for absorption of CO(2). The MF approach can be extended to studies of other gases with a distinct, temperature-dependent solubility in liquids.