Thrombolysis in a case of lateral medullary syndrome: CT angiographic findings.
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Biomedical subjects
Publications and source records attributed to S Prabhakar.
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Electrospray ionisation mass spectrometry studies and quantum chemical calculations indicate that bidentate ligation of Li+ ion to the diamines leads to symmetric bridging and exhibits contrasting relative affinity orderings compared to that of proton for alpha,omega-diamines.
Dimeric complex ions of the type [M(A-H)A]+, where M=metal ion (Co, Ni, Cu, and Zn) and A=ligand (lactic acid, methyl lactate or ethyl lactate), were generated in the gas phase under electrospray ionization conditions. The collision-induced dissociation spectra of [M(A-H)A]+ ions were recorded to study the behaviour of ligand and metal ions in decomposition of these dimeric complex ions. Based on the fragmentation pathways observed for complex ions of lactic acid, it is found that both the carboxylic and hydroxyl groups of lactic acid are involved in the complex formation following displacement of a proton by the metal ion. The dimeric complex ions of Co, Ni, and Zn dissociated to yield similar types of ions, whereas that of Cu behaved differently. The dissociations of Co-, Ni-, and Zn-bound dimeric complexes involved losses of neutral molecules while keeping the oxidation state of the metal ion unchanged. However, elimination of radicals is found in the dissociation of dimeric complex ions of Cu, and the oxidation state of copper is reduced from Cu(II) to Cu(I) in the resulting fragment ions. The deprotonated ligand is involved in the fragmentation pathway of Cu complexes, whereas it is intact in other complexes. The oxidation state of the metal ion, nature of the ligand, and site of attachment to the metal ion are found to control the dissociation of these dimeric complex ions.
The complexes of transition-metal ions (M2+, where M = Fe, Co, Ni, Cu, Zn, Cd, and Hg) with 2-acetylbenzimidazolethiosemicarbazone (L) are studied under electrospray ionization (ESI) conditions. The ESI mass spectra of Fe and Co complexes showed the complex ions corresponding to [M+2L-2H]+, and those of Ni and Zn complexes showed [M+2L-H]+ ions, wherein the metal/ligand ratio is 1:2 and the oxidation state of the central metal ion is +3 in the case of Fe and Co and +2 in the case of Ni and Zn. The Cd and Cu complexes showed preferentially 1:1 complex ions, i.e., [M+L-H]+ or [M+L+Cl]+, whereas Hg formed both 1:1 and 1:2 complex ions. During formation of the above complex ions one or two ligands are deprotonated after keto-enol tautomerism, depending on the nature and oxidation state of central metal ion. The structures and coordination numbers of the metal ions in the complex ions were studied by their collision-induced dissociation spectra and ion-molecule reactions with acetonitrile or propylamine in the collision cell. Based on these results it is concluded that Fe, Co, Ni and Zn form stable octahedral complexes, whereas tetrahedral or square planar complexes are formed preferentially for other metals. In addition, the Cu complex showed a [2L+2Cu-3H]+ ion with a Cu-Cu bond.
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BACKGROUND: Hyperhomocysteinemia has been proposed as an important risk factor for ischemic stroke worldwide, but data available from the Indian subcontinent is scarce. AIM: To study homocysteine levels in patients with ischemic stroke and compare it with age- and sex-matched controls. SETTINGS AND DESIGN: Case-control prospective study. MATERIALS AND METHODS: Fifty-seven patients with ischemic stroke and 30 controls were recruited for the study. They were subdivided into two subgroups (< 40 years and> 40 years of age) and plasma fasting total homocysteine (tHcy) levels were measured. STATISTICAL ANALYSIS USED: Student's 't' test and chi-square test. RESULTS: The tHcy were significantly high in patients with stroke, compared to controls (9.91 +/- 2.25 vs 8.00 +/- 2.74 micromol/l; P vs 8.45 +/- 2.72 micromol/l; P = 0.01) and female patients compared to controls (9.08 +/- 1.81 vs 6.79 +/- 2.60 micromol/l; P = 0.04). The tHcy levels were significantly high in patients with hypertension compared to normotensive patients (10.96 vs 9.49 micromol/l; P = 0.01) and smokers compared to nonsmokers (11.17 vs 9.33 micromol/l; P = 0.01). CONCLUSIONS: Hyperhomo-cysteinemia emerged as an important independent risk factor for ischemic stroke. A strong positive correlation was also observed between hypertension, smoking, and high-tHcy levels in the present study.
BACKGROUND AND OBJECTIVES: The clinical diagnosis of neurosyphilis is very rarely encountered today in the developed world although syphilis remains a significant health problem in few areas of the industrialized countries and in most of the third world nations. This apparent decline may be due to increase in number of asymptomatic neurosyphilis and cases presenting as subtle, illdefined syndromes rather than classic presentation of tabes dorsalis and general paresis in the post penicillin era. This retrospective study was carried out to report the neurosyphilis cases diagnosed at a tertiary care hospital in North India, and to analyse the laboratory and clinical parameters of these cases. METHODS: Suspected cases of neurosyphilis presenting at Postgraduate Institute of Medical Education and Research (PGIMER), Chandigarh over a period of 13 yr (January 1990 to December 2002) were identified. Diagnosis of neurosyphilis was based on clinical presentation, prior history of syphilis, routine CSF biochemistry (protein and leukocytes) and serological evidence [serum and CSF venereal disease research laboratory (VDRL) and Treponema pallidum particle agglutination (TPPA) tests]. RESULTS: A total of 25 cases of neurosyphilis were identified, 18 (72%) with reactive CSF-VDRL, 22 (88%) with elevated CSF protein and 24 (96%) with CSF mononuclear leukocytosis. Serum VDRL was reactive in all 25 cases. Three patients were asymptomatic (2 primary syphilis; 1 early latent stage), 8 had secondary and 14 had tertiary syphilis. Two of the neurosyphilis cases were also seropositive for HIV. Radiology was abnormal in 7 (28%) patients. INTERPRETATION AND CONCLUSION: Neurosyphilis still remains a problem in a country like India and a high index of suspicion and clinical expertise are required for appropriate diagnosis and proper management especially in the era of AIDS pandemic.
A simple method to differentiate underivatized diastereomeric hexosamine monosaccharides, glucosamine, galactosamine, and mannosamine is reported by applying the kinetic method using N-acetylhexosamines or naturally occurring amino acids as reference bases under electrospray ionization conditions. The observed differences to distinguish the diastereomeric hexosamines are found mainly due to the proton affinity (PA) differences between the analyte and the reference base. The PA values of the hexosamines are not available in the literature, and hence, we estimated them by the kinetic method using N-acetylhexosamines as reference bases. The determined PA values are 223.97 kcal/mol for glucosamine, 224.99 kcal/mol for mannosamine, and 224.71 kcal/mol for galactosamine. The similar PA values were also obtained by using amino acids as reference bases. We have applied the same methodology to quantify these hexosamines in a mixture following the three-point calibration method suggested in the literature.
The removal of various species of sulfur from beamhouse of tannery wastewater and also from synthetic samples was studied by electro-flotation technique. Consumable anodes of iron and aluminum and insoluble anode of titanium were tested as anodes. It was found that iron and aluminum anodes were effective for the removal of suspended solids, sulfide, sulfite and sulfate. Progress of simultaneous coagulation of suspended solids during electro-flotation was measured using particle size analysis. Coagulation was found to be essential for effective flotation of suspended solids. Metal ions generated in situ by electrolytic oxidation of anode were found to react with dissolved sulfide ions. Metal sulfides thus formed as colloidal suspension were coagulated and floated simultaneously by hydrogen bubbles generated from cathode. Simultaneous occurrence of precipitation, coagulation and flotation was observed during electro-flotation. X-ray diffraction studies were conducted to identify the nature of sulfide phase formed during electrolytic precipitation. The effect of pH, current density and initial concentration of pollutants was studied and the results are discussed. The removal of sulfite and sulfate ions is explained by zeta-potential measurements.
A solid-phase extraction (SPE) method involving selective usage of solvents has been developed for trace level identification of chemical warfare agents (CWAs) present in a complex organic background. The total ion chromatograms obtained from direct gas chromatography-electron ionization mass spectrometric analysis of samples spiked with CWAs in the presence of diesel are very complex and dominated by hydrocarbon peaks and the same after treatment with SPE show distinct peaks corresponding to spiked chemicals. The recovery of samples from SPE is found to be 70-85% at the 10 ppm level.
BACKGROUND: Epidemiology of acute stroke in developing countries differs from that in the developed world, for example, the age at stroke, risk factors, subtypes of stroke and prognosis. Hypertension remains a dominant risk factor and prognostic indicator in patients with stroke in all communities. The risk of stroke is directly related to elevations of blood pressure. A number of clinical studies have shown that the control of hypertension leads to a reduction in the incidence of stroke in a community. However there is still considerable controversy surrounds the changes in blood pressure in various subtypes of strokes and problem of management of elevated BP after stroke. We studied the circadian rhythm of blood pressure in patients following acute stroke. METHODS: To study the circadian rhythm of blood pressure, fifty consecutive patients with an acute stroke who were admitted to medical emergency within 120 hours of onset were included in the study. After a detailed history and clinical examination, a continuous blood pressure monitor (Spacelab 90207) was attached on the side ipsilateral to intracranial lesion (unaffected arm). The blood pressure was recorded for 24 hours at 15 minutes interval during daytime (6.00 am-6.00 pm) and 20 minutes interval overnight (6 pm to 6 am). RESULTS: Risk factors for stroke in 50 patients included hypertension in 31(62%), diabetes mellitus in 4 (8%), smoking in 13 (26%) and previous history of transient ischemic attack in 7 (14%) patients. Mean systolic pressure and diastolic pressure at admission were higher in patients with hemorrhagic stroke -29 patients (177 +/- 24 mmHg and 105 +/- 19 mmHg respectively) compared to patients with ischemic strokes-21 patients (150 +/- 36 mm Hg and 89 +/- 18 mm Hg respectively, p value <0.01 in both comparisons). The normal diurnal variation in blood pressure (night time dipping of more than 10%) was abolished in 44 (88%) of patients. Out of 44 nondippers, 29 patients showed reverse dipping i.e. rise of BP during night time compared to day time levels. None of the risk factors, clinical or laboratory variables, type of stroke or blood pressure changes differed significantly between these two groups. CONCLUSIONS: Therefore, we showed a pathologically reduced or abolished circadian BP variation after stroke. Absence of normal dipping results in a higher 24 hour blood pressure load and may have more target organ damage than those with normal diurnal variation of blood pressure.
The negative ion electrospray ionization (ESI) mass spectra of a series of dicarboxylic acids, a pair of isomeric (cis/trans) dicarboxylic acids and two pairs of isomeric (positional) substituted benzoic acids, including a pair of hydroxybenzoic acids, were recorded in the presence of halide ions (F(-), Cl(-), Br(-) and I(-)). The ESI mass spectra contained [M--H](-) and [M+X](-) ions, and formation of these ions is found to be characteristic of both the analyte and the halide ion used. The analytes showed a greater tendency to form adduct ions with Cl(-) under ESI conditions compared with the other halide ions used. The isomeric compounds yielded distinct spectra by which the isomers could be easily distinguished. The collision-induced dissociation mass spectra of [M+X](-) ions reflected the gas-phase basicities of both the halide ion and [M--H](-) ion of the analyte. However, the relative ordering of gas-phase basicities of all analyte [M--H](-) and halide ions could not account for the dominance of chloride ion adducts in ESI mass spectra of the analytes mixed with equimolar quantities of the four halides.
The gas-phase coordination behavior of the [Cr(III)(Salen)]PF(6) complex at the free axial positions has been studied in the presence of amines as ligands (propylamine and a series of diamines) under electrospray ionization conditions. The [Cr(III)(Salen)](+) complex formed stable five- and six-coordinated complex ions, [Cr(III)(Salen)(L)](+) and [Cr(III)(Salen)(L)(2)](+), respectively, where L = solvent molecule or amine. When diamines were used as ligands, abundant [Cr(III)(Salen)(L)](+) ions were observed in which two axial positions of the [Cr(III)(Salen)](+) species are occupied by the two amino groups of the diamine ligand. The relative abundances of ligated complex ions, fragment ions, and solvent adducts of fragment ions in the ESI mass spectra, were found to depend on the cone voltage used to record the spectrum. The ESI mass spectra of [Cr(III)(Salen)](+) in the presence of diamines as ligands, and experiments on ligand-pickup in the collision cell, clearly demonstrated that the [Cr(III)(Salen)(L)](+) complex ion is stable for 1,2-diaminoethane and 1,3-diaminopropane. The stability of [Cr(III)(Salen)(L)](+) ions gradually decreased from 1,4-diaminobutane to 1,6-diaminohexane, and then showed a slight increase for 1,7-diaminoheptane and 1,8-diaminooctane. The collision-induced dissociation spectra of [Cr(III)(Salen)(L)](+) ions support the above observations.
A series of meso-cycloalkyl calix(4)pyrroles (I) and meso-dialkyl calix(4)pyrroles (II) has been studied under electron ionization (EI) mass spectral conditions. All the calix(4)pyrroles showed prominent molecular ions. The cleavage of the C--C bond linked at position 2 of the pyrrole ring (beta-cleavage) is the foremost and dominant fragmentation process. The beta-cleavage process, either through ring opening or directly, results in the loss of an alkyl radical from the molecular ion. The collision-induced dissociation (CID) spectra of I showed specific sequential expulsion of pyrrole and/or cycloalkyl rings from the molecular ion with or without hydrogen migrations, revealing more information on the structure of individual compounds than was available from the EI spectra. The isomeric cycloalkyl calix(4)pyrroles showed distinguishable CID spectra, indicating structure specificity in initial ring opening whereas, in the case of II, the EI mass spectrum contains all the structure-indicative fragment ions. The CID spectra of II resulted in a dominant [M-R]+ ion, with other characteristic ions being less abundant.
A series of O,O-dialkyl N,N-dialkyl phosphoramidates (1-25) were analyzed under GC-EIMS conditions. Clear-cut differences are found in the fragmentation of O,O-dialkyl N,N-dimethyl phosphoramidates (Series 1) and O,O-dimethyl N,N-dialkyl phosphoramidates (Series 2). The phosphoramidates comprising of mixed/crossed alkyl groups on nitrogen and oxygen (Series 3) showed mixed fragmentation pattern corresponding to both Series 1 and 2 depending on the nature of alkyl groups. All the possible isomers among the studied compounds showed distinguishable EI mass spectra. Although the major ions in the EI mass spectra for the isomers containing O-n-propyl or O-isopropyl and N,N-diethyl or N-isopropyl N-methyl are similar, the isomers could be distinguished by characteristic ions of low abundance at low mass region. The differences are prominent in the metastable ion spectra of characteristic ions.
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The gene for histone-like protein (hupB [Rv2986c]) of Mycobacterium tuberculosis has been identified as a singular target which allows differentiation of two closely related mycobacterial species, namely, M. tuberculosis and M. bovis of the MTB complex, by a PCR assay. The N and S primer-generated PCR amplicons differed in M. tuberculosis and M. bovis; these amplicons were determined to be 645 and 618 bp, respectively. This difference was localized to the C-terminal part of the gene by using primers M and S. The C-terminal PCR amplicons of M. tuberculosis and M. bovis were determined to be 318 and 291 bp, respectively. The differences in the C-terminal portion of the gene were confirmed by restriction fragment length polymorphism analysis and sequencing. Sequence analysis indicated that in M. bovis there was a deletion of 27 bp (9 amino acids) in frame after codon 128 in the C-terminal part of the hupB gene. In the present study 104 mycobacterial strains and 11 nonmycobacterial species were analyzed for hupB gene sequences. Of the 104 mycobacterial strains included, 62 belonged to the MTB complex and 42 were non-MTB complex strains and species. Neither the hupB gene-specific primers (N and S) nor the C-terminal primers (M and S) amplify DNA from any other mycobacteria, making the assay suitable for distinguishing members of the MTB complex from other mycobacterial species, as well as for differentiating between members of the MTB complex, namely, M. tuberculosis and M. bovis.
BACKGROUND: Low serum sodium is uncommon in peritoneal dialysis (PD), which is surprising in view of the important role of normal kidney function to regulate water and sodium balance. METHODS: We report 2 cases of persistent hyponatremia with balance studies in Case 1. We performed measurements of dialysate sodium and volume output over 24 hours in a group of chronic PD patients. RESULTS: The low serum sodium concentration did not vary too much with overall fluid removal via dialysis in patient 1, mainly because large quantities of sodium were removed in the dialysate. In the 24-hour studies, a significant relationship was found between net daily PD sodium removal and net daily dialysate volume removed (r = 0.65). There was no relationship between net daily PD sodium removal and serum sodium concentration. There was a linear direct correlation between serum and dialysate sodium concentration (r = 0.8) as shown by others previously. CONCLUSIONS: These results suggest that the main determinant of PD sodium loss is net dialysate ultrafiltration volume. Water loss via dialysis is necessarily associated with sodium loss. In order to maintain a normal serum sodium concentration salt intake must be proportional to the water loss induced by dialysis. The stimuli that allow dialysis patients to maintain this delicate balance between water and salt intake are of considerable interest but remain undetermined.