Hepatic abscesses.

Hepatic abscesses are potentially lethal diseases if early diagnosis and treatment are not instituted. They are prevalent all over the globe and pyogenic abscesses are predominant over amoebic. With better control of intra abdominal and systemic infections by a spectrum of antibiotics, aetiology of pyogenic abscesses are secondary to interventions and diseases in the biliary tree to a large extent today. The common organisms isolated are the Gram negative group. Amoebic abscesses continue to plague some regions of the world where hygiene and sanitation are questionable. Over the years, diagnosis, treatment and prognosis have evolved remarkably. Imaging modalities like ultrasonography and CT scan have become the cornerstone of diagnosis. The absence of ionizing radiation makes MRI an attractive alternative in patients who require multiple follow up scans. Serological testing in amoebic abscesses has become more reliable. Though antibiotics have remained the principal modality of management, percutaneous drainage of abscesses have vastly improved the chances of cure and bring down the morbidity drastically in pyogenic abscesses. Amoebic abscesses respond well to medical treatment with nitroimidazoles, and minimally invasive surgical drainage is an option in cases where open surgery is indicated.

Perforator flap: A novel method for providing skin cover to lower limb defects.

BACKGROUND: Soft tissue defects in the lower limb pose a formidable challenge due to lack of reliable local flap options. Due to thin non-expendable soft tissues and predisposition to massive edema formation, even small defects become problematic. Perforator flaps represent the latest trends in soft tissue coverage. The aim of this study was to evaluate the effectiveness of perforator flaps as coverage of soft tissue defects in lower limbs. MATERIAL AND METHODS: A series of patients with soft tissue defects of various etiologies in the lower limb were treated using perforator flap at a tertiary care service hospital. Six were free flaps and fourteen pedicled flaps. Doppler ultrasound was used to identify recipient and donor vessels pre-operatively. RESULTS: Only one flap was lost due to venous congestion. In another case of carcinoma penis there was delayed healing due to persistent lymphorrhoea as a result of post-operative status following lymph node dissection and radiotherapy. Fifteen donor sites required split skin grafting, as they could not be closed directly. CONCLUSION: Perforator flaps are a reliable option for closure of soft tissue defects of lower limb irrespective of size, location and depth. There is minimal donor site morbidity. It has the advantage of rapid dissection, flap elevation and reliable skin territory. As no special equipment is required it can be replicated in smaller centers also.

Factores que inciden en la compra de alimentos en distintos ámbitos de comercialización y su relación con la implementación de educación alimentaria nutricional (EAN) / Factors influencing the purchase of foods in different marketing settings, and their relation to the implementation of food and nutrition education (FNE)

La Educación Alimentaria Nutricional (EAN) promueve la adquisición por parte de la población de conductas saludables permanentes relativas a la producción, selección, compra, preparación y utilización de alimentos, valiéndose de variados espacios sociales. Los canales minoristas de comercialización de alimentos urbanos –categorizados en dos grandes grupos: ferias/mercados y supermercados/hipermercados- constituyen espacios potenciales para la EAN, con diferencias importantes entre ellos. Los primeros ofrecerían canales de comunicación interpersonales más directos que los segundos. Ambos canales proponen un desafío en cuanto a estrategias y redes comunicacionales alternativas. Los dos escenarios están siendo estudiados para conocer y comprendermotivaciones, conductas, hábitos, orientaciones en las acciones, valores, conocimientos sobre hábitos de alimentación saludables y nutrición; canales de comunicación utilizados; información provista por consumidores y vendedores sobre conductas alimentarias y nutricionales; factores determinantes de la compra de alimentos para, a partir de esos insumos, proponer el desarrollo de posibles intervenciones de EAN. En el marco de un estudio cualitativo exploratorio y descriptivo, trabajando con datos de fuente primaria obtenidos mediante distintas técnicas cualitativas de investigación (observaciones, entrevistas) se plantea como objetivo general identificar y caracterizar distintos factores que influyen en el proceso de selección y compra de alimentos en canales minoristas de comercialización de Capital Federal con la finalidad de plantear acciones posibles de Educación Alimentaria. Se considera que existen diferencias significativas entre estos dos tipos de canales de comercialización y en los clientes que predominantemente concurren a unos y a otros comercios...

Factores que inciden en la compra de alimentos en distintos ámbitos de comercialización y su relación con la implementación de educación alimentaria nutricional (EAN) / Factors influencing the purchase of foods in different marketing settings, and their relation to the implementation of food and nutrition education (FNE)

La Educación Alimentaria Nutricional (EAN) promueve la adquisición por parte de la población de conductas saludables permanentes relativas a la producción, selección, compra, preparación y utilización de alimentos, valiéndose de variados espacios sociales. Los canales minoristas de comercialización de alimentos urbanos ¹categorizados en dos grandes grupos: ferias/mercados y supermercados/hipermercados- constituyen espacios potenciales para la EAN, con diferencias importantes entre ellos. Los primeros ofrecerían canales de comunicación interpersonales más directos que los segundos. Ambos canales proponen un desafío en cuanto a estrategias y redes comunicacionales alternativas. Los dos escenarios están siendo estudiados para conocer y comprendermotivaciones, conductas, hábitos, orientaciones en las acciones, valores, conocimientos sobre hábitos de alimentación saludables y nutrición; canales de comunicación utilizados; información provista por consumidores y vendedores sobre conductas alimentarias y nutricionales; factores determinantes de la compra de alimentos para, a partir de esos insumos, proponer el desarrollo de posibles intervenciones de EAN. En el marco de un estudio cualitativo exploratorio y descriptivo, trabajando con datos de fuente primaria obtenidos mediante distintas técnicas cualitativas de investigación (observaciones, entrevistas) se plantea como objetivo general identificar y caracterizar distintos factores que influyen en el proceso de selección y compra de alimentos en canales minoristas de comercialización de Capital Federal con la finalidad de plantear acciones posibles de Educación Alimentaria. Se considera que existen diferencias significativas entre estos dos tipos de canales de comercialización y en los clientes que predominantemente concurren a unos y a otros comercios...(AU)

Reconstruction in Warfare Injuries.

Traumatic injuries, especially in the combat setting, stress the surgical team that may be sited in a remote forward area, battling against paucity of time, resources and infrastructure. The lone surgeon may be faced with the arduous challenge of saving life. There is seldom thought given to reconstruction in this high-pressure situation. If the patient survives, morbidity for want of reconstruction can be severe and quality of life can suffer significantly. Reconstruction after 3 to 5 days is fraught with complications and usually does compromise outcome in the post-operative phase. The reconstructive surgeon should be involved early in the management as he can provide coverage for large soft tissue defects after aggressive debridement with panache. If the patient is haemodynamically stable, he should be transferred urgently, preferrably by air, to a higher centre with multi-specialty care, especially being equipped with an orthopaedic and trauma reconstructive surgeon. It has been proved beyond doubt that the healing improves significantly and there is marked decrease in morbidity if coverage of wounds is provided early, before colonized wounds get infected.

3D echocardiography: "The most powerful predictor of masked CVD in metabolic syndrome".

UNLABELLED: AIMS & OBJECTIVE: To evaluate the impact of the Metabolic Syndrome (MetS) on various echo variables by 3D Echocardiography. MATERIALS AND METHODS: 100 patients of MetS from indoor and outdoor patient departments were subjected to Echocardiographic and Carotid Doppler evaluation. They were divided into three groups: Group A, Group B and Group C on the basis of age <40 yrs, 40-60 yrs and >60 yrs respectively. The echo variables included left ventricular myocardial performance index (LVMPI), left ventricular mass index (LVMi), left ventricular diastolic dysfunction (LVDD), systolic function (LVEF), left atrial volume index (LAVi) and composite common carotid intima media thickness (CCIMT). RESULTS: The mean LVMPI was abnormal in all the groups and showed an increasing trend with prolonged LVMPI (> 0.4) in 74% of the total population. Prolonged LVMPI in Group A, Group B and Group C were 12.1%, 52.7% and 35.1% respectively. There was also a strong correlation between LVMPI & LVDD (p-value < 0.0001). Only 9% had systolic dysfunction (LVEF < 50%), but 68% of patients had abnormal diastolic function, of which 53% had grade I LVDD, 12% had grade II LVDD and 3% had grade III diastolic dysfunction. None of our patients had grade IV diastolic dysfunction. The mean LA Vi was normal in all the groups, but LAVi increased with worsening LVDD. The mean LVMi indexed to Body Surface Area (BSA) was normal in all the groups, but showed a statistically significant increasing trend from Group A to Group C (p-value < 0.05). Statistically significant higher LVMi values were observed for males as compared to females (p-value < 0.0001). On analysis of patients having left ventricular hypertrophy (LVH), 76% had concentric remodeling; only 11 % had concentric hypertrophy, but none had eccentric hypertrophy. Most of our patients in Group B & Group C had higher mean Composite CCIMT (0.73 +/- 0.33 & 0.84 +/- 0.42 respectively) which was statistically very significant (p-value < 0.001) CONCLUSION: Metabolic Syndrome is associated with masked cardiovascular disease (CVD) as evident by 3D Echo in this series of patients. LVMPI was an early indicator and the most robust marker of early LVDD. Impaired relaxation was highly prevalent; while LAVi was less robust predictor of LVDD in this series of patients. Concentric left ventricular remodeling was the most common pattern of LVH. Most of our series of patients had increased Composite CCIMT. Thus 3D Echocardiography has great potential and is very useful for early detection and timely therapeutic interventions in patients with subclinical CVD in MetS.

Synthesis and structure determination of some sugar amino acids related to alanine and 6-deoxymannojirimycin.

(5'R)-5'-Methyl-5'-[methyl (4S)-2,3-O-isopropylidene-beta-L-erythrofuranosid-4-C-yl]-imidazolidin-2',4'-dione was synthesised starting from methyl 6-deoxy-2,3-O-isopropylidene-alpha-D-lyxo-hexofuranosid-5-ulose applying the Bucherer-Bergs reaction. Its 5'-R configuration was confirmed by X-ray crystallography. Corresponding alpha-amino acid-methyl (5R)-5-amino-5-C-carboxy-5,6-dideoxy-alpha-D-lyxo-hexofuranoside (alternative name: 2-[methyl (4S)-2,3-O-isopropylidene-beta-L-erythrofuranosid-4-C-yl]-D-alanine) was obtained from the above hydantoin by acid hydrolysis of the isopropylidene group followed by basic hydrolysis of the hydantoin ring. Total deprotection afforded 5-C-carboxy-6-deoxymannojirimycin. Analogously, methyl (5S)-5-amino-5-C-carboxy-5,6-dideoxy-alpha-L-lyxo-hexofuranoside and 5-C-carboxy-6-deoxy-L-mannojirimycin were prepared from the corresponding (5'S)-5'-methyl-5'-[methyl (4R)-2,3-O-isopropylidene-beta-D-erythrofuranosid-4-C-yl]-imidazolidin-2',4'-dione starting from methyl 6-deoxy-2,3-O-isopropylidene-alpha-L-lyxo-hexofuranosid-5-ulose.

Copper(II)-mediated oxidative coupling of 2-aminonaphthalene homologues. Competition between the straight dimerization and the formation of carbazoles.

Whereas the Cu(II)-mediated oxidative coupling of 2-aminonaphthalenes 7a and 7b results in the clean formation of 1,1'-binaphthyls 13a and 13b, respectively, their higher homologues and congeners 8-12 have been found to exhibit a different reaction pattern. Thus, 2-aminoanthracene (8) gave a approximately 1:1 mixture of the expected bianthryl derivative 15 and the carbazole 16, whereas the 9-aminophenanthrene (10), 3-phenyl-1-aminonaphthalene (11), and 2-aminochrysene (12) produced almost exclusively the corresponding carbazoles 19, 20, and 21, respectively. By contrast, the isomeric 3-aminophenanthrene (9) gave rise to the azo compound 17 as a result of the preferential oxidation on the nitrogen. The carbazoles have been shown to arise directly from the coupling reactions rather than from the primarily formed binaphthyls. Alternatively, carbazole 19 can also be prepared from 1b on reaction with hydrazine. On the other hand, treatment of 3a with hydrazine resulted in the formation of a approximately 2:7 mixture of amine 11 and arylhydrazine 22. 2,2'-Diamino-1,1'-bianthryl (15) has been resolved into enantiomers via cocrystallization with (-)-N-benzylcinchonidinium chloride and shown to have (R)-(-)-15 configuration by X-ray crystallography.

Preparation and structure determination of two sugar amino acids via corresponding hydantoin derivatives.

(4R)-2,3-O-Isopropylidene-methylspiro[4,6-dideoxy-alpha-L-lyxo+ ++-hexopyranosid-4,5'-imidazolidin]-2',4'-dione and (4R)-2,3-O-isopropylidene-methylspiro[4,6-dideoxy-beta-D-ribo-h exopyranosid-4,5'-imidazolidin]-2',4'-dione were prepared under various reaction conditions starting from methyl 6-deoxy-2,3-O-isopropylidene-alpha-L-lyxo-hexopyranosid-4-++ +ulose. Corresponding alpha-amino acids methyl (4R)-4-amino-4-C-carboxy-4,6-dideoxy-alpha-L-lyxo-hexopyranosid e and methyl (4R)-4-amino-4-C-carboxy-4,6-dideoxy-beta-D-ribo-hexopyranoside were obtained from the above hydantoins by selective acid hydrolysis of the isopropylidene group, followed by basic hydrolysis of the hydantoin ring. The crystal structures of both hydantoin derivatives are also presented.

PINDY: A novel, pinene-derived bipyridine ligand and its application in asymmetric, Copper(I)-catalyzed allylic oxidation

The title bipyridine ligand (+)-6(PINDY), prepared in five steps from (-)-beta-pinene, forms a stable complex with CuCl(2) (8) that has been characterized by X-ray crystallography to reveal an unusual geometry at Cu. Triflate 9 proved to catalyze asymmetric allylic oxidation (10 --> 11; rt, approximately 30 min, 49-75% ee).

Absolute configuration of a diaryldiacyloxy spiroselenurane and resolution of a carbon analog.

The enantiomers of 3,3'-spirobi(3-selenaphthalide) (2) were obtained via direct separation by liquid chromatography on a chiral stationary phase. Determination of the absolute configuration was made by X-ray crystallography with the use of the anomalous dispersion technique. The first eluted (+)-form (lambda = 302 and 365 nm) of 2 was found to have (S)-configuration. By a comparison of CD-spectra, the same (S)-configuration could be assigned to the (+)-forms of the sulfur (1) and tellurium (7) analogs of 2. An asymmetric dichloro-substituted spirobilactone (4) was also synthesized and separated into its enantiomers. Relative configurations between 4 and its parent compound (3) were established from the corresponding chiroptical data obtained. Chirality 12: 71-75, 2000.

Structure of

The crystal structure of the title compound, dimethylammonium tetrachlorocobaltate(II), has been determined at four temperatures between 297 and 366 K, in order to investigate possible phase transitions at 313 and 353 K [Kapustianik, Polovinko & Kaluza et al. (1996). Phys. Status Solidi A, 153, 117-122]. We found that there is no significant change either in the hydrogen-bonding network or in the cell parameters, apart from a linear dilatation with temperature. This study reveals that the anomalous variation in electric conductivity and some of the other physical properties of the compound cannot be explained by structural changes.

Improved hardware and software for single-crystal NMR spectroscopy.

Design of state-of-the-art instrumentation and software for acquisition and analysis of single-crystal NMR spectra is presented. The design involves highly accurate rotation of a goniometer, and the acquisition of all the spectra for each rotation axis is automatically controlled by the host computer of the spectrometer using a homebuilt interface between the computer and the single-crystal probe. Moreover, a software package (ASICS) for fast and routine assignment/analysis of complex single-crystal spectra has been developed. Employing this equipment, the acquisition and complete analysis of single-crystal NMR spectra may be performed in about the same time as required for powder methods (spinning or static). The hardware and software are compared to recent alternative approaches within single-crystal NMR. Finally, it has been observed that single-crystal NMR techniques may provide the desired data for samples where powder methods fail.

X-ray structure determination and characterization of the Pseudomonas aeruginosa azurin mutant Met121Glu.

The Met121Glu azurin mutant has been crystallized and the structure determined at a resolution of 2.3 A. In the crystal structure a carboxyl oxygen of Met121Glu is coordinated to the metal at a distance of 2.2 A. Single-crystal resonance Raman spectroscopy was used to show that the glutamic acid residue in the copper site was in the protonated state. Titration of this residue gives rise to a number of unusual, pH-dependent properties: as the pH is increased from 4 to 8, the S(Cys)-Cu ligand-to-metal charge transfer bands are blue shifted and their intensity ratio is reversed, the EPR signal changes from type 1 copper to a new form of protein-bound copper, and the redox potential changes from 370 to 180 mV. The spectroscopic changes in this pH interval are consistent with a two-state model. From the pH dependence of the optical and EPR spectra, pKa = 5.0 for the glutamic acid in the oxidized protein was determined.

The metal site of Pseudomonas aeruginosa azurin, revealed by a crystal structure determination of the Co(II) derivative and Co-EPR spectroscopy.

The crystal structure of cobalt-substituted azurin from Pseudomonas aeruginosa has been determined to final crystallographic R value of 0.175 at 1.9 A resolution. There are four molecules in the asymmetric unit in the structure, and these four molecules are packed as a dimer of dimers. The dimer packing is very similar to that of the wild-type Pseudomonas aeruginosa azurin dimer. Replacement of the native copper by the cobalt ion has only small effects on the metal binding site presumably because of the existence of an extensive network of hydrogen bonds in its immediate neighborhood. Some differences are obvious, however. In wild-type azurin the copper atom occupies a distorted trigonal bipyramidal site, while cobalt similar to zinc and nickel occupy a distorted tetrahedral site, in which the distance to the Met121,S(delta) atom is increased to 3.3-3.5 A and the distance to the carbonyl oxygen of Gly45 has decreased to 2.1-2.4 A. The X-band EPR spectrum of the high-spin Co(II) in azurin is well resolved (apparent g values gx' = 5.23; gy' = 3.83; gz' = 1.995, and hyperfine splittings Ax' = 31; Ay' = 20-30; Az' = 53 G) and indicates that the ligand field is close to axial.

Mutant Met121Ala of Pseudomonas aeruginosa azurin and its azide derivative: crystal structures and spectral properties.

The crystal structures of the azurin mutant Met121Ala and its azide derivative Met121Ala-azide from Pseudomonas aeruginosa have been determined. The final crystallographic R values are 21.3 and 19.4% for the two structures, respectively. In the Met121Ala mutant, the distance between the copper ion and His117 increases by 0.34 A compared with the wild-type structure. The removal of the methionine in the apical position induces a shortening of the distance from the copper ion to the carbonyl O atom of Gly45 from 2.97 to 2.74 A. In the Met121Ala-azide structure, the azide anion occupies the cavity created by replacing the Met121 side chain with the smaller methyl group of Ala. The azide anion binds with a terminal N atom to the copper ion at a distance of about 2.04 A. In addition, the copper ion has moved out of the trigonal plane by about 0.26 A towards the azide anion. Thus, the copper site in this structure has a distorted tetrahedral arrangement. The spectroscopic characteristics show, in addition, that the copper sites in the two structures are distinctively different. The Met121Ala mutant still maintains the properties of an ordinary type 1 copper site while the Met121Ala-azide derivative has an absorption maximum at about 409 nm and the copper hyperfine coupling has increased to a value intermediate between those of type 2 copper and the wild-type azurin.

Structure of the azurin mutant nickel-Trp48Met from Pseudomonas aeruginosa at 2.2 A resolution.

The structure of the azurin mutant nickel-Trp48Met from Pseudomonas aeruginosa has been determined by difference Fourier synthesis using phases from the wild-type azurin model. The final crystallographic R value is 0.170 for 17 394 reflections to a resolution of 2.2 A. The mutant crystallized in the orthorhombic space group P2(1)2(1)2(1), a = 57.4, b = 80.4, c = 110.3 A. The four molecules in the asymmetric unit are packed as a dimer of dimers. The nickel metal site of this mutant structure is similar to the zinc metal site in the azurin Asp47 mutant. The site-specific mutation was performed at residue Trp48, which is located in the center of the protein in a highly hydrophobic environment, to investigate its suggested role in the long-range electron-transfer pathway between the disulfide bond on one side of the protein to the Cu centre. The structure around the mutation site Met48 showed no significant change compared with the wild-type structure.

Structure of the azurin mutant Phe114Ala from Pseudomonas aeruginosa at 2.6 A resolution.

The crystal structure of azurin mutant Phe114Ala from Pseudomonas aeruginosa has been solved by molecular replacement. The final crystallographic R value is 0.185 for 9832 reflections to a resolution of 2.6 A. The root-mean-square deviation for main-chain atom positions is 0.020 A between the four independent monomers in the asymmetric unit. The mutant Ala114 crystallized from PEG 4000 in a new crystal form and the crystals are monoclinic, P2(1), a= 51.0, b = 83.6, c= 66.4 A and beta = 110.5 degrees. The four molecules in the asymmetric unit are packed as a dimer of dimers and are related by an approximate twofold axis. The dimer packing and the dimer contact region are very similar to that of the Alcaligenes denitrificans azurin dimer. The mutation was performed at residue Phe114, which exhibits a pi-electron overlap with the copper ligand His117, to investigate its suggested role in the electron self-exchange reaction. Removal of steric constrains from the phenylalanine side chain created a somewhat different geometry around the copper site with an increased mobility of His117 resulting in an enlarged Cu-N length which may be responsible for the slight differences obtained in the spectral properties of the mutant versus the wild-type protein.