AN EQUILIBRIUM BETWEEN SPIROPHOSPHORANIC AND TETRACOORDINATED PHOSPHORUS COMPOUNDS HAVING THE PHOSPHORUS-BORON BOND

Abstract

A new adduct was isolated from the reaction of borane-dimethyl-sulfide complex and conjugate bases of spirophosphorane prepared from benzilic acid. In solution, it exists as equilibrium between a spirophosphorane and a tetracoordinated phosphorus compound bearing a phosphorus-boron bond.     

Rapid characterization of high/low producer CHO cells using matrix‐assisted laser desorption/ionization time‐of‐flight

An intact‐cell mass spectrometry (ICM) method using matrix‐assisted laser desorption/ionization time‐of‐flight (MALDI‐TOF) was evaluated for the screening of stable recombinant Chinese hamster ovary (CHO) cell lines, an important mammalian cell line in bioprocessing. With rapid and simple cell pretreatments, viabilities of cells could be rapidly distinguished on the different fingerprints of mass spectra. Detectable m/z values on cell surfaces and their relative intensities were processed by two biostatistical methods, principle components analysis (PCA) and partial least squares (PLS), with promising results. Discrimination among cell lines with different expressed recombinant proteins or different productivities could be achieved. The ICM method has the advantage of providing multiple parameters simultaneously and possesses the potential to become a powerful method for routine monitoring of bioprocesses. Copyright © 2010 John Wiley & Sons, Ltd.     

Dye molecular structure device open-circuit voltage correlation in Ru(II) sensitizers with heteroleptic tridentate chelates for dye-sensitized solar cells

Dicarboxyterpyridine chelates with π-conjugated pendant groups attached at the 5- or 6-position of the terminal pyridyl unit were synthesized. Together with 2,6-bis(5-pyrazolyl)pyridine, these were used successfully to prepare a series of novel heteroleptic, bis-tridentate Ru(II) sensitizers, denoted as TF-11-14. These dyes show excellent performance in dye-sensitized solar cells (DSCs) under AM1.5G simulated sunlight at a light intensity of 100 mW cm(-2) in comparison with a reference device containing [Ru(Htctpy)(NCS)(3)][TBA](3) (N749), where H(3)tctpy and TBA are 4,4',4"-tricarboxy-2,2':6',2"-terpyridine and tetra-n-butylammonium cation, respectively. In particular, the sensitizer TF-12 gave a short-circuit photocurrent of 19.0 mA cm(-2), an open-circuit voltage (V(OC)) of 0.71 V, and a fill factor of 0.68, affording an overall conversion efficiency of 9.21%. The increased conjugation conferred to the TF dyes by the addition of the π-conjugated pendant groups increases both their light-harvesting and photovoltaic energy conversion capability in comparison with N749. Detailed recombination processes in these devices were probed by various spectroscopic and dynamics measurements, and a clear correlation between the device V(OC) and the cell electron lifetime was established. In agreement with several other recent studies, the results demonstrate that high efficiencies can also be achieved with Ru(II) sensitizers that do not contain thiocyanate ancillaries. This bis-tridentate, dual-carboxy anchor configuration thus serves as a prototype for future omnibearing design of highly efficient Ru(II) sensitizers suited for use in DSCs.     

Translational diffusion of macromolecules and nanoparticles modeled as non-overlapping bead arrays in an effective medium

There are three objectives to the present work. First, starting from a boundary element (BE) formulation of low Reynolds number hydrodynamics, model the translational diffusion of macromolecules modeled as an array of non-overlapping beads, and show how this approach is equivalent to previous formulations of "bead hydrodynamics" and under what conditions. Second, show how this approach can be improved upon by accounting for the variation in forces over the surfaces of individual beads and also extending the approach to a gel modeled as an effective medium, EM. Third, develop a "combined obstruction and hydrodynamic effect" model of the translational diffusion of irregularly shaped macromolecules in a gel. In one of the cases studied, the BE approach is shown to be equivalent to previous "bead model" formulations in which intersubunit hydrodynamic interaction is modeled using the Rotne-Prager tensor. A bead model that accounts for the variation in hydrodynamic stress forces over the individual bead surfaces is shown to be in best agreement with exact results for simple bead arrays made up of 2-4 subunits. The translational diffusion of rods, modeled as strings of from 2 to 100 touching beads in dilute gels is examined. Interpolation formulas valid over a range of gel concentrations and rod lengths are derived for the parallel and perpendicular components of the diffusion tensor as well as the orientationally averaged diffusion tensor. The EM model accounts for the long-range hydrodynamic interaction exerted by the gel support matrix on the diffusing particle of interest but does not account for the reduction in diffusion caused by the direct obstruction of the gel, or steric effect. Both effects are accounted for by writing the translational diffusion in a gel as the product of two terms representing long-range hydrodynamic interaction and steric effects. Finally, the diffusion of a 564 base pair DNA in a 2% agarose gel is examined and model results are compared to experiment (Pluen, A.; Netti, P. A.; Jain, R. K.; Berk, D. A. Biophys. J. 1999, 77, 542-552). For reasonable choices of model parameters, fair agreement between theory and experiment is achieved.     

Growth, structural, vibrational, optical, laser and dielectric aspects of L-alanine alaninium nitrate single crystal

Bulk single crystals of l-alanine alaninium nitrate [abbreviated as LAAN], an intriguing material for frequency conversion has been grown from its aqueous solution by both slow solvent evaporation and by slow cooling techniques. The optimized pH value to grow good quality LAAN single crystal was found to be 2.5. The grown crystals were subjected to single crystal X-ray diffraction studies to determine the unit cell dimensions and morphology. Vibrational frequencies of the grown crystals by Fourier transform infrared spectroscopic technique were investigated. Also, the presence of hydrogen and carbon atoms in the grown sample was confirmed using proton and carbon NMR analyses. The dielectric constant and dielectric loss measurements of the as grown crystal at different temperatures and frequencies of the applied field are measured and reported. LAAN has good optical transmission in the entire visible region with cutoff wavelength within the UV region confirms its suitability for device fabrications. The existence of second harmonic generation signals was observed using Nd:YAG laser with fundamental wavelength of 1064 nm. Its Laser Damage Threshold (LDT) was measured and also tested by using a Q-switched Nd:YAG laser and the value of LDT of LAAN is 17.76GW/cm2 respectively, is found to be better than certain organic and semiorganic materials.     

Structure, electronic properties and catalytic behaviour of an activity-enhancing CYP102A1 (P450(BM3)) variant

The substrate-free crystal structure of a five-mutation directed evolution variant of CYP102A1 (P450(BM3)) with generic activity-enhancing properties ("KT2") has been determined to 1.9-? resolution. There is a close resemblance to substrate-bound structures of the wild-type enzyme (WT). The disruption of two salt bridges that link the G- and I-helices in WT causes conformational changes that break several hydrogen bonds and reduce the angle of the kink in the I-helix where dioxygen activation is thought to take place. The side-chain of a key active site residue, Phe87, is rotated in one molecule of the asymmetric unit, and the side-chains of Phe158 and Phe261 cascade into the orientations found in fatty-acid-bound forms of the enzyme. The iron is out of the porphyrin plane, towards the proximal cysteine. Unusually, the axial water ligand to the haem iron is not hydrogen-bonded to Ala264. The first electron transfer from the reductase domain to the haem domain of substrate-free KT2 is almost as fast as in palmitate-bound WT even though the reduction potential of the haem domain is only slightly more oxidising than that of substrate-free WT. However, NADPH is turned over slowly in the absence of substrate, so the catalytic cycle is gated by a step subsequent to the first electron transfer-a contrast to WT. Propylbenzene binding slightly raises the first electron transfer rate in WT but not in KT2. It is proposed that the generic rate accelerating properties of KT2 arise from the substrate-free form being in a catalytically ready conformation, such that substrate-induced changes to the structure play a less significant role in promoting the first electron transfer than in WT.     

MgZnAl hydrotalcite-like compounds preparation by a green method: effect of zinc content

A series of MgZnAl hydrotalcite-like compounds with different zinc content (1–25 mass % of nominal zinc content) were prepared by a simple and environmentally-friendly method. The solids were characterized by X-ray powder diffraction (XRD), thermogravimetric (TG), nitrogen adsorption-desorption at ?196°C (BET), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and CO₂ temperature-programmed desorption (CO₂-TPD). Transesterification of castor oil with methanol was selected as a probe reaction to stress the effect of zinc incorporation. From the XRD analysis of fresh samples it was demonstrated that the incorporation of zinc is feasible in the nominal range of 1–10 mass % while in the samples with higher zinc content, zinc nitrate and ZnO as secondary crystalline phases were observed. Furthermore, the analysis of samples calcined at 450°C indicated the coexistence of the ZnO and MgO crystalline phases. From the EDS and TG characterizations, the zinc percentage and thermal decomposition of the samples were determined. It was revealed that the samples exhibited the characteristic platy-like habit of hydrotalcite-like compounds. The BET analysis confirmed that the calcined samples presented an increment in their specific surface area values compared with the pristine ones. It was established that the amount of basic sites diminished with the zinc incorporation, which also affected the conversion degree of the transesterification reaction.     

Normal‐to‐Abnormal NHC Rearrangement of AlIII,GaIII, and InIII Trialkyl Complexes: Scope,Mechanism, Reactivity Studies,and H2 Activation

The present contribution reports experimental and theoretical mechanistic investigations on a normal‐to‐abnormal (C2‐to‐C4‐bonded) NHC rearrangement processes occurring with bulky group 13 metal NHC adducts, including the scope of such a reactivity for Al compounds. The sterically congested adducts (nItBu)MMe₃ (nItBu=1,3‐di‐tert‐butylimidazol‐2‐ylidene; M=Al, Ga, In; 1 a – c ) readily rearrange to quantitatively afford the corresponding C4‐bonded complexes (aItBu)MMe₃ ( 4 a – c ), a reaction that may be promoted by THF. Thorough experimental data and DFT calculations were performed on the nNHC‐to‐aNHC process converting the Al‐nNHC ( 1 a ) to its aNHC analogue 4 a . A nItBu/aItBu isomerization is proposed to account for the formation of the thermodynamic product 4 a through reaction of transient aItBu with THF–AlMe₃. The reaction of benzophenone with (nItBu)AlMe₃ afforded the zwitterionic species (aItBu)(CPh₂‐O‐AlMe₃) ( 6 ), reflecting the unusual reactivity that such bulky adducts may display. Interestingly, the nItBu/Al(iBu)₃ Lewis pair behaves like a frustrated Lewis pair (FLP) since it readily reacts with H₂ under mild conditions. This may open the way to future reactivity developments involving commonly used trialkylaluminum precursors.     

In-line and real-time prediction of recombinant antibody titer by in situ Raman spectroscopy

The Food and Drug Administration's (FDA) process analytical technology (PAT) framework has been initiated to encourage drug manufacturers to develop innovative techniques in order to better understand their processes and institute high level quality control which allows action at any point in the manufacturing process. While Raman spectroscopy and chemometrics have been successfully used to predict concentration of conventional metabolites in cell cultures, it is really not the case for active substances. Thus, we propose, for the first time, an in-line and real-time prediction of recombinant antibody titer using an immersion probe link to a spectrometer without the tacking of samples. A good robustness of the method is observed on different culture batches and the contamination risk is drastically reduced which is an important issue in biotechnology manufacturing processes.