Real-time detection of methyl radicals by diode laser absorption at 608 cm−1

A time-resolved technique has been developed for the detection of CH₃ radicals in the gas phase by diode laser absorption at 608 cm^?1 on a rotation-vibration transition of the v₂ mode of CH₃. The usefulness of the technique as a probe of the reaction kinetics is demonstrated by the measurement of the recombination rate of CH₃ radicals and the third-body reaction rate of CH₃ with O₂ at room temperature.     

Spectrofluorimetric study of the beta-cyclodextrin:vitamin K3 complex and determination of vitamin K3

Vitamin K(3) (menadione) is an oil-soluble vitamin and not naturally fluorescent but yields fluorescence when it is reduced. However, it is possible to yield a fluorescent derivative in the region of 407 nm in aqueous medium when complexed to beta-cyclodextrin (CD). A 1:1 stoichiometric ratio and a formation constant of 373+/-34 l mol(-1) were obtained for the binary inclusion complex between menadione and beta-CD. The measurements were performed at pH 6.2 adjusted by adding 0.1 mol l(-1) citrate buffer solution and 6.4 x 10(-3) mol l(-1) of beta-CD concentration. The calibration graph was linear over the range 0.1-2.0 mg l(-1) with a repeatability of 2.2%; the detection limit was 0.022 mg l(-1) and the limit of quantification limit was 0.073 mg l(-1). The procedure was applied to pharmaceutical formulations.     

Preparation and properties of stable mono-, tris-, tetrakis- or hexakis(pentahalophenyl)thalliate(III) complexes

Reaction of TlR₂X, TlX₃ and [TlX₄^? with RLi ( R = C₆F₅ or C₆Cl₅) leads to derivatives containing anions of the types [TlR₄]^?, [TlR₂R′₂]^? or [TlR₆]^3?. Reactions of TlCl₃ with [TlR₄]^? lead to [(μ-Cl)(TlR₂Cl)₂]^? (R = C₆F₅) or [TlRCl₃]^? (R = C₆Cl₅) while addition of X^? (X = Br^? or SCN^?) to Tl(C₆Cl₅)₃ gives [Tl- (C₆Cl₅)₃X]^?. All the novel anions were isolated as salts of bulky cations (Me₄N, Bu₄N, PPN or Ph₃BzP).     

Tunable photoluminescence of closed-shell heterobimetallic Au-Ag dicyanide layered systems

The excited-state properties of the layered La[Ag(CN)(2)](3) and La[Au(CN)(2)](3) systems have been examined and compared with mixed-metal systems of varying metal ratios such as La[Ag(0.78)Au(0.22)(CN)(2)](3), La[Ag(0.55)Au(0.45)(CN)(2)](3), La[Ag(0.33)Au(0.67)(CN)(2)](3), and La[Ag(0.19)Au(0.81)(CN)(2)](3). We have found that these mixed-metal systems luminesce quite strongly at room temperature at an energy that is tunable and depends on the Au:Ag stoichiometric ratio. The emission energy of the mixed-metal samples lies between those of the pure Au and Ag systems. This provides evidence that the excited states responsible for this emission are delocalized over the Ag and Au centers. The strong luminescence of the mixed-metal systems at ambient temperatures is in stark contrast to the weak luminescence behavior of pure La[Au(CN)(2)](3) and La[Ag(CN)(2)](3) samples, which makes the mixed-metal systems more viable than the pure systems for practical applications.     

Chalcogenide centred gold complexes

Chalcogenide-centred gold complexes are an important class of compounds in which a central chalcogen is surrounded by several gold atoms or gold and other metals. They have special characteristics such as unusual geometries, electron deficiency and properties such as luminescence or non-linear optical properties. The best known species are the trinuclear [E(AuPR(3))(3)](+), 'oxonium' type species, that have high synthetic applicability, not only in other chalcogen-centred species, but in many other organometallic derivatives. The aurophilic interactions play an important role in the stability, preference for a particular geometry and luminescence properties in this type of derivatives (critical review, 117 references).     

Synthesis, characterization, and in vitro cytotoxicity of some gold(I) and trans platinum(II) thionate complexes containing water-soluble PTA and DAPTA ligands. X-ray crystal structures of [Au(SC4H3N2)(PTA)], trans-[Pt(SC4H3N2)2(PTA)2], trans-[Pt(SC5H4N)2(PTA)2], and trans-[Pt(SC5H4N)2(DAPTA)2

A series of gold(I) and platinum(II) complexes of the type [Au(SR)(P)] and trans-[Pt(SR) 2(P) 2] [SR = 2-thiopyridine (SPy), 2-thiopyrimidine (SPyrim); P = 1,3,5-triaza-7-phosphaadamantane (PTA), 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane (DAPTA)] were prepared and characterized, and their in vitro cytotoxicities against a panel of seven human cancer cell lines were evaluated. The highly water soluble gold(I) complexes [Au(SR)(P)] [P = PTA and SR = SPy ( 1), SPyrim ( 2); P = DAPTA and SR = SPy ( 3), SPyrim ( 4)] showed low cytotoxicity, while the platinum(II) complexes trans-[Pt(SR) 2(P) 2] [P = PTA and SR = SPyrim ( 5), SPy ( 6); P = DAPTA and SR = SPyrim ( 7), SPy ( 8)] demonstrated potent cytotoxicity for ovarian, colon, renal, and melanoma cancer cell lines on the basis of a comparison with ID 50 values for some established cytotoxic drugs. Single crystals of 2, 5, 6, and 8 suitable for X-ray structural characterization were obtained, and the study revealed the trans configuration for 5, 6, and 8 in their solid states.     

General purpose heuristics for integer programming—Part I

In spite of the many special purpose heuristics for specific classes of integer programming (IP) problems, there are few developments that focus on general purpose integer programming heuristics. This stems partly from the perception that general purpose methods are likely to be less effective than specialized procedures for specific problems, and partly from the perception that there is no unifying theoretical basis for creating general purpose heuristics. Still, there is a general acknowledgment that methods which are not limited to solving IP problems on a class by class basis, but which apply to a broader range of problems, have significant value. We show that certain ideas proposed in the 1970s, which are often overlooked, can be reformulated and linked with more recent developments to give a useful theoretical framework for generating general purpose IP heuristics. This framework, which has the appeal of being highly visual, makes use of cutting plane derivations that also give a natural basis for marrying heuristics with exact branch and cut methods for integer programming problems.