Two dimensional nucleation and growth—Impedance/frequency response

The impedance spectra due to two dimensional nucleation and growth have been calculated.     

PtII diimine chromophores with perfluorinated thiolate ligands: nature and dynamics of the charge-transfer-to-diimine lowest excited state

The synthesis of new Pt(II) diimine complexes bearing perfluorinated thiolate ligands, Pt(II)(NN)(4-X-C(6)F(4)-S)(2), where NN = 2,2'-bipyridine or 1,10-phenanthroline and X = F or CN, is reported, together with an investigation of the nature and dynamics of their lowest excited states. A combined UV-vis, (spectro)electrochemical, resonance Raman, and time-resolved infrared (TRIR) study has suggested that the HOMO is mainly composed of thiolate(pi)/S(p)/Pt(d) orbitals and that the LUMO is largely localized on the pi*(diimine) orbital, thus revealing the [charge-transfer-to-diimine] nature of the lowest excited state. An enhancement of the thiolate ring vibrations, C-F vibrations, and the vibration of the CN-substituent on the thiolate moiety was observed in the resonance Raman spectra, whereas no such enhancement was seen for the nonfluorinated analogues. Thus, the introduction of fluorine substituents on the thiolate moiety probably leads to a more pronounced contribution of the intrathiolate modes to the HOMO compared to the analogous complexes with nonfluorinated thiolates. Furthermore, the introduction of the p-CN group into the thiolate moiety has allowed the dynamics of the lowest excited state of Pt(bpy)(4-CN-C(6)F(4)-S)(2) to be monitored by picosecond TRIR spectroscopy. The dynamics of the lowest [charge-transfer-to-diimine] excited state are governed by ca. 2-ps vibrational cooling and 35-ps back electron transfer.     

Rapid determination of furan in heated foodstuffs by isotope dilution solid phase micro-extraction-gas chromatography--mass spectrometry (SPME-GC-MS)

An analytical method is reported to determine trace amounts of furan in several different commercial foodstuffs that are subjected to thermal treatment. The SPME-GC-MS method is rapid and robust, and entails the following steps: addition of deuterated furan to the sample, sodium chloride-assisted extraction into the headspace, cryofocussing, and finally fibre desorption and GC-MS analysis. Furan is quantified by the use of an external calibration curve, achieving a decision limit (CC alpha) and detection capability (CC beta) of 17 pg and 43 pg, respectively, as absolute furan concentration in a 10 ml headspace vial. The method is applicable to a wide variety of foods, including fruits juices, baby foods in jars, canned foods, pet food, coffee and coffee substitutes. Typical amounts of furan found in selected foodstuffs range from about 1 microg kg(-1) (fruit juice) to 110 microg kg(-1) (baby food containing cooked vegetables). In-house validation data show good precision and accuracy of the method, with a typical repeatability of between 5 and 16% in different food matrices, and trueness determined in orange juice and coffee as 87 and 93%, respectively. Moreover, the measurement uncertainty has been evaluated for two matrices (fruit juice and coffee). Studies on short-term stability of furan in certain foods are also presented, and show that the furan content decreases in food while heating for preparation or reconstitution.     

Spectroscopic characterization of hydroxide and aqua complexes of Fe(II)-protoheme, structural models for the axial coordination of the atypical heme of membrane cytochrome b6f complexes

Electronic absorption and resonance Raman (RR) spectra are reported for hydroxide and aqua complexes of iron(II)-protoporphyrin IX (Fe(II)PP) respectively formed in alkaline and neutral aqueous solutions. These compounds with weak axial ligand(s) represent a biomimetic approach of the unusual coordination of the atypical heme c(i) of membrane cytochrome b6f complexes. Absorption spectra and spectrophotometric titrations show that Fe(II)PP in alkaline aqueous cetyltrimethylammonium bromide (CTABr) binds one hydroxide ion, forming a five-coordinated high-spin (HS) complex. In alkaline aqueous ethanol, we confirm the formation of a dihydroxy complex of Fe(II)PP. In the RR spectra of Fe(II)PP dissolved in neutral aqueous CTABr, a mixture of a four-coordinated intermediate spin form with an HS monoaqua complex (Fe(II)PP(H2O)) was observed. The spectroscopic information obtained for Fe(II)PP(OH-), Fe(II)PP(H2O), and Fe(II)PP(OH-)2 was compared with that previously reported for the 2-methylimidazole and 2-methylimidazolate complexes of Fe(II)PP, representative of the most common axial ligation in HS heme proteins. This investigation reveals a very remarkable analogy in the spectral properties of, in one hand, the Fe(II)PP(H2O) and mono-2-methylimidazole complexes and, in the other hand, the Fe(II)PP(OH-) and mono-2-methylimidazolate complexes. The comparisons of the absorption and RR spectra of Fe(II)PP(OH-) and Fe(II)PP(OH-)2 clearly establish that both a redshift of the pi-pi electronic transitions and an upshift of the v8 RR frequency are spectral parameters indicative of porphyrin doming in HS ferrous complexes. Based upon isotopic substitutions (16OH-,16OD-, and 18OH-), stretching modes of the Fe-OH bond(s) of a ferrous porphyrin were assigned for the first time, i.e., at 435 cm(-1) for Fe(II)PP(OH-) (nu(Fe(II)-OH-)) and at 421 cm(-1) for Fe(II)PP(OH-)2 (nu(s)(Fe(II)-(OH-)2). The spectroscopic and redox properties of Fe(II)PP(H2O), Fe(II)PP(OH-), and heme c(i) were discussed and favor a water coordination for the heme c(i) iron.     

Manipulation and characterization of red blood cells with alternating current fields in microdevices

The motion of a suspension of erythrocytes (red blood cells, RBCs) in response to a high-frequency alternating current (AC) field in a microfluidic device is examined with parallel and orthogonal electrode configurations to delineate the various fundamental driving forces. Cell repulsion from the platinum electrodes due to electrode polarization interacting with cell membrane polarizations is observed to be the strongest force acting on the particles in the first few seconds of field application. We exploit this strong repulsion to concentrate the bioparticles between the microelectrodes to amplify multiparticle aggregation phenomenon and dielectrophoretic (DEP) manipulation in a small and well-characterized region within the microfluidic device. Secondary motions include RBC pearl chain formation along field lines due to particle polarization followed by classical dielectrophoretic motion of the chains across field lines to regions of weaker field. These are driven by far weaker dipole-dipole and field-dipole interactions than the preliminary electrode repulsions. RBC chain length and total aggregated cells are presented for a variety of AC frequencies and are significantly amplified by the electrode repulsion. Motion of particles away from the polarized electrode is found to be species- and age-sensitive and can stand by itself as a promising identification and separation mechanism. In a 0.1 S/m isotonic phosphate buffer saline medium, we observe the largest cell mobilities at an optimal frequency of approximately 1 MHz, corresponding to the inverse diffusion time across the double layer of the cell and across the electrode's polarized layer. This suggests that the dielectric responses of both particles and electrodes in the low MHz frequency range are mostly determined by normal electromigration of ions from the bulk to their interfaces. Sensitivity to RBC age and species suggests that the surface proteins and membrane ion channels can affect the capacitance of the interface to accommodate the ions from the bulk. Such surface ion accumulation and polarization mechanisms are different from the classical dielectric theories. The resonant frequency of electrode polarization at around 1 MHz falls between positive and negative dielectrophoretic resonant frequency peaks - suggesting that the double-layer polarization mechanism is a distinct and potentially important bioparticle manipulation tool.     

Trace level determination of acrylamide in cereal-based foods by gas chromatography-mass spectrometry

A quantitative method has been developed for the determination of trace levels (<50 microg/kg) of acrylamide in cereal-based foods. The method is based on extraction of acrylamide with water, acidification and purification with Carrez I and II solutions, followed by bromination of the acrylamide double bond. The reaction product (2,3-dibromopropionamide) is extracted with ethyl acetate/hexane (4:1, v/v), dried over sodium sulfate, and cleaned up through a Florisil column. The derivative is then converted to 2-bromopropenamide by dehydrobromination with triethylamine and analyzed by gas chromatography coupled to mass spectrometry (GC-MS), employing (13C3)acrylamide as internal standard. In-house validation data for commercial and experimental cereal products showed good precision of the method, with repeatability and intermediate reproducibility relative standard deviations below 10%. The limit of detection and limit of quantitation are estimated at 2 and 5 microg/kg, respectively, and recoveries of acrylamide from samples spiked at levels of 5-500 microg/kg ranged between 93 and 104% after correction of analyte loss by the internal standard. Finally, a comparative test organized with two independent laboratories provided additional confidence in the good performance of the method, particularly at very low concentration levels.     

Reactions of bis(tetrazole)phenylenes. Surprising formation of vinyl compounds from alkyl halides

The reactions of 1,2-bis(tetrazol-5-yl)benzene (1), 1,3-bis(tetrazol-5-yl)benzene (2), 1,4-bis(tetrazol-5-yl)benzene (3), 1,2-(Bu₃SnN₄C)₂C₆H₄ (4), 1,3-(Bu₃SnN₄C)₂C₆H₄ (5) and 1,4-(Bu₃SnN₄C)₂C₆H₄ (6) with 1,2-dibromoethane were carried out by two different methods in order to synthesise pendant alkyl halide derivatives of the parent bis-tetrazoles. This lead to the formation of several alkyl halide derivatives, substituted at either N1 or N2 on the tetrazole ring, as well as the surprising formation of several vinyl derivatives. The crystal structures of both 1,2-[(2-vinyl)tetrazol-5-yl)]benzene (1-N,2-N′) (1b) and 1,3-bis[(2-bromoethyl)tetrazol-5-yl]benzene (2-N,2-N′) (5d) are discussed.     

Novel Trinuclear MnII/MnII/MnII Complexes – Crystal Structures and Catalytic Properties

The trinuclear manganese(II) complexes [Mn₃(L¹)₂(μ‐OAc)₄]·2Et₂O {HL¹ = (1‐hydroxy‐4‐nitrobenzyl)((2‐pyridyl)methyl)((1‐methylimidazol‐2‐yl)methyl)amine} ( 1·2EtOH ), [Mn₃(L²)₂(μ‐OAc)₄] {HL² = ((1‐methylimidazol‐2‐yl)methyl)(1‐hydroxybenzyl)amine} ( 2 ) and [Mn₃(L³)₂(μ‐OAc)₆] {L³ = bis(1‐methylimidazol‐2‐yl)methanone} ( 3 ) were synthesized. The compounds were characterized by X‐ray crystallography, mass spectrometry, IR, UV‐vis spectroscopy, and elemental analysis. The manganese atoms in 1 and 2 are bridged by phenol moieties of the ligands and acetates. In 3 they are only bridged by acetates in a mono‐ and bi‐dentate way. The resulting Mn···Mn distances are 3.233(1) Å ( 1 ), 3.364(1) Å ( 2 ) and 3.643(7) Å ( 3 ). In the present compounds different limiting cases for the phenomenon of the carboxylate shift are realized. Besides symmetric mono‐ and bi‐dentate bridging an unusual intermediate is also observed. 1·2EtOH is the first example of a trinuclear model for the OEC that shows catalase activity. Furthermore it was characterized by temperature dependent magnetic susceptibility measurements and a total spin ground state of S_t = 5/2 was found. The results for 1 reveals antiferromagnetic coupling between the central and the terminal manganese ions, with J = ?1.2 cm^?1, g = 2.00 (fixed), χ_TIP = 150×10^?6 cm³mol^?1.     

Boundary discretization for high‐order discontinuous Galerkin computations of tidal flows around shallow water islands

In this paper some preliminary results concerning the application of the high‐order discontinuous Galerkin (DG) method for the resolution of realistic problems of tidal flows around shallow water islands are presented. In particular, tidal flows are computed around the Rattray island located in the Great Barrier Reef. This island is a standard benchmark problem well documented in the literature providing useful in situ measurements for validation of the model. Realistic elements of the simulation are a tidal flow forcing, a variable bathymetry and a non‐trivial coastline. The computation of tidal flows in shallow water around an island is very similar to the simulation of the Euler equations around bluff bodies in quasi‐steady flows. The main difference lies in the high irregularity of islands' shapes and in the fact that, in the framework of large‐scale ocean models, the number of elements to represent an island is drastically limited compared with classical engineering computations. We observe that the high‐order DG method applied to shallow water flows around bluff bodies with poor linear boundary representations produces oscillations and spurious eddies. Surprisingly those eddies may have the right size and intensity but may be generated by numerical diffusion and are not always mathematically relevant. Although not interested in solving accurately the boundary layers of an island, we show that a high‐order boundary representation is mandatory to avoid non‐physical eddies and spurious oscillations. It is then possible to parametrize accurately the subgrid‐scale processes to introduce the correct amount of diffusion in the model. The DG results around the Rattray island are eventually compared with current measurements and reveal good agreement. Copyright © 2008 John Wiley & Sons, Ltd.     

Spatial and spectral superconvergence of discontinuous Galerkin method for hyperbolic problems

In this paper, we analyze the spatial and spectral superconvergence properties of one-dimensional hyperbolic conservation law by a discontinuous Galerkin (DG) method. The analyses combine classical mathematical arguments with MATLAB experiments. Some properties of the DG schemes are discovered using discrete Fourier analyses: superconvergence of the numerical wave numbers, Radau structure of the X spatial error.