Minimal lattice-subspaces

In this paper the existence of minimal lattice-subspaces of a vector lattice containing a subset of is studied (a lattice-subspace of is a subspace of which is a vector lattice in the induced ordering). It is proved that if there exists a Lebesgue linear topology on and is -closed (especially if is a Banach lattice with order continuous norm), then minimal lattice-subspaces with -closed positive cone exist (Theorem 2.5).

In the sequel it is supposed that is a finite subset of , where is a compact, Hausdorff topological space, the functions are linearly independent and the existence of finite-dimensional minimal lattice-subspaces is studied. To this end we define the function where . If is the range of and the convex hull of the closure of , it is proved:

(i)

There exists an -dimensional minimal lattice-subspace containing if and only if is a polytope of with vertices (Theorem 3.20).

(ii)

The sublattice generated by is an -dimensional subspace if and only if the set contains exactly points (Theorem 3.7).

This study defines an algorithm which determines whether a finite-dimensional minimal lattice-subspace (sublattice) exists and also determines these subspaces.

     

Study of the isotropic and anisotropic fluorescence of two oligothiophenes by femtosecond time-resolved spectroscopy

The excited-state dynamics of two oligothiophenes, 5,5'-dicarboxyhaldehyde 2,2',5',2' '-terthiophene and 5-carboxyhaldehyde 2,2',5',2' '-terthiophene, were studied by time-resolved fluorescence spectroscopy, in the femtosecond regime. The isotropic and anisotropic parameters of their fluorescence were calculated. The angle (alpha) between the absorption and emission molecular dipoles was estimated from the initial fluorescence anisotropy. The effect of the chemical substituents, at the ends of the main chain of the molecule, on the temporal behavior of the fluorescence was investigated. Particularly, the nonsymmetric oligothiophene molecule (containing one aldehyde group) exhibits shorter excited-state isotropic decay time than the symmetric one (containing two aldehyde groups). This is due to the higher value of the emission dipole moment of the nonsymmetric oligothiophene in comparison with that of the symmetric one. Additionally, the two materials have almost the same anisotropic fluorescence parameters, and this is attributed to the same rotational motions in the excited state due to their similar molecular structures.     

Structural transitions at solid-liquid interfaces

In this paper we present the findings of our investigations using molecular dynamics, on molecularly thin films of n-octane confined between topographically smooth solid surfaces. We focus on the effect of increasing solid surface-methylene unit energetic affinity and the effect of increasing pressure (normal load) of the film in inducing liquid-solid phase transitions. We observed an abrupt transition in the structural features of the film at a critical value of the characteristic energy that quantified the affinity between solid surfaces and methylene units. This energetically driven transition was evident from the discontinuous increase of intermolecular order, a precipitous extension of the octane molecules and freezing of molecular migration and rotation. Increasing pressure had a similar effect in inducing a liquid-solid phase transition. The characteristics of the transition showed that it is a mild first order transition from a highly ordered liquid to a poorly organized solid. These findings demonstrate that the solidification of nanoscopically thin films of linear alkanes is a general phenomenon (driven either energetically or by increasing pressure), and does not require the aid of commensurate surface topography.     

Thermal transformation of arylamidoximes in the presence of phosphorus ylides. Unexpected formation of 3‐aryl‐5‐arylamino‐1,2,4‐oxadiazoles

The unexpected formation of 3‐aryl‐5‐arylamino‐1,2,4‐oxadiazoles took place, when arylamidoximes reacted thermally with ethoxycarbonylmethylene(triphenyl)phosphorane. Furoxans, nitriles, ureas were also isolated suggesting aryl cyanide oxides as intermediates. 3‐Aryl‐5‐arylamino‐1,2,4‐oxadiazoles were formed via an aryl migration from the carbon atom to the nitrogen atom of the amidoxime, and the structure was further proved from the X‐ray crystal structure of the N‐(4‐bromobenzoyl) derivative.     

Factors affecting multiresidue determination of priority herbicides when using solid-phase microextraction

A solid-phase microextraction (SPME) procedure was developed for the determination of 10 selected organonitrogen herbicides (s-ethyl dibropylthiocarbamate [EPTC], molinate, propachlor, trifluralin, simazine, atrazine, propazine, terbuthylazine, alachlor, and prometryn) and was tested with various natural waters. Gas chromatography coupled with flame thermionic and mass spectrometric detection was used for quantitation. For this purpose, polydimethylsiloxane and polyacrylate fibers were used and the factors affecting the SPME process such as pH, ionic strength, methanol content, memory effect, stirring rate, and adsorption-time profile were investigated and optimized. By using spiked liquid chromatography water, optimal factors were determined to be 25% salt, <0.5% methanol, stirring rate of 960 rpm, pH 4, and an equilibrium time of 30 min. These conditions were used in further studies of the fibers and in analysis of natural water samples. The method was applied to spiked natural waters such as ground water, sea water, lake water, and river water at a concentration range of 0.5-10 microg/L. Limits of detection ranged from 5 to 90 ng/L, and precision ranged from 5 to 15% (as relative standard deviation), depending on the pesticide, fiber, and detector used. The recoveries of herbicides were 70.2-118.4%, and the average r2 values of the calibration curves were >0.99 for all analytes. The results demonstrate the suitability of the SPME method to determine these organonitrogen herbicides in various natural waters. River water samples originating from the Epirus region (Northwestern Greece) were analyzed to verify the performance of the optimized method by comparing the results obtained by SPME with those obtained by using conventional solid-phase extraction of the selected herbicides.     

Reduced and excited states of (bpym)[PtCl(2)](n)() (bpym = 2,2'-bipyrimidine; n = 1, 2): experiments and DFT calculations

The complexes (bpym)PtCl(2) (1) and the new (micro-bpym)[PtCl(2)](2) (2), bpym = 2,2'-bipyrimidine, were synthesized and, in the case of 1, crystallized in solvent-free form for X-ray diffraction. The molecules 1 exhibit two different kinds of stacking motifs in the crystal with an interstack CH--N interaction. Complexes 1 and 2 were found to be sufficiently soluble for cyclic voltammetry, spectroscopy (absorption and emission), and spectroelectrochemical studies (UV-vis, EPR). As a result of single or double coordination of the strongly sigma-accepting [PtCl(2)] fragment to bpym, the paramagnetic anions 1(*)(-)() and 2(*)(-)() and the dianions 1(2-) and 2(2-) could be reversibly generated, despite the presence of metal-halide bonds. DFT calculations of A((195)Pt) and g tensor components confirm that the singly occupied MOs of the monoanionic species have mainly pi(bpym) character with nonnegligible platinum d orbital participation. The assignments of the electronic absorption and emission and resonance Raman spectra for both complexes are supported by DFT calculations.     

Synthesis and analysis of compounds having the skeleton of ergot alkaloids with the nitrogen atom in the D-ring transposed

Alkylation-amination of the enamine 2 in the presence of ethyl α,α-bis(dibromomethyl)acetate, triethyl-amine, and methylamine lead to the construction of the aza-transposed ergoline 3 . Sequential reduction, hydrolysis, reesterification, and indolization of 3 , produced three diastereomers of 6 . The structure of these three diastereomers was assigned on the basis of nmr and ir spectral analysis to be (α-cis) syn, (β-cis) anti, and (α-trans) syn. The isomer (β-cis) anti was reduced with lithium aluminum hydride to the corresponding alcohol.     

Complexes of Zn(2+), Cd(2+), and Hg(2+) with 2-(alpha-Hydroxybenzyl)thiamine Monophosphate Chloride

The binding sites of Zn(2+), Cd(2+), and Hg(2+) in complexes with 2-(alpha-hydroxybenzyl)thiamine monophosphate chloride, (LH)(+)Cl(-), have been investigated in the solid state [2-(alpha-hydroxybenzyl)thiamin monophosphate chloride monoprotonated at the phosphate group and protonated at N(1)' is denoted as (LH)(+)Cl(-); therefore, the ligand monoprotonated at the phosphate group and deprotonated at N(1)' is L]. Complexes of formulae MLCl(2), M(LH)Cl(3), and (MCl(4))(2)(-)(LH)(2)(+) (M = Zn(2+), Cd(2+), and Hg(2+)) were isolated in aqueous and methanolic solutions, depending on pH. The crystal structure of the complex of formula HgL(2)Cl(2) was solved, together with that of the free ligand (LH)(+)Cl(-), by X-ray crystallography. HgL(2)Cl(2) crystallizes in C2/c, with a = 32.968(6) ?, b = 7.477(2) ?, c = 21.471(4) ?, beta = 118.19(1) degrees, V = 4665(2) ?(3), and Z = 4. (LH)(+)Cl(-) crystallizes in Cc, with a = 10.951(3) ?, b = 17.579(4) ?, c = 13.373(3) ?, beta = 105.36(2) degrees, V = 2482.4(10) ?(3), and Z = 4. Mercury(II) binds to the N(1') of the pyrimidine ring. Both ligands are in the S conformation [Phi(T) = -98.1(9) degrees and Phi(P) = 176.1(10) degrees for HgL(2)Cl(2) and Phi(T) = 104.1(5) degrees and Phi(P) = 171.9(6) degrees for (LH)(+)Cl(-)]. (31)P and (13)C NMR spectra, together with vibrational spectra (IR/Raman), are used to deduce the binding sites of the metal and the protonation states of the ligand at various pH values. It is found that solid-state (31)P NMR spectroscopy is particularly useful in characterizing these complexes as the (31)P shielding tensors are sensitive to the state of the phosphate group. On the other hand, the (31)P NMR spectra indicate that direct bonding between Zn(2+) and Cd(2+) to the phosphate can occur under certain preparation conditions. Solid-state (13)C NMR and vibrational (IR/Raman) spectroscopic results are also in agreement with the other techniques.     

Proficiency testing in analytical chemistry, microbiology and laboratory medicine: working group discussions on current practice and future directions

A summary of the working group (WG) discussions on proficiency testing (PT) and external quality assessment (EQA) held at the joint EURACHEM/CITAC/EQALM workshop, Bracknell, UK, 16–18 February 2003 is provided. The nine WGs covered a range of issues concerned with current practice and future directions; PT/EQA as a tool for regulators (WG1); PT/EQA as a tool for accreditation (WG2); evaluation of performance and uncertainty (WG3); frequency of PT/EQA participation (WG4); selection of appropriate PT/EQA schemes (WG5); added value of PT/EQA and cost benefit evaluation (WG6); global harmonisation and rationalisation (WG7); new technical areas and challenges in PT/EQA (WG8); and accreditation of PT/EQA providers (WG9). Participants with different backgrounds were on each WG in order to capture a range of views and experience from different sectors. The discussions reflected on the keynote lectures and built, in many cases, on discussions at previous workshops in 2000 and 2002.     

PHOTOTHROMBOSIS USING TWO DIFFERENT PHTHALOCYANINE ADMINISTRATION ROUTES: CONTINUOUS I.V. INFUSIO versus BOLUS I.V. INJECTION*

Chloraluminum sulfonated phthalocyanine was administered in 22 albino rabbits either by means of bolus i.v. (intravenous) injection (6 mg/kg) or as continuous i.v. infusion. Eight animals were used for the comparison of plasma phthalocyanine change as a factor of time, using the two administration methods. Photothrombosis of corneal neovascularization was carried out in the remaining 14 animals either after bolus phthalocyanine injection or after continuous i.v. infusion. Irradiation of the right eye's vessels started 10 min after the injection in the bolus group and 35 min after initiation of infusion in the continuous infusion group. The vessels of each animal's left eye were irradiated 1 h after the irradiation of the right eye. The initial peak of phthalocyanine concentration after bolus injection was followed by a rapid decrease of plasma levels. In the continuous infusion group,30–40 min after the initiation of infusion, plasma phthalocyanine concentration reached a plateau that remained stable for the rest of the80–90 min of infusion. Using bolus injection, a significant decrease of phthalocyanine concentration was accompanied by a significant increase of irradiation time necessary for neovascularization thrombosis in the two eyes. Irradiation time as well as phthalocyanine concentration did not differ between the two eyes using continuous infusion. Vascular photosensitivity seemed to be higher using continuous i.v. infusion of phthalocyanine. Continuous i.v. infusion represents an interesting alternative to bolus injection for phthalocyanine-mediated corneal neovascularization photothrombosis.