Search

The principles and parameters to consider when choosing an NMR probe for analysis of a volume- or mass-limited sample are identified and discussed. In particular, a capillary-based microflow probe is described which has a mass sensitivity comparable to cryoprobes (observe volume ~40 [micro]L), but with several distinct advantages. The microflow probe has a flowcell volume of 5 [micro]L and an observe volume of 1.5 [micro]L and is equipped with proton and carbon observe channels, deuterium lock, and z-gradient capability. The entire flow path is fused silica; inlet and outlet capillary inner diameters are 50 [micro]m to minimize sample dispersion, making it well-suited to volume-limited samples. An injected sample of 1 nmol of sucrose (0.34 [micro]g in 3 [micro]L, 0.33 mM; MW = 342 g/mol) yields a 1D proton spectrum in 10 min on a spectrometer of 500 MHz or higher. In another example, 15 [micro]g of sucrose (in 3 [micro]L; 15 mM, 45 nmol) is injected and parked in the probe to yield a heteronuclear multiple-quantum coherence (HMQC) spectrum in less than 15 h. The natural product muristerone A (75 [micro]g in 3 [micro]L, 50 mM, 150 nmol; MW = 497 g/mol) was delivered to the flow cell, and a gradient correlation spectroscopy spectrum was acquired in 7 min, a gradient HMQC in 4 h, and a gradient heteronuclear multiple-bond correlation in 11 h. Four basic modes of sample injection into the probe vary in degree of user intervention, speed, solvent consumption, and sample delivery efficiency. Manual, manual-assisted (employing a micropump), automated (using an autosampler), and capillary HPLC modes of operation are described.

Several studies are conducted to explain the chemistry, X-ray diffraction structure and the properties of iridium corroles. The iridium corroles are shown to exhibit extremely high reactivity and hence are used for the synthesis of several other compounds.

The rapid and reversible reaction taking place between [Ni[([P.sup.cy][N.sub.2.sup.Bz]).sub.2]][(BF4).sub.2] complex and carbon monoxide is discussed. The second coordination sphere of the molecule is found to be essential for controlling the reactivity.

Half-wave potentials of mononuclear and dinucelar nickel(II) diphosphine/dithiolate complexes was investigated. It was found that the half-wave potentials of the Ni(II/I) couples for mononuclear complexes Ni(diphsophine)(dithiolate) shift to more positive values as the chelate ring size of the dithiolate is increased, however dinuclear Ni(II) complexes with terminal diphosphine do not show a systematic change in the half-wave potentials as the chelate ring size is varied.

The design, synthesis, and characterization of highly efficient electrocatalysts for both hydrogen evolution and hydrogen oxidation are described. The results have shown that a precisely positioned base results not only in fast proton transport between the solution and the active metal site but also in a significant decrease in the activation barrier for hydrogen-hydrogen bond cleavage or formation.

Electroporation is used to create pores within the membrane of living cells in order to deliver a substance, for example, a gene, into the cytoplasm. To achieve the high electric field gradients required to porate the membrane, current electroporation devices deliver voltage pulses in the kV range to the cell medium. We describe a new device based on gold-microtube membranes that can accomplish electroporation with voltage pulses that are orders of magnitude smaller, ≤5 V. This is possible because the voltage pulses are applied to the gold microtubes resulting in large electric field gradients down the length of the tubes. We used COMSOL simulations to calculate the electric field gradients, and these theoretical results were compared with known experimental values required to electroporate Escherichia coli. We developed two fluorescence-based methods to demonstrate successful electroporation of E. coli. The percentages of electroporated bacteria were found to be more than an order of magnitude higher than obtained with a commercial electroporator, although the voltage employed was 500 times lower. Furthermore, this microtube membrane device is flow through and is therefore capable of continuous, as opposed to batch-wise, electroporation and cell analysis. Cell throughput of >30 million cells per min, higher than any previously reported device, were obtained. [ABSTRACT FROM AUTHOR]

Thermodynamic studies of a series of [H2Rh(PP)2]+ and [HRh(PP)2(CH3CN)]2+ complexes have been carried out in acetonitrite. Seven different diphosphine (PP) ligands were selected to allow variation of the electronic properties of the ligand substituents, the cone angles, and the natural bite angles (NBAs). Oxidative addition of H2 to [Rh(PP)2]+ complexes is favored by diphosphine ligands with large NBAs, small cone angles, and electron donaring substituents, with the NBA being the dominant factor. Large pKa values for (HRh(PP)2(CH3CN)]2+ complexes are favored by small ligand cone angles, small NBAs, and electron donating substituents with the cone angles playing a major role. The hydride donor abilities of [H2Rh(PP)2]+ complexes increase as the NBAs decrease, the cone angles decrease, and the electron donor abilities of the substituents increase. These results indicate that if solvent coordination is involved in hydride transfer or proton transfer reactions, the observed trends can be understood in terms of a combination of two different steric effects, NBAs and cone angles, and electron-donor effects of the ligand substituents. [ABSTRACT FROM AUTHOR]

The complex [Ni(PCy2NBz2)2)(BF4)2, 1, reacts rapidly and reversibly with carbon monoxide (1 atm) at 25 °Cto form [Ni(CO)(PCy2NBz2)2](BF4)2, 2, which has been characterized by spectroscopic data and by an X-ray diffraction study. In contrast, analogous Ni(II) carbonyl adducts were not observed in studies of several other related nickel(II) diphosphine complexes. The unusual reactivity of 1 is attributed to a complex interplay of electronic and structural factors, with an important contribution being the ability of two positioned amines in the second coordination sphere to act in concert to stabilize the CO adduct. The proposed interaction is supported by X-ray diffraction data for 2 which shows that all of the chelate rings of the cyclic ligands are in boat conformations, placing two pendant amines close (3.30 and 3.38 A) to the carbonyl carbon. Similar close C-N interactions are observed in the crystal structure of the more sterically demanding isocyanide adduct, [Ni(CNCy)(PCy2NBz2)2]2(BF4)2, 4. The data suggest a weak electrostatic interaction between the lone pairs of the nitrogen atoms and the positively charged carbon atom of the carbonyl or isocyanide ligand, and illustrate a novel (non-hydrogen bonding) second coordination sphere effect in controlling reactivity. [ABSTRACT FROM AUTHOR]

Highly efficient electrocatalysts for both hydrogen evolution and hydrogen oxidation have been designed, synthesized, and characterized. The catalysts in their resting states are air-stable, mononuclear nickel(II) complexes containing cyclic diphosphine ligands with nitrogen bases incorporated into the ligand backbone. X-ray diffraction studies have established that the cation of [Ni(PPh2NPh2)2(CH3CN)](BF4)2, 6a, (where PPh2NPh2 is 1 ,3,5,7-tetraphenyl-1 ,5-diaza-3,7-diphosphacyclooctane) is a trigonal bipyramid with bonds to four phosphorus atoms of the two bidentate diphosphine ligands and the nitrogen atom of an acetonitrile molecule. Two of the six-membered rings formed by the diphosphine ligands and Ni have boat conformations with an average Ni- - -N distance to the two pendant bases of 3.4 Å. The cation of [Ni(PCy2NBz)2](BF4)2, 6b, (where Cy = cyclohexyl and Bz = benzyl) is a distorted square planar complex. For 6b, all four six- membered rings formed upon coordination of the diphosphine ligands to the metal are in the boat form. In this case, the average Ni- - -N distance to the pendant base is 3.3 Å. Complex 6a is an electrocatalyst for hydrogen production in acidic acetonitrile solutions, and compound 6b is an electrocatalyst for hydrogen oxidation in basic acetonitrile solutions. It is demonstrated that the high catalytic rates observed with these complexes are a result of the positioning of the nitrogen base so that it plays an important role in the formation and cleavage of the H-H bond. [ABSTRACT FROM AUTHOR]

Forward osmosis (FO) has emerged as a new technology for desalination and exhibits potentials for applications where reverse osmosis is incapable or uneconomical for treating streams with high salinity or fouling propensity. However, most of current draw agents in FO are salts and difficult to be recycled cost- and energy-effectively. In this work, we demonstrate a new and facile approach to efficiently recover water from the FO process with enhanced water purity by using a binary ion liquid/hydrogel system. The hybrid ion liquid/hydrogel draw solution system demonstrated in this work synergistically leverages the thermoresponsive properties of both the ionic liquid (IL) and hydrogel to improve the overall FO performance. Our findings corroborate that the hydrogel mitigates the water flux decline of the IL as the draw agent and provide a ready route to contiguously and effectively regenerate water from the FO process. Such a route allows for an efficient recovery of water from the draw solute/water mixture with enhanced water purity, compared with conventional thermal treating of lower critical solution temperature IL draw solute/water. Furthermore, hydrogels can be used in a continuous and readily recyclable process to recover water without heating the entire draw solute/water mixture. Our design principles open the door to use low-grade/waste heat or solar energy to regenerate draw agents and potentially reduce energy in the FO process considerably., Competing Interests: The authors declare no competing financial interest.

A density functional theory (DFT) analysis has been performed to explore the impact of steric interactions on the function of switchable polarity solvents (SPS) and their implications on a quantitative structure-activity relationship (QSAR) model previously proposed for SPS. An X-ray crystal structure of the N,N-dimethylcyclohexylammonium bicarbonate (Hdmcha) salt has been solved as an asymmetric unit containing two cation/anion pairs, with a hydrogen bonding interaction observed between the bicarbonate anions, as well as between the cation and anion in each pair. DFT calculations provide an optimized structure of Hdmcha that closely resembles experimental data and reproduces the cation/anion interaction with the inclusion of a dielectric field. Relaxed potential energy surface (PES) scans have been performed on Hdmcha-based computational model compounds, differing in the size of functional group bonded to the nitrogen center, to assess the steric impact of the group on the relative energy and structural properties of the compound. Results suggest that both the length and amount of branching associated with the substituent impact the energetic limitations on rotation of the group along the N-R bond and NC-R bond, and disrupt the energy minimized position of the hydrogen bonded bicarbonate group. The largest interaction resulted from functional groups that featured five bonds between the ammonium proton and a proton on a functional group with the freedom of rotation to form a pseudo six membered ring which included both protons.