Effects of pore structure and molecular size on diffusion in chromatographic adsorbents

Two computational approaches, namely Brownian dynamics and network modeling, are presented for predicting effective diffusion coefficients of probes of different sizes in three chromatographic adsorbents, the structural properties of which were determined previously using electron tomography. Three-dimensional reconstructions of the adsorbents provide detailed, explicit characteristics of the pore network, so that no assumptions have to be made regarding pore properties such as connectivity, pore radius and pore length. The diffusivity predictions obtained from the two modeling approaches were compared to experimental diffusivities measured for dextran and protein probes. Both computational methods captured the same qualitative results, while their predictive capabilities varied among adsorbents.     

Chemistry surrounding monomeric copper(I) methyl, phenyl, anilido, ethoxide, and phenoxide complexes supported by N-heterocyclic carbene ligands: reactivity consistent with both early and late transition metal systems

Monomeric copper(I) alkyl complexes that possess the N-heterocyclic carbene (NHC) ligands IPr, SIPr, and IMes [IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene, SIPr = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene, IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene] react with amines or alcohols to release alkane and form the corresponding monomeric copper(I) amido, alkoxide, or aryloxide complexes. Thermal decomposition reactions of (NHC)Cu(I) methyl complexes at temperatures between 100 and 130 degrees C produce methane, ethane, and ethylene. The reactions of (NHC)Cu(NHPh) complexes with bromoethane reveal increasing nucleophilic reactivity at the anilido ligand in the order (SIPr)Cu(NHPh) < (IPr)Cu(NHPh) < (IMes)Cu(NHPh) < (dtbpe)Cu(NHPh) [dtbpe = 1,2-bis(di-tert-butylphosphino)ethane]. DFT calculations suggest that the HOMO for the series of Cu anilido complexes is localized primarily on the amido nitrogen with some ppi(anilido)-dpi(Cu) pi-character. [(IPr)Cu(mu-H)]2 and (IPr)Cu(Ph) react with aniline to quantitatively produce (IPr)Cu(NHPh)/dihydrogen and (IPr)Cu(NHPh)/benzene, respectively. Analysis of the DFT calculations reveals that the conversion of [(IPr)Cu(mu-H)]2 and aniline to (IPr)Cu(NHPh) and dihydrogen is favorable with DeltaH approximately -7 kcal/mol and DeltaG approximately -9 kcal/mol.     

Current efficiency and titration efficiency in coulometric titrations with electrogenerated ceric ion determination of iodide

The current efficiency for the electrogeneration of cerie ion at a platinum anode falls considerably below 100% at both very small and at large current densities in both sulfuric and perchloric acid media. The maximal current efficiency is about 99.8%.Iodide ion can be titrated to iodine with an error of only about +0.3%, even under conditions where the cerie ion generation efficiency is only 98%. High titration efficiency, in spite of poor efficiency for ceric ion generation, is obtained because iodine is oxidized to iodate ion at a potential slightly in advance of the potential at which cerous ion is oxidized. Since the electrogenerated iodate ion oxidizes iodide ion only a minor fraction of the total quantity of electricity results from ceric ion generation, so the effect of its inefficient generation is greatly minimized. Satisfactory titrations of iodide ion to iodine can be performed without any cerous salt present, provided the generating current density is smaller than the limiting current density for oxidation of iodine to iodate ion.     

Synthesis and structural investigation of tungsten imido amidinate and guanidinate complexes

The tungsten imido guanidinate and amidinate complexes W(NR)Cl(3)[R'NC(NMe(2))NR'] and W(NR)Cl(3)[R'NC(Me)NR'] (R = Ph, (i)Pr, Cy; R' = (i)Pr, (t)Bu, TMS) were synthesized by reacting the corresponding imido complex W(NR)Cl(4)(OEt(2)) with the appropriate lithium amidinate or guanidinate. Crystallographic structure determination of W(N(i)Pr)Cl(3)[(i)PrNC(NMe(2))N(i)Pr] and W(N(i)()Pr)Cl(3)[(i)PrNC(Me)N(i)Pr] allows comparison of structural features between the guanidinate and amidinate ligand in the presence of an identical ancillary ligand set.     

Surfactant-Mediated and Morphology-Controlled Nanostructured LiFePO4/Carbon Composite as a Promising Cathode Material for Li-Ion Batteries

The synthesis of morphology-controlled carbon-coated nanostructured LiFePO₄ (LFP/Carbon) cathode materials by surfactant-assisted hydrothermal method using block copolymers is reported. The resulting nanocrystalline high surface area materials were coated with carbon and designated as LFP/C123 and LFP/C311. All the materials were systematically characterized by various analytical, spectroscopic and imaging techniques. The reverse structure of the surfactant Pluronic® 31R1 (PPO-PEO-PPO) in comparison to Pluronic® P123 (PEO-PPO-PEO) played a vital role in controlling the particle size and morphology which in turn ameliorate the electrochemical performance in terms of reversible specific capacity (163 mAh g⁻¹ and 140 mAh g⁻¹ at 0.1 C for LFP/C311 and LFP/C123, respectively). In addition, LFP/C311 demonstrated excellent electrochemical performance including lower charge transfer resistance (146.3 Ω) and excellent cycling stability (95 % capacity retention at 1 C after 100 cycles) and high rate capability (163.2 mAh g⁻¹ at 0.1 C; 147.1 mAh g⁻¹ at 1 C). The better performance of the former is attributed to LFP nanoparticles (<50 nm) with a specific spindle-shaped morphology. Further, we have also evaluated the electrode performance with the use of both PVDF and CMC binders employed for the electrode fabrication.     

Non-collapsing in fully non-linear curvature flows

We consider compact, embedded hypersurfaces of Euclidean spaces evolving by fully non-linear flows in which the normal speed of motion is a homogeneous degree one, concave or convex function of the principal curvatures, and prove a non-collapsing estimate: Precisely, the function which gives the curvature of the largest interior ball touching the hypersurface at each point is a subsolution of the linearized flow equation if the speed is concave. If the speed is convex then there is an analogous statement for exterior balls. In particular, if the hypersurface moves with positive speed and the speed is concave in the principal curvatures, the curvature of the largest touching interior ball is bounded by a multiple of the speed as long as the solution exists. The proof uses a maximum principle applied to a function of two points on the evolving hypersurface. We illustrate the techniques required for dealing with such functions in a proof of the known containment principle for flows of hypersurfaces.     

Quantifying the implications of nonlinear cochlear tuning for auditory-filter estimates

The relation between auditory filters estimated from psychophysical methods and peripheral tuning was evaluated using a computational auditory-nerve (AN) model that included many of the response properties associated with nonlinear cochlear tuning. The phenomenological AN model included the effects of dynamic level-dependent tuning, compression, and suppression on the responses of high-, medium-, and low-spontaneous-rate AN fibers. Signal detection theory was used to evaluate psychophysical performance limits imposed by the random nature of AN discharges and by random-noise stimuli. The power-spectrum model of masking was used to estimate psychophysical auditory filters from predicted AN-model detection thresholds for a tone signal in fixed-level notched-noise maskers. Results demonstrate that the role of suppression in broadening peripheral tuning in response to the noise masker has implications for the interpretation of psychophysical auditory-filter estimates. Specifically, the estimated psychophysical auditory-filter equivalent-rectangular bandwidths (ERBs) that were derived from the nonlinear AN model with suppression always overestimated the ERBs of the low-level peripheral model filters. Further, this effect was larger for an 8-kHz signal than for a 2-kHz signal, suggesting a potential characteristic-frequency (CF) dependent bias in psychophysical estimates of auditory filters due to the increase in strength of cochlear nonlinearity with increases in CF.     

Diode-pumped passively mode-locked Nd:KGd(WO(4))(2) laser with 1-W average output power

Continuous-wave passive mode locking of a diode-pumped Nd:KGd(WO(4))(2) laser is demonstrated. The use of a saturable Bragg reflector as the mode-locking element permits the generation of 6.3-ps pulses, assuming a sech(2) pulse shape. An output power of 1 W was obtained, which corresponds to a slope efficiency of 34.5%.     

Effect of heat treatment on UV-laser-induced positive ion desorption in CaHPO4·2H2O

We have investigated KrF excimer-laser-induced positive ion desorption from single-crystal brushite (CaHPO₄·2H₂O), a model biomineral containing water, and we show the effect of heat treatment on ion desorption. Time-of-flight peaks of Ca⁺ desorption from the heated-cleaved surface are similar to those from as-cleaved ones, but the ion intensity is 2 to 4 orders of magnitude larger. In addition to Ca⁺, desorption of CaO⁺, PO⁺, and P⁺ from the heated surface is also strongly enhanced. The heated-cleaved surface shows rough, platelet-like fine structures due to recrystallization. Surface defects created during recrystallization strongly couple with the 5 eV photons and dramatically enhance ion desorption.