Three-dimensional Schwarzschild spacetimes

In the following we find all of the three-dimensional flat spacetimes which are static and rotationally symmetric.     

Sufficient conditions of non‐uniqueness for the Coulomb friction problem

We consider the Signorini problem with Coulomb friction in elasticity. Sufficient conditions of non‐uniqueness are obtained for the continuous model. These conditions are linked to the existence of real eigenvalues of an operator in a Hilbert space. We prove that, under appropriate conditions, real eigenvalues exist for a non‐local Coulomb friction model. Finite element approximation of the eigenvalue problem is considered and numerical experiments are performed. Copyright © 2003 John Wiley & Sons, Ltd.     

2,4,6‐Trifluoropyrimidine. Reactions with nitrogen nucleophiles

In a continuation of our studies involving the nucleophilic displacement of one of the chlorines from 2,4,6‐trichloropyrimidine, we now report the initial displacement of one of the fluorine atoms from 2,4,6‐trifluoropyrimidine using both aliphatic and aromatic amines. The monosubstitution products favor 2‐substitution with ammonia and ethanolamine while aniline gave the 4‐substituted derivative as the preferred product.     

The interaction between TEOS and some polyols

Hybrid organic-inorganic materials, silica – polyols (ethylene-glycol – EG; 1,2 propane diol – 1,2PG; 1,3 propane diol – 1,3PG and glycerol – GL), were prepared by a sol-gel process starting from tetraethylorthosilicate (TEOS) and polyols, in acid catalysis. The resulting materials were studied by thermal analysis (in air and nitrogen), FTIR and solid state ²⁹Si-NMR spectroscopy. These techniques evidenced the presence of polyols in the silica matrix both hydrogen bounded and chemically bounded in the silica network. The thermal analysis proves to be the most appropriate technique to evidence the organic chains linked in the matrix network and to follow the thermal evolution of the gels to the SiO₂ matrix.     

Pyrimidine N-oxides. Preparation of 6-chloro-2,4-diaminopyrimidine 3-N-oxide and its reactions

The peroxyacid oxidation of 6-chloro-2,4-diaminopyrimidine ( 1 ) led to two products, 6-chloro-2,4-diaminopyrimidine 3-N-oxide ( 2 ) and 2,4-diamino-5,6-dichloropyrimidine 3-N-oxide ( 3 ). The assignment of structure of both of these compounds was made on the basis of ir, uv, nmr, and mass spectral data. A discussion of the pathways involved in the formation of 3 is presented.     

Use of an ion-selective membrane electrode for the determination of the active components in intestopan

The conditions for the determination of broxyquinoline and brobenzoxaldine, the active components of "Intestopan", by use of ion-selective membrane electrodes are described. Broxyquinoline is determined directly through precipitation with CuSO(4), and brobenzoxaldine is first hydrolysed in alkaline solution and the product precipitated with CuSO(4). In both cases the CuSO(4) in excess is determined by potentiometric titration at pH 5.6 with EDTA, a Cu(2+)-selective electrode being used for end-point detection.     

Parametric analysis of oscillatory oxidation reactions

A complete parametric analysis, concerning an overall kinetic model for oscillating catalytic deep oxidation of alcohols, carbon monoxide or hydrogen, is presented. The model contains four parameters.     

(Fluoren-9-ylidene)methanedithiolato complexes of platinum: synthesis, reactivity, and luminescence

Platinum(II) complexes with (fluoren-9-ylidene)methanedithiolato and its 2,7-di-tert-butyl- and 2,7-dimethoxy-substituted analogues were obtained by reacting different chloroplatinum(II) precursors with the piperidinium dithioates (pipH)[(2,7-R2C12H6)CHCS2] [R = H (1a), t-Bu (1b), or OMe (1c)] in the presence of piperidine. The anionic complexes Q2[Pt{S(2)C=C(C12H6R(2)-2,7)}2] [R = H, (Pr(4)N)(2)2a; R = t-Bu, (Pr4N)(2)2b, (Et4N)(2)2b; R = OMe, (Pr4N)(2)2c] were prepared from PtCl(2), piperidine, the corresponding QCl salt, and 1a-c in molar ratio 1:2:2:2. In the absence of QCl, the complexes (pipH)(2)2b and [Pt(pip)(4)]2b were isolated depending on the PtCl(2):pip molar ratio. The neutral complexes [Pt{S2C=C(C12H6R(2)-2,7)L(2)] [L = PPh(3), R = H (3a), t-Bu (3b), OMe (3c); L = PEt(3), R = H (4a), t-Bu (4b), OMe (4c); L(2) = dbbpy, R = H (5a), t-Bu (5b), OMe (5c) (dbbpy = 4,4'-di-tert-butyl-2,2'-bipyridyl)] were similarly prepared from the corresponding precursors [PtCl2L2] and 1a-c in the presence of piperidine. Oxidation of Q(2)2b with [FeCp2]PF6 afforded the mixed Pt(II)-Pt(IV) complex Q2[Pt2{S2C=C[C12H6(t-Bu)(2)-2,7]}4] (Q(2)6, Q = Et4N+, Pr4N+). The protonation of (Pr4N)(2)2b with 2 equiv of triflic acid gave the neutral dithioato complex [Pt2{S2CCH[C12H6(t-Bu)(2)-2,7]}4] (7). The same reaction in 1:1 molar ratio gave the mixed dithiolato/dithioato complex Pr4N[Pt{S2C=C[C12H6(t-Bu)(2)-2,7]}{S2CCH[C12H6(t-Bu)(2)-2,7]}] (Pr(4)N8) while the corresponding DMANH+ salt was obtained by treating 7 with 2 equiv of 1,8-bis(dimethylamino)naphthalene (DMAN). The crystal structures of 3b and 5c.CH2Cl2 have been solved by X-ray crystallography. All the platinum complexes are photoluminescent at 77 K in CH2Cl2 or KBr matrix, except for Q(2)6. Compounds 5a-c and Q8 show room-temperature luminescence in fluid solution. The electronic absorption and emission spectra of the dithiolato complexes reveal charge-transfer absorption and emission energies which are significantly lower than those of analogous platinum complexes with previously described 1,1-ethylenedithiolato ligands and in most cases compare well to those of 1,2-dithiolene complexes.     

Isomerisation of ω-hydroxyalkenes under hydroxycarbonylation conditions in palladium catalysed aqueous phase systems

The ω-hydroxyolefins 3-buten-1-ol, 3-buten-1-methyl-1-ol and 4-penten-1-ol were subjected to hydroxycarbonylation conditions in water in the presence of PdCl₂(PhCN)₂ and 4-8 equiv. of water soluble tris(3-sodiumsulfonatophenyl)phosphine (TPPTS), or N-bis(N′,N′-diethyl-2-aminoethyl)-4-aminomethylphenyl-diphenylphosphine (N3P). Under conditions of high conversion, the olefins primarily undergo isomerisation through a chain walking mechanism with selectivities for aldehyde ranging from 65% to 98%, with the lower values for longer chain alcohols. The lactones formed as the minor product are almost exclusively branched, indicating that in the first step 2,1-insertion is strongly favoured over 1,2-insertion. In the N3P system also linear lactone is produced at lower conversion. Running the reaction in D₂O produces multiple deuterium incorporation in all positions of the carbon chain. A mechanism is discussed.     

Analytical contributions to the evaluation of painting authenticity from Princely church of Curtea de Arges

The present study contains the analyses performed for pigment samples taken from the Princely church of Curtea de Arges, one of the oldest churches in Romania. The results of our investigations have shown the source of these samples, thus being identified the pigments: natural ultramarine, cinnabar, red earth, and calcium carbonate in the painting from the 14th century, the pigments: lead white, zinc white, and Prussian blue in the repainting from the 19th century and the pigments zinc white, titanium dioxide white, bone white, yellow ochre, red ochre, green earth, artificial ultramarine, and mars red in the interventions carried out in the 20th century. The analyses consisted of light microscopy (LM) and microchemical tests, as well as energy dispersive X-ray (EDX) analysis. This system of analyses allows one to precisely determine the authenticity of certain pigments, thus avoiding the dating errors for different interventions carried out on the original mural painting from the Saint Nicholas Princely church of Curtea de Arges.