Comparison of the electrophilic and free-radical addition of halogens with hexafluoro-1,3-butadiene and 1,3-butadiene

Ionic and photochemical reaction of chlorine (Cl₂), bromine (Br₂) and iodine monochloride (ICl) to hexafluoro-1,3-butadiene (1) and 1,3-butadiene (2) were carried out under conditions that would provide product distributions under controlled ionic or free-radical conditions. Product distributions for ionic reaction of Cl₂ and Br₂ with 1 are similar and suggest a weakly-bridged halonium ion species. Theoretical calculations support weakly-bridged chloronium and bromonium ions for both dienes 1 and 2. There are more of the 1,4-dihalo-2-butene products from ionic halogenation of 1 than 2 which correlates with the greater charge density on carbon-4 of halonium ions from 1. Ionic and free-radical reactions of ICl with 1 give 8 and 2% of 3-chloro-4-iodohexafluoro-1-butene and 4-chloro-3-iodohexafluoro-1-butene, respectively. The minor cis-1,4-dihalo-2-butene products from 1 and 2 are reported when formed.     

Supramolecular chirogenesis in zinc porphyrins: equilibria, binding properties, and thermodynamics

Complexation mechanism, binding properties and thermodynamic parameters of supramolecular chirality induction in the achiral host molecule, syn (face-to-face conformation) ethane-bridged bis(zinc porphyrin), upon interaction with chiral monoamine and monoalcohol guests have been studied by means of the UV-vis, CD, (1)H NMR, and ESI MS techniques. It was found that the chirogenesis process includes three major equilibria steps: the first guest ligation to a zinc porphyrin subunit of the host (K(1)), syn to anti conformational switching (K(S)), and further ligation by a second guest molecule to the remaining ligand-free zinc porphyrin subunit (K(2)), thus forming the final bis-ligated species possessing supramolecular chirality. The validity of this equilibria model is confirmed by the excellent match between the calculated and experimentally observed spectral parameters of the bis-ligated species. The second ligation proceeds in a cooperative manner as K(2) > K(1) for all supramolecular systems studied, regardless of the structure of the chiral ligand used. The binding properties are highly dependent on the nature of the functional group (amines are stronger binders than alcohols) and on the structure of the chiral guests (primary and aliphatic amines have overall binding constant values greater than those of secondary and aromatic amines, respectively).     

Quantitative separation of gold from cadmium, indium, zinc and other elements by cation-exchange chromatography in hydrochloric acid-acetone medium

Gold(III) can be separated from Cd, In. Zn, Ni, Cu(II), Mn(II), Co(II), Mg, Ca, Al, Fe(III), Ga and U(VI) by adsorbing these elements on a column of AG50W-X8 sulphonated polystyrene cation-exchange resin from 0.1M HCl containing 60% v v acetone, while Au(III) passes through and can be eluted with the same reagent. Separations are sharp and quantitative. The amounts of gold retained by the resin are between 1 and 2 orders of magnitude lower than encountered during adsorption from aqueous 0.1M HCl. Recoveries for mg amounts of gold are 99.9% or better and for ng amounts are still better than 99%, as shown by radioactive tracer methods. Hg(II), Bi, Sn(IV), the platinum metals and some elements which tend to form oxy-anions in dilute acid accompany gold. All other elements, though not investigated in detail, should be retained, according to their known distribution coefficients. Relevant elution curves, results of quantitative separations of binary mixtures and of recovery tests are presented.     

Toeplitz operators in n-dimensions

The interplay between the theory of Toeplitz operators on the circle and the theory of pseudodifferential operators on the line (i. e. Wiener-Hopf operators) is by now well-known and well-understood. In this article we show that there is a parallel situation in higher dimensions. To begin with, by using pseudodifferential multipliers, one can simplify the composition rules for Toeplitz operators, (§ 3), and describe precisely how Toeplitz operators of Bergmann type are related to Toeplitz operators of Szegö type (§ 9). Furthermore, it turns out that the ring of pseudodifferential operators on a compact manifold, M, is isomorphic with the ring of Toeplitz operators on an appropriate Grauert tube about M (§ § 4–6), and the ring of Weyl operators on ⁿ is isomorphic with the ring of Toeplitz operators on the complex ball in ⁿ (§ § 7–10).     

On the origin of dynamic instability of molecular systems

The vibronic origin of dynamic instability of molecular systems considered earlier, is here given a more complete and rigorous treatment. It is shown that the nonvibronic contribution to the curvature of the adiabatic potential arising due to nuclear displacements under fixed electronic density distribution, is always positive, and hence the only reason for dynamic instability is the pseudo Jahn-Teller effect. For some examples of special interest (planar equilateral NH₃, planar square CH₄ and linear H ₃ ⁺ ) the molecular excited states, responsible for the instability of the ground state, are revealed by means of ab initio calculations.     

Oxygen atom transfer in models for molybdenum enzymes: isolation and structural, spectroscopic, and computational studies of intermediates in oxygen atom transfer from molybdenum(VI) to phosphorus(III)

Intermediates in the oxygen atom transfer from Mo(VI) to P(III), [Tp(iPr)MoOX(OPR3)] (Tp(iPr) = hydrotris(3-isopropylpyrazol-1-yl)borate; X = Cl-, phenolates, thiolates), have been isolated from the reactions of [Tp(iPr)MoO2X] with phosphines (PEt3, PMePh2, PPh3). The green, diamagnetic oxomolybdenum(IV) complexes possess local C(1) symmetry (by NMR spectroscopy) and exhibit IR bands assigned to nu(Mo==O) (approximately 950 cm(-1)) and nu(P==O) (1140-1083 cm(-1)) vibrations. The X-ray crystal structures of [Tp(iPr)MoOX(OPEt3)] (X = OC6H4-2-sBu, SnBu), [Tp(iPr)MoO(OPh)(OPMePh2)], and [Tp(iPr)MoOCl(OPPh3)] have been determined. The monomeric complexes exhibit distorted octahedral geometries, with coordination spheres composed of tridentate fac-Tp(iPr) and mutually cis monodentate terminal oxo, phosphoryl (phosphine oxide), and monoanionic X ligands. The electronic structures and stabilities of the complexes have been probed by computational methods, with the three-dimensional energy surfaces confirming the existence of a low-energy steric pocket that restricts the conformational freedom of the phosphoryl ligand and inhibits complete oxygen atom transfer. The reactivity of the complexes is also briefly described.     

Synthesis of cationic carbonyl complexes of manganese(I) with bidentate ligands

Summary Bidentate ligands can readily replace acetone in thefac-[Mn(CO)₃(chel)(OCMe₂)]⁺ complexes or the perchlorate group fromfac-[Mn(CO)₃(chel)(OClO₃)] yieldingfac-[Mn(CO)₃(chel)(L-L)]⁺ or [{fac-Mn(CO)₃(chel)}₂(L-L)]²⁺ [chel = 1,10-phenanthroline (phen), 2,2-bipyridine (bipy), 1,2-bis(diphenylphosphine)ethane (dpe); L-L = bis(diphenylphosphine)methane (dpm), dpe, 1,4-bis(diphenylphosphine)butane (dpb), succinonitrile (suc), and glutaronitrile (glu)]. Some of these mononuclear complexes are precursors for binuclear complexes which are linked by bridging phosphines or nitriles.     

Cationic Carbonyl complexes of manganese(I) with diphosphines

The bromo-carbonyls fac-BrMn(CO)₃(diphos)(diphos  Ph₂P(CH₂)_nPPh₂ for n = 1(dpm), 2(dpe), 3(dpp) and 4(dbp)) react with AgClO₄ in dichloromethane solution to give the neutral fac-O₃ClOMn(CO)₃(diphos). The reaction of the latter complexes at room temperature with a variety of ligands L  phosphines (PR₃), phosphites (P(OR)₃), pyridine (Py), acetonitrile (MeCN), tetrahydrothiophene (THT) or acetone (Me₂CO) leads to the cationic species fac-[Mn(CO)₃(diphos)L]ClO₄ (or to the [Mn(CO)₄(diphos))]ClO₄, when L  CO). When L is a phosphorus ligand, the cationic fac-tricarbonyls isomerize upon heating to the mer isomers, which could only be isolated by this method for diphos  dpm, the reaction being accompanied by decomposition in the other cases. UV irradiation of the mer-[Mn(CO)₃(diphos)L]ClO₄ in the presence of a large excess of L gives the corresponding trans-[Mn(CO)₂(diphos)L₂]ClO₄.     

A versatile microfabricated platform for electrophoresis of double- and single-stranded DNA

We demonstrate a versatile microfabricated electrophoresis platform, incorporating arrays of integrated on-chip electrodes, heaters, and temperature sensors. This design allows a range of different sieving gels to be used within the same device to perform separations involving both single- and double-stranded DNA over distances on the order of 1 cm. We use this device to compare linear and cross-linked polyacrylamide, agarose, and thermo-reversible Pluronic-F127 gels on the basis of gel casting ease, reusability, and overall separation performance using a 100 base pair double-stranded DNA ladder as a standard sample. While cross-linked polyacrylamide matrices provide consistently high-quality separations in our system over a wide range of DNA fragment sizes, Pluronic gels also offer compelling advantages in terms of the ability to remove and reload the gel. Agarose gels offer good separation performance, however, additional care must be exercised to ensure consistent gel properties as a consequence of the need for elevated gel loading temperatures. We also demonstrate the use of denaturing cross-linked polyacrylamide gels at concentrations up to 19% to separate single-stranded DNA fragments ranging in size from 18 to 400 bases in length. Primers differing by 4 bases at a read length of 30 bases can be separated with a resolution of 0.9-1.0 in under 20 min. This level of performance is sufficient to conduct a variety of genotyping assays including the rapid detection of single nucleotide polymorphisms (SNPs) in a microfabricated platform. The ability to use a single microelectrophoresis system to satisfy a wide range of separation applications offers molecular biologists an unprecedented level of flexibility in a portable and inexpensive format.     

PHYTOCHROME STATES IN ETIOLATED PEA SEEDLINGS: FLUORESCENCE AND PRIMARY PHOTOREACTIONS AT LOW TEMPERATURES

Emission spectra of the red phytochrome form (Pr) and fluence time-response curves of the Pr fluorescence intensity changes were measured in etiolated pea seedlings at low temperatures (80–150 K) in connection with its phototransformations into the initial photoproduct (Lr) and back upon actinic red (667 nm) and far-red (696 nm) illumination. The variable fluorescence reaches 45% at 85 K and decreases with the rise of temperature. Three kinetic components of the changes were found in the direct (Pr→Lr) and back (Lr→Pr) photoreactions belonging to three states of phytochrome: “slow”, “fast” and “very fast” (respective indices: s, f and vf). The amplitudes of the components and rate constants to reach photoequilibrium were determined in the direct and back photoreactions at different temperatures, and from this, their quantum yields, extent of the Pr?Lr phototransformation and activation energy of the reactions were evaluated for the three Pr and Lr states. The yields differ from each other by approximately a factor of 10 and those for the direct and back photoreactions are close to each other. The proportion of the amplitudes of the variable fluorescence of the three phytochrome states changes with temperature and upon the Pr→Lr photo-transformation and the Pr states differ in the position of their emission spectra by 3–5 nm. A close similarity between the Pr and Lr properties was observed, which implies a symmetrical scheme of their photoreactions. It is suggested that the three phytochrome species may originate in different conformational states of the chromophore and they independently transform in parallel photoreactions into the respective photoproducts: Prvf?Lrvf, Prf?Lrf and Prs?Lrs.