Synthesis, reactivities, and magnetostructural properties of FeIII, FeIII-O-FeIII, and ZnIIFeIII-O-FeIIIZnII complexes of a tetraiminodiphenolate macrocycle

The mononuclear iron(III) complexes [Fe(LH2)(H2O)Cl](ClO4)2.2H2O (1) and [Fe(LH2)(H2O)2](ClO4)3.H2O (2) have been prepared by reacting [Pb(LH(2))](ClO4)2 with FeCl3.6H2O and Fe(ClO(4))(3).6H(2)O, respectively. Complex 2 upon treatment with 1 equiv of alkali produces the oxo-bridged dimer [{Fe(LH2)(H2O)}2(mu-O)](ClO4)4.2H2O (3). In these compounds, LH2 refers to the tetraiminodiphenol macrocycle in the zwitterionic form whose two uncoordinated imine nitrogens are protonated and hydrogen-bonded to the metal-bound phenolate oxygens. The aqua ligands of complexes 1-3 get exchanged in acetonitrile. Reaction equilibria involving binding and exchange of the terminal ligands (Cl-/H2O/CH3CN) in these complexes have been studied spectrophotometrically. The equilibrium constant for the aquation reaction (K(aq)) [1]2+ + H2O <==> [2]3+ + Cl- in acetonitrile is 8.65(5) M, and the binding constant (K(Cl)-) for the reaction [1]2+ + Cl- [1Cl]+ + CH3CN is 4.75(5) M. The pK(D) value for the dimerization reaction 2[2]3+ + 2OH- <==> [3]4+ + 3H(2)O in 1:1 acetonitrile-water is 9.38(10). Complexes 1-3 upon reaction with Zn(ClO4)(2).6H(2)O and sodium acetate (OAc), pivalate (OPiv), or bis(4-nitrophenyl)phosphate (BNPP) produce the heterobimetallic complexes [{FeLZn(mu-X)}2(mu-O)](ClO4)2, where X = OAc (4), OPiv (5), and BNPP (6). The pseudo-first-order rate constant (k(obs)) for the formation of 4 at 25 degrees C from either 1 or 3 with an excess of Zn(OAc)2.2H2O in 1:1 acetonitrile-water at pH 6.6 is found to be the same with k(obs) = 1.6(2) x 10(-4) s(-1). The X-ray crystal structures of 3, 4, and 6 have been determined, although the structure determination of 3 was severely affected because of heavy disordering. In 3, the Fe-O-Fe angle is 168.6(6) degrees, while it is exactly 180.0 degrees in 4 and 6. Cyclic and square-wave voltammetric (CV and SWV) measurements have been carried out for complexes 1-4 in acetonitrile. The variation of the solvent composition (acetonitrile-water) has a profound effect on the E(1/2) and DeltaE(p) values. The binding of an additional chloride ion to an iron(III) center in 1-3 is accompanied by a remarkable shift of E(1/2) to more negative values. The observation of quasi-reversible CV for complexes containing a Fe(III)-O-Fe(III) unit (3 and 4) indicates that in the electrochemical time scale unusual Fe(III)-O-Fe(II) is produced. The 1H NMR spectra of complexes 3-6 exhibit hyperfine-shifted signals in the range 0-90 ppm with similar features. The metal-hydrogen distances obtained from T(1) measurements are in good agreement with the crystallographic data. Variable-temperature (2-300 K) magnetic susceptibility measurements carried out for 3 and 4 indicate strong antiferromagnetic exchange interaction (H = -2JS1.S2) between the high-spin iron(III) centers in the Fe-O-Fe unit with J = -114 cm(-1) (3) and -107 cm(-1) (4).     

Novel solid-phase extraction method to separate 4-desmethyl-, 4-monomethyl-, and 4,4'-dimethylsterols in vegetable oils

Conventional methods for sterol fractions separation by TLC have some drawbacks such as low recovery and time consuming. A new solid-phase extraction (SPE) method was developed with stepwise elution by increasing the polarity of solvents mixture: n-hexane and diethyl ether. This method was applied to separate sterol fractions of hazelnut and virgin olive oils, and our results were compared with those of TLC method. The recovery of spiked authentic sample of 4-desmethylsterols in oil was higher with the SPE method (94%) compared with the TLC method (62%). The amount of 4,4'-dimethylsterols and 4-desmethylsterols separated with SPE in both hazelnut and virgin olive oil samples were at least 75% and 35%, respectively, higher than that of TLC. Generally, both methods obtained similar results for 4-monomethylsterols of the two oils. This new SPE method to separate phytosterol fractions was less time consuming, simpler and can be used instead of preparative TLC to detect adulteration of virgin olive oil with hazelnut oil.     

Electrokinetic flow control in microfluidic chips using a field-effect transistor

A field-effect transistor is developed to control flow in microfluidic chips by modifying the surface charge condition. In this investigation, zeta potential at a particular location is altered locally by applying a gate voltage, while zeta potential at other locations is maintained at its original value. This non-uniform zeta potential results in a secondary electroosmotic flow in the lateral direction, which is used for flow control in microgeometries. Here, microchannel structures and field-effect transistors are formed on polydimethylsiloxane (PDMS) using soft lithography techniques, and a micro particle image velocimetry technique is used to obtain high resolution velocity distribution in the controlled region. The flow control is observed at relatively low gate voltage (less than 50 V), and this local flow control is primarily due to current leakage through the interface between PDMS and glass layers. A leakage capacitance model is introduced to estimate the modified zeta potential for the straight channel case, and excellent agreement is obtained between the predicted and experimental zeta potential results. This leakage-current based field-effect is then applied to a T-channel junction to control flow in the branch channel. Experiments show that the amount of discharge in the branch channel can be controlled by modulating gate voltage.     

Electrophoretic mobility of linear and star-branched DNA in semidilute polymer solutions

Electrophoresis of large linear T2 (162 kbp) and 3-arm star-branched (N(Arm) = 48.5 kbp) DNA in linear polyacrylamide (LPA) solutions above the overlap concentration c* has been investigated using a fluorescence visualization technique that allows both the conformation and mobility mu of the DNA to be determined. LPA solutions of moderate polydispersity index (PI approximately 1.7-2.1) and variable polymer molecular weight Mw (0.59-2.05 MDa) are used as the sieving media. In unentangled semidilute solutions (c* < c < c(e)), we find that the conformational dynamics of linear and star-branched DNA in electric fields are strikingly different; the former migrating in predominantly U- or I-shaped conformations, depending on electric field strength E, and the latter migrating in a squid-like profile with the star-arms outstretched in the direction opposite to E and dragging the branch point through the sieving medium. Despite these visual differences, mu for linear and star-branched DNA of comparable size are found to be nearly identical in semidilute, unentangled LPA solutions. For LPA concentrations above the entanglement threshold (c > c(e)), the conformation of migrating linear and star-shaped DNA manifest only subtle changes from their unentangled solution features, but mu for the stars decreases strongly with increasing LPA concentration and molecular weight, while mu for linear DNA becomes nearly independent of c and Mw. These findings are discussed in the context of current theories for electrophoresis of large polyelectrolytes.     

Mechanism of nanoparticle formation in self-assembled colloidal templates: population balance model and Monte Carlo simulation

Modeling the nanoparticle formation mechanism in water-in-oil microemulsion, a self-assembled colloidal template, has been addressed in this paper by two formalisms: the deterministic population balance equation (PBE) model and stochastic Monte Carlo (MC) simulation. These are based on time-scale analysis of elementary events consisting of reactant mass transport, solid solubilization, reaction, coalescence-exchange of drops, and finally nucleation and growth of nanoparticles. For the first time in such a PBE model, realistic binomial redistribution of molecules in the daughter drops (after coalescence-exchange of two drops) has been explicitly implemented. This has resulted in a very general model, applicable to processes with arbitrary relative rates of coalescence-exchange and nucleation. Both the deterministic and stochastic routes could account for the inherent randomness in the elementary events and successfully explained temporal evolution of mean and variance of nanoparticle size distribution. This has been illustrated by comparison with different yet broadly similar experiments, operating either under coalescence (lime carbonation to make CaCO(3) nanoparticles) or nucleation (hydride hydrolysis to make Ca(OH)(2) nanoparticles) dominant regimes. Our calculations are robust in being able to predict for very diverse process operation times: up to 26 min and 5 h for carbonation and hydrolysis experiments, respectively. Model predictions show that an increase in the external reactant addition rate to microemulsion solution is beneficial under certain general conditions, increasing the nanoparticle production rate significantly without any undesirable and perceptible change in particle size.     

Production and Characterization of an Alkaline Thermostable Crude Lipase from an Isolated Strain of <Emphasis Type="Italic">Bacillus cereus</Emphasis> C<Subscript>7</Subscript>

A bacterial strain isolated from spoiled coconut and identified as Bacillus cereus was found capable of producing alkaline thermostable extracellular lipase. Optimum temperature, time, and pH for enzyme substrate reaction were found to be 60 °C, 10 min, and 8.0 respectively. Common surfactants except Triton X 100 and cetyltrimethylammonium bromide have no or very little inhibitory effects on enzyme activity. The enzyme was found to be stable in presence of oxidizing agents and protease enzyme. The maximum lipase production was achieved at 30–33 °C, pH 8.0 on 24 h of fermentation using 50 ml medium in a 250-ml Erlenmeyer flask. The superior carbon and nitrogen sources for lipase production were starch (2%) and ammonium sulfate (nitrogen level 21.2 mg/100 ml), peptone (nitrogen level 297 mg/100 ml), and urea (nitrogen level 46.62 mg/100 ml) in combination, respectively. The maximum enzyme activity obtained was 33 ± 0.567 IU/ml.     

The use of ECD/ETD to identify the site of electrostatic interaction in noncovalent complexes

Electrostatic interactions play an important role in the formation of noncovalent complexes. Our previous work has highlighted the role of certain amino acid residues, such as arginine, glutamate, aspartate, and phosphorylated/sulfated residues, in the formation of salt bridges resulting in noncovalent complexes between peptides. Tandem mass spectrometry (MS) studies of these complexes using collision-induced dissociation (CID) have provided information on their relative stability. However, product-ion spectra produced by CID have been unable to assign specifically the site of interaction for the complex. In this work, tandem MS experiments were conducted on noncovalent complexes using both electron capture dissociation (ECD) and electron-transfer dissociation (ETD). The resulting spectra were dominated by intramolecular fragments of the complex with the electrostatic interaction site intact. Based upon these data, we were able to assign the binding site for the peptides forming the noncovalent complex.     

Control of the Supramolecular Excimer Formation of Thioflavin T within a Cucurbit[8]uril Host: A Fluorescence On/Off Mechanism

On or off? A new excimer band at λ=570 nm was visualized during the noncovalent host–guest interaction between thioflavin T (ThT) and cucurbit[8]uril (CB8). Controlled dissociation of this assembly in the presence of Ca²⁺ was demonstrated as an on/off fluorescence switch (see picture).

     

Fluctuations of eigenvalues and second order Poincaré inequalities

Linear statistics of eigenvalues in many familiar classes of random matrices are known to obey gaussian central limit theorems. The proofs of such results are usually rather difficult, involving hard computations specific to the model in question. In this article we attempt to formulate a unified technique for deriving such results via relatively soft arguments. In the process, we introduce a notion of ‘second order Poincaré inequalities’: just as ordinary Poincaré inequalities give variance bounds, second order Poincaré inequalities give central limit theorems. The proof of the main result employs Stein’s method of normal approximation. A number of examples are worked out, some of which are new. One of the new results is a CLT for the spectrum of gaussian Toeplitz matrices.