1-Furoyl-3-[3-(trifluoromethyl)phenyl]thiourea

The title compound, C(13)H(9)F(3)N(2)O(2)S, crystallizes with two independent molecules in the asymmetric unit. The central thiourea core is roughly coplanar with the furan and benzene rings, showing O-C-N-C(S) torsion angles of 2.3 (4) and -11.4 (2) degrees and (S) C -N-C-C torsion angles of -2.4 (4) and -28.8 (4) degrees, respectively, in the two independent molecules. The trans-cis geometry of the thiourea fragment is stabilized by an intramolecular N-H center dot center dot center dot O hydrogen bond between the H atom of the cis thioamide and the carbonyl O atom. In the crystal structure, intermolecular N-H center dot center dot center dot S hydrogen bonds form centrosymmetric dimers extending along the b axis.

Redetermination of 1-benzyl-3-furoyl-1-phenylthiourea

The title compound, C(19)H(16)N(2)O(2)S, was synthesized from furoyl isothiocyanate and N-benzylaniline in dry acetone and the structure redetermined. The structure [Otazo-Sanchez et al. (2001). J. Chem. Soc. Perkin Trans. 2, pp. 2211-2218] has been re-determined in order to establish the intramolecular and intermolecular interactions. The thiourea group is in the thioamide form. The thiourea group makes a dihedral angle of 29.2 (6)degrees with the furoyl group. In the crystal structure, molecules are linked by intermolecular C-H center dot center dot center dot O interactions, forming one-dimensional chains along the a axis. An intramolecular N-H center dot center dot center dot O hydrogen bond is also present.

Crystallization and preliminary X-ray diffraction analysis of recombinant chlorocatechol 1,2-dioxygenase from Pseudomonas putida

Chlorocatechol 1,2-dioxygenase from the Gram-negative bacterium Pseudomonas putida (Pp 1,2-CCD) is considered to be an important biotechnological tool owing to its ability to process a broad spectrum of organic pollutants. In the current work, the crystallization, crystallographic characterization and phasing of the recombinant Pp 1,2-CCD enzyme are described. Reddish-brown crystals were obtained in the presence of polyethylene glycol and magnesium acetate by utilizing the vapour-diffusion technique in sitting drops. Crystal dehydration was the key step in obtaining data sets, which were collected on the D03B-MX2 beamline at the CNPEM/MCT - LNLS using a MAR CCD detector. Pp 1,2-CCD crystals belonged to space group P6(1)22 and the crystallographic structure of Pp 1,2-CCD has been solved by the MR-SAD technique using Fe atoms as scattering centres and the coordinates of 3-chlorocatechol 1,2-dioxygenase from Rhodococcus opacus (PDB entry 2boy) as the search model. The initial model, which contains three molecules in the asymmetric unit, has been refined to 3.4 A resolution.

Low-intensity Ultrasound Increases FAK, ERK-1/2, and IRS-1 Expression of Intact Rat Bones in a Noncumulative Manner

Background Low-intensity pulsed ultrasound stimulation (LIPUS) reportedly increases osteogenesis in fracture models but fails in intact bone, suggesting LIPUS does not act on mechanotransduction and growth factor pathways of intact bone. Questions/Purposes We asked whether daily 20-minute LIPUS applied to intact tibias would act on bone proteins involved in mechanotransduction (focal adhesion kinase [FAK], and extracellular signal-regulated kinase-1/2 [ERK-1/2]), and growth factor signaling (insulin receptor substrate-1 [IRS-1]) pathways at 7, 14, and 21 days of treatment. Methods Immunoblotting was performed to detect FAK, ERK-1/2, and IRS-1 expression and activation from the stimulated intact tibias at 7, 14, and 21 days of daily 20-minute LIPUS. Results LIPUS increased FAK expression (at 7 days), ERK-1/2 (at 14 days), and IRS-1 (at 7 days), but expression decreased 7 days later, indicating a noncumulative effect of LIPUS. As only FAK expression was detected at 21 days, these observations suggest LIPUS influences nuclear reactions that may be modulated by a major cellular mechanism preferentially inhibiting IRS-1 expression and not FAK expression. Increased ERK-1/2 expression at 14 days suggests the differing mechanisms for promoting ERK-1/2, FAK, and IRS-1 syntheses. IRS-1 expression behaved similarly to FAK expression; therefore, LIPUS may modulate growth factor pathways. LIPUS increased sustained FAK and ERK-1/2 activation, but not IRS-1, suggesting sustained ERK-1/2 activation is not the result of mechanically induced growth factor activation. Conclusions LIPUS acts on mechanotransduction and growth factor pathways in intact bone in a noncumulative manner. Clinical relevance These data suggest LIPUS applied to intact bone acts on proteins involved in osteogenesis.

Flow boiling heat transfer of R134a and R245fa in a 2.3 mm tube

This paper presents new experimental flow boiling heat transfer results in micro-scale tubes. The experimental data were obtained in a horizontal 2.3 mm I.D stainless steel tube with heating length of 464 mm, R134a and R245fa as working fluids, mass velocities ranging from 50 to 700 kg m(-2) s(-1), heat flux from 5 to 55 kW m(-2), exit saturation temperatures of 22, 31 and 41 degrees C, and vapor qualities ranging from 0.05 to 0.99. Flow pattern characterization was also performed from images obtained by high-speed filming. Heat transfer coefficient results from 1 to 14 kW m(-2) K(-1) were measured. It was found that the heat transfer coefficient is a strong function of heat flux, mass velocity and vapor quality. The experimental data were compared against ten flow boiling predictive methods from the literature. Liu and Winterton [3], Zhang et al. [5] and Saitoh et al. [6] worked best for both fluids, capturing most of the experimental heat transfer trends. (C) 2010 Elsevier Ltd. All rights reserved.

Crystal structure of 1,2-bis(4-fluoro-2-methylphenyl)ditelluride, [Te(C7H6F)](2)

C14H12F2Te2, monoclinic, C12/c1 (no. 15), a = 23.650(2) angstrom, b = 7.792(1) angstrom, c = 7.556(1) angstrom, beta = 106.47(1)degrees, V = 1335.2 angstrom(3), Z = 4, R-gt(F) = 0.041, wR(ref)(F-2) = 0.123, T= 98 K.

Synthesis and characterization of the [Ru(3)O(CH(3)COO)(6)(py)(2)(BPE)Ru(bpy)(2)Cl](PF(6))(2) dimer

The polymetallic [Ru(3)O(CH(3)COO)(6)(py)(2)(BPE)Ru( bpy)(2)Cl](PF(6))(2) complex (bpy = 2,2`-bipyridine, BPE = trans- 1,2-bis(4-pyridil) ethylene and py = pyridine) was assembled by the combination of an electroactive [Ru(3)O] moiety with a [ Ru( bpy) 2( BPE) Cl] photoactive centre, and its structure was determined using positive ion electrospray (ESI-MS) and tandem mass (ESI-MS/MS) spectrometry. The [Ru(3)O(CH(3)COO)(6)(py)(2)(BPE)Ru(bpy)(2)Cl] (2+) doubly charged ion of m/z 732 was mass-selected and subject to 15 eV collision-induced dissociation, leading to a specific dissociation pattern, diagnostic of the complex structure. The electronic spectra display broad bands at 409, 491 and 692 nm ascribed to the [Ru(bpy)(2)(BPE)] charge-transfer bands and to the [Ru(3)O] internal cluster transitions. The cyclic voltammetry shows five reversible waves at - 1.07 V, 0.13 V, 1.17 V, 2.91 V and - 1.29 V (vs SHE) assigned to the [Ru(3)O](-1/0/+ 1/+ 2/+3) and to the bpy (0/-1) redox processes; also a wave is observed at 0.96 V, assigned to the Ru (+2/+ 3) pair. Despite the conjugated BPE bridge, the electrochemical and spectroelectrochemical results indicate only a weak coupling through the pi-system, and preliminary photophysical essays showed the compound decomposes under visible light irradiation.

Functionalization of (2S)-Isopropyl-5-iodo-2,3-dihydro-4(H)-pyrimidin-4-ones by a Suzuki-Miyaura Cross-Coupling Reaction Using Aryltrifluoroborate Salts: Convenient Enantioselective Preparation of alpha-Substituted beta-Amino Acids

A simple protocol for the Pd(OAc)(2)-catalyzed cross-coupling reaction of 1-benzoyl-(2S)-isopropyl-5-iodo-2,3-dihydro-4(H)-pyrimidin-4-ones with potassium aryltrifluoroborates was developed. The reaction is performed at 110 degrees C with a ligand-free catalyst. In all cases, complete conversion of the 1-benzoyl-(2S)-isopropyl-5-iodo-2,3-dihydro-4(H)-pyrimidin-4-ones and aryltrifluoroborates into the C-C coupling products was observed within 30-360 min. It is noteworthy that a large variety of groups present in the potassium aryltrifluoroborates (-CF(3), -OMe, -SEt, -CN, -CHO, -Cl, -Cbz, -NCbz, -OH, -CO(2)H) could be tolerated. Hydrogenation of the endocyclic double bonds in the Suzuki-Miyaura products followed by acid hydrolysis afforded highly enantioenriched alpha-aryl-substituted beta-amino acids.

The line structure of balanced ternary designs with block size three, index three and rho(2) = 1, 2

In this paper necessary and sufficient conditions for a vector to be the fine structure of a balanced ternary design with block size 3, index 3 and rho(2) = 1 and 2 are determined with one unresolved case.

Spin states of C-60(3-) and C120On- (n=2, 3, 4) anions using electron spin transient nutation spectroscopy

Electron spin transient nutation (ESTN) experiments show that the spin multiplicity of the ground state of C-60(3-) in frozen solution is a doublet with S = 1/2. In purified samples, there is no evidence for excited states or other species with higher multiplicity. In the anions Of C120On- (n = 2, 3, 4), where the CW EPR experiments have shown that a mixture of species is present, ESTN experiments confirm that a doublet with S = 1/2 is associated with the 3- anion and triplets with S = 1 are associated with the 2- and 4- anions. A weak nutation peak attributable to m(s) = -1/2 1/2 transitions within a quartet state may arise from association of anions with spins of 1/2 and 1 in solute aggregates.

Stereochemistry of cyclopentane derivatives from (2,3)J(CH) dependence on dihedral angle (theta H-C-C-X)

The (2,3)J(CH) dependence on dihedral angle (theta H-C-C-X) for cyclopentane derivatives was investigated. We observed that the combined use of experimentally obtained (2,3)J(CH) values and the theoretically determined dihedral angles between the corresponding nuclei can be used to infer the relative stereochemistry of the ring substituents in cyclopentane derivatives. There is a good correlation between the magnitude of (3)J(CH) and the dihedral angle between the hydrogen and the coupled carbon (R-2 = 0.88). Copyright (C) 2008 John Wiley & Sons, Ltd.

One-pot synthesis of mixed (Z)-1,2-bis(organylchalcogene)-1-alkenes precursors of the novel beta-organylthio vinyllithium intermediates

One-pot hydrochalcogenation of 1-phenylthioacetylenes using organylselenolate and organyltellurolate anions generated by the insertions of selenium and tellurium in n-organyl lithium produced (Z)-1,2-bis(organylchalcogene)-1-alkenes. The chemical reactivity of these mixed 1,2-bis(organylchalcogene)-1-alkenes was studied by Te/Li and Se/Li stereoretentive exchanges carried out with n-butyl lithium, furnishing the new intermediate species (Z)-beta-organylthio vinyllithium anions, which were trapped with aldehydes, to give the (Z)-3-hydroxy vinyl thioethers with total control of the regio- and stereochemistry. (c) 2010 Elsevier Ltd. All rights reserved.

Serological patterns and temporal trends of HTLV-1/2 infection in high-risk populations attending public health units in Sao Paulo, Brazil

Background: HTLV-1/2 diagnosis in high-risk populations from Sao Paulo, Brazil has been problematic due a high proportion of seroindeterminate results. Objectives: To confirm and extend previous findings regarding HTLV-1/2 diagnosis in this geographic area. Study design: Sera from 2312 patients were tested for HTLV-1/2 antibodies using enzyme immunoassay (EIA) and Western blot (WB) analysis. Patients were from AIDS Reference Centers (Group 1; 1393 patients) and HTLV out-patient clinics (Group 11; 919 patients). Results were analyzed according to patients` age, gender, and clinic type. Results: HTLV-1 and HTLV-2 were detected in both groups. Among seropositive females, HTLV-2 was slightly more common in Group 1 (54.5%), while HTLV-1 prevailed in Group II (73.9%). Males from Group II had a higher percentage of HTLV-seroindeterminate results. No correlation between HTLV serological results and age was detected. Temporal analyses disclosed a high number of HTLV-seroindeterminate samples, and a large spectrum of indeterminate WB profiles. GD21 and/or rgp46-II bands were detected in 34.6% of sera from Group 1, and a p24 or p19 band was detected in 35.3% of sera from Group II. Conclusions: High rates of HTLV-indeterminate serological patterns during temporal analyses were confirmed in high-risk populations from Sao Paulo, Brazil. (c) 2008 Elsevier B.V. All rights reserved.

Reduced Red Cell 2,3-Diphosphoglycerate Concentrations in Critical Illness without Decreased In Vivo P50

We investigated whether red cell 2,3-diphosphoglycerate (2,3-DPG) concentrations are reduced in critical illness, whether acidaemia, hypophosphataemia or anaemia influence 2,3-DPG, and whether there is any net effect on in vivo P50. Twenty healthy, non-smoking, male volunteers were compared with 20 male intensive care patients with APACHE 2 scores > 20 on the preceding day. Those transfused in this time were excluded. Venous red cell 2,3-DPG concentrations were measured in both groups. In the patient group, routine multichannel biochemical profile and arterial blood gas analysis were also performed and in vivo P50 calculated. The mean 2,3-DPG concentration was significantly lower in the patient group than in the controls (4.2 +/-1.3 mmoll/l vs 4.9 +/-0.5 mmol/l, P=0.016). The patients were well oxygenated (lowest arterial PO2=75 mm Hg) and showed a tendency to acidaemia (median pH 7.37, range 7.06 to 7.48) and anaemia (median haemoglobin concentration 113 g/l, range 89 to 154 g/l). By linear regression of patient data, pH had a significant effect on 2,3-DPG concentrations (r=0.6, P=0.011). Haemoglobin and phosphate concentrations did not, but there were few abnormal phosphate values. There was no correlation between 2,3-DPG concentrations and in vivo P50 (r(2) less than or equal to 0.08). We conclude that 2,3-DPG concentrations were reduced in a broad group of critically ill patients. Although this would normally reduce the P50, the reduction was primarily linked with acidaemia, which increases the P50. Overall, there was no net effect on the P50 and thus no affinity-related decrease in tissue oxygenation.

Synthesis of fluorinated 2-phenyl-4-quinolones from pyrrole-2,3-diones

A series of substituted 2-phenyl-4-quinolones 8-11 have been synthesized in good yields via ash vacuum thermolysis (FVT) of 1-aryl-4-cyano-5-phenylpyrrole-2,3-diones 7a-e and 1-aryl-4-methoxycarbonyl-5-phenylpyrrole-2,3-diones 7f-j. The pyrrolediones 7 were prepared from amines 3 and benzoylacetonitriles 5a-e or methyl 3-arylamino-3-phenylprop-2-enoates 5f-j.