Synthesis, spectral, thermal and anti-fungal studies of organotin(IV) thiohydrazone complexes.

The reaction of tribenzyltin(IV) chloride and di(para-chlorobenzyl)tin(IV) dichloride with thiohydrazones derived by condensation of 2-phenylethyl N-thiohydrazide with benzaldehyde, salicaldehyde, p-methylacetophenone and cinnamaldehyde have been investigated in 1:1 molar ratio. These ligands act as neutral, bidentate species and coordinate to the central tin (IV) atom through the thiosulphur and azomethine nitrogen. The newly synthesized complexes have been characterized by elemental analysis and molecular weight determination. The mode of bonding of the complexes has been suggested on the basis of infrared, electronic and (1)H NMR spectroscopy, and probable structures have been assigned to these complexes. Phenomenological and kinetic parameters have been calculated using thermogravimetric (TG) and differential thermal analytical (DTA) curves and their variations have been correlated with some structural parameters of the complexes. The ligands and their tin(IV) complexes have been screened in vitro for their fungicidal activity against Rhizoctonia solanii and Sclerotium rolfsii and found to be quite active in this respect.

Spectral and thermal studies with anti-fungal aspects of some organotin(IV) complexes with nitrogen and sulphur donor ligands derived from 2-phenylethylamine.

Some complexes of 2-phenylethyl dithiocarbamate, thiohydrazides and thiodiamines with dibenzyltin(IV) chloride, tribenzyltin(IV) chloride and di(para-chlorobenzyl)tin(IV) dichloride have been synthesized and investigated in 1:2 and 1:1 molar ratio. The dithiocarbamate ligand act as monoanionic bidentate and thiohydrazide, thiodiamines act as neutral bidentate ligand. The synthesized complexes have been characterized by elemental analysis and molecular weight determination studies and their bonding pattern suggested on the basis of electronic, infrared, 1H and 13C NMR spectroscopy. Using thermogravimetric (TG) and differential thermal analysis (DTA) various thermodynamic and kinetic parameters viz. reaction order (n), apparent activation energy (Ea), apparent activation entropy (S#) and heat of reaction (DeltaH) have been calculated and correlated with the structural aspects for solid-state decomposition of complexes. The ligands and their tin complexes have also been screened for their fungitoxicity activity against Rhizoctonia solanii and Sclerotium rolfsii and their ED50 values calculated.

Nickel(II) thiohydrazide and thiodiamine complexes: synthesis, characterization, antibacterial, antifungal and thermal studies.

Nickel(II) complexes of type [Ni(L)(2)Cl(2)] and [Ni(L)(2)(OCOCH(3))(2)], where L=N,N-diphenyl-N-thiohydrazide (L(1)) and (N,N-diphenyl-N-thio)-1,3-propanediamine (L(2)), have been synthesized. The thiodiamines coordinate as a bidentate N-S ligand. The synthesized nickel(II) complexes of the thiodiamines were characterized by elemental analysis, IR, mass, electronic and (1)H NMR spectroscopic and TG/DTA studies. Various kinetic and thermodynamic parameters like order of reaction (n), activation energy (E(a)), apparent activation entropy (S(#)) and heat of reaction (DeltaH) have also been carried out for one complex. These complexes were also screened for in vitro antifungal and in vitro antibacterial activities and significant activity have been found.

Synthesis, characterization, cytotoxicity, antibacterial and antifungal evaluation of some new platinum (IV) and palladium (II) complexes of thiodiamines.

Some new platinum (IV) and palladium (II) thiodiamine complexes of type [Pt(L)2Cl2] and [Pd(L)Cl2], [where, L=(cyclohexyl-N-thio)-1,2-ethylenediamine (L(1)) and (cyclohexyl-N-thio)-1,3-propanediamine (L(2))] have been synthesized. The thiodiamines coordinate as a bidentate N-S ligand. The synthesized platinum (IV) and palladium (II) complexes of the thiodiamines were characterized by elemental analysis, IR, mass, electronic and (1)H NMR spectroscopic studies. These complexes were also screened for cytotoxicity, in vitro antifungal and in vitro antibacterial activities. Thermodynamic parameters such as activation energy (Ea), apparent activation entropy (S(#)) and enthalpy change (DeltaH) for the dehydration and decomposition reactions of one complex has also been evaluated.

Platinum (IV) thiohydrazide, thiodiamine and thiohydrazone complexes: a spectral, antibacterial and cytotoxic study.

Some platinum (IV) complexes [Pt(L)2Cl2] [where, L=2-aminopyridine-N-thiohydrazide (L1), (2-aminopyridine-N-thio)-1,3-propanediamine (L2), benzaldehyde-2-aminopyridine-N-thiohydrazone (L3) and salicylaldehyde-2-aminopyrtidine-N-thiohydrazone (L4)] have been synthesized. The thiohydrazides, thiodiamine and thiohydrazones can exist as thione-thiol tautomer and coordinate as a bidentate N-S ligand. The ligands found to act in monobasic bidentate fashion. Analytical data reveals that metal to ligand stoichiometry is 1:2. The complexes have been characterized by elemental analysis, IR, mass, electronic and 1H NMR spectroscopic studies. In vitro antibacterial and cytotoxic study have also been carried out for some complexes.

Clinicopathological and radiological evaluation of cervical lymph node metastasis in head and neck malignancies.

The cervical lymphadenopathy due to metastasis carry poor prognosis. The status of cervical nodes is of critical interest to surgical, radiation and medical oncologists who manage patients with head and neck cancers. We conducted a prospective randomized study to assess the role of palpation, ultrasound and CT in detection of cervical metastasis in 25 patients presented to us with head and neck malignancy irrespective of cervical nodal status. It was observed that clinical examination was least sensitive (73.33%) when compared with computerized tomography (80%) and ultrasound (93.93%). The computerized tomography was found to be most specific (90%) when compared to clinical examination or ultrasonography (70% each).

Synthesis, characterization, antibacterial and cytotoxic study of platinum (IV) complexes.

Platinum (IV) complexes [Pt (L)2Cl2] [where, L= benzyl-N-thiohydrazide (L1), (benzyl-N-thio)-1,3-propanediamine (L2), benzaldehyde-benzyl-N-thiohydrazone (L3) and salicylaldehyde-benzyl-N-thiohydrazone (L4)] have been synthesized. The thiohydrazide, thiodiamine and thiohydrazones can exist as thione-thiol tautomer and coordinate as a bidentate N-S ligand. The ligands were found to act in monobasic bidentate fashion. Analytical data reveal that metal to ligand stoichiometry is 1:2. The complexes have been characterized by elemental analysis, IR, mass, electronic and 1H NMR spectroscopic studies. In vitro antibacterial and cytotoxic studies have been carried out for some complexes. Various kinetic and thermodynamic parameters like order of reaction (n), activation energy (Ea), apparent activation entropy (S#) and heat of reaction (DeltaH) have also been carried out for some complexes.

Organotin(IV) complexes of thiohydrazides and thiodiamines: synthesis, spectral and thermal studies.

Organotin(IV) complexes of tribenzyltin(IV) chloride and di(para-chlorobenzyl)tin(IV) dichloride with thiohydrazides have been reported. The ligands synthesized were bidentate coordinating through sulphur and terminal nitrogen atoms. These form 1:1 metal-ligand complexes. The following organotin(IV) complexes have been synthesized: (C(6)H(5)CH(2))(3)Sn(L(1))Cl, (p-ClC(6)H(4)CH(2))(2)Sn(L(1))Cl(2), (C(6)H(5)CH(2))(3)Sn(L(1))Cl, (p-ClC(6)H(4)CH(2))(2)Sn(L(2))Cl(2), (C(6)H(5)CH(2))(3)Sn(L(3))Cl, (p-ClC(6)H(4)CH(2))(2)Sn(L(3))Cl(2), where (L(1)): 2-phenylethyl N-thiohydrazide, (L(2)): N-(2-phenylethyl-N-thio)-1,3-propane diamine, (L(3)): N-(2-phenylethyl-N-thio)-1,2-ethane diamine. The complexes were synthesized by directly mixing, refluxing and stirring the ligands with organotin(IV) chlorides in a suitable solvent. The complexes were found to be pure and were characterized by elemental analysis, electronic, infrared, (1)H and (13)C NMR spectroscopy. These complexes were also studied for their thermal decomposition by thermogravimetry (TG) and differential thermal analysis (DTA). Various kinetic and thermodynamic parameters, viz. activation energy (E(a)), order of reaction (n), apparent activation entropy (S(#)) and heat of reaction (DeltaH) have been determined by using Horowitz-Metzger method. It was observed that these complexes are highly stable and the thermal degradation of these complexes is a spontaneous process. The ligands and their tin complexes have also been screened for their fungitoxicity activity and found to be quite active in this respect.

In vitro antitumour and antibacterial studies of some Pt(IV) dithiocarbamate complexes.

A few Pt(IV) complexes of the type [Pt(L)(2)Cl(2)] [where L=morpholine dithiocarbamate (L(1)), aniline dithiocarbamate (L(2)), N-(methyl, cyclohexyl) dithiocarbamate (L(3)) and N-(ethyl, cyclohexyl) dithiocarbamate (L(4))] were synthesized. The complexes have been characterized by elemental analysis, molar conductance, IR, electronic, (1)H and (13)C NMR spectroscopic studies. The ligands found to act in monobasic bidentate fashion. Cyclicvoltammetric studies, antibacterial and in vitro antitumour studies were also carried out.

Organotin(IV) complexes of thiohydrazones: synthesis, characterization and antifungal study.

Some new organotin(IV) complexes with salicylaldehyde aniline-N-thiohydrazone (L1) and cinamaldehyde aniline-N-thiohydrazone (L2) of the type (p-ClC6H4)3Sn[L] Cl and (p-ClC6H4)2Sn[L]Cl2 have been synthesized (where L = L1 and L2). The complexes and ligands were characterized by elemental analysis and spectral (UV-vis, IR and 1H NMR) studies. In all the complexes, ligands act as bidentate, coordination through sulphur and azomethane nitrogen. Complexes are 1:1 metal ligands complexes. Antifungal studies of some complexes against Rhizoctonia bataticola fungal strain have been carried out.

Triphenyl phosphine adducts of platinum(IV) and palladium(II) dithiocarbamates complexes: a spectral and in vitro study.

Triphenyl phosphine adducts of dithiocarbamate complexes of platinum(IV) and palladium(II) of the type [Pt(L)2PPh3Cl2] and [Pd(L)2PPh3] [L: morpholine dithiocarbamate (L1), aniline dithiocarbamate (L2) and N-(methyl, cyclohexyl) dithiocarbamate (L3)] were prepared and characterized by elemental analysis, electronic, IR, 1H NMR and 13C NMR spectral studies. Thermal studies of the complexes were carried out. In vitro antitumor activity has been screened towards human adenocarcinoma cell lines and showed significant inhibition even at very low concentration.

Stroke at moderate altitude.

OBJECTIVE: To know the clinical profile, presence of various risk factors for stroke at moderate altitude and to study its relationship with hypertension and polycythemia at moderate altitude. METHODS: We analyzed the data of 100 patients, consecutively admitted to a hospital situated at an moderate altitude of 2200 meters MSL of Sub-Himalayan ranges and studied the age, gender, geographical distribution, clinical features and presence of various risk factors in relation to stroke. This is not only the first study conducted in Himachal Pradesh but also first study in India to be conducted at moderate altitude (2000-3000 meters MSL). RESULTS: Males outnumbered females (66% males, 34% females) with rural predominance (73% rural, 27% urban). Cerebral infarction (69%) was more common but primary intracerebral haemorrhage (26%) was more common than found in the West. Hypertension (62%) and smoking (60%) were most common risk factors present and polycythemia was not a significant risk factor at this altitude. CONCLUSION: Incidence of stroke was found to be lower than the study conducted at low altitude. incidence of various types of stroke was similar to other Indian studies. The combination of opposite effects of decreased hypertension and increased haematocrit could not be demonstrated at this altitude and smoking was more common than in other studies and other risk factors prevalent were same as that for low altitude.

The toxicity of a neem insecticide to populations of culicidae and other aquatic invertebrates as assessed in in situ microcosms.

Microcosm trials were conducted with the botanical insecticide Margosan-O(R) to assess the potential hazards of the product to aquatic organisms. Laboratory chronic bioassays with water from the treated microcosms were conducted to provide an estimate of the residual effect of Margosan-O. Results from chronic tests showed Margosan-O toxicity to be greater in the laboratory exposures than in situ with Culicidae larvae exposed to the same concentrations. Residue analyses of the active ingredient, azadirachtin, determined that it had a half-life of 36 to 48 h in water exposed to natural sunlight. Two applications of Margosan-O at the recommended application rate for pests did not harm aquatic invertebrates that are categorized as planktonic and filter feeding (Culex sp. and Daphnia sp.). However, the benthic invertebrate (Chironomus riparius) was affected by multiple applications of neem. These results show that the use of Margosan-O and possibly other neem extracts in or near aquatic environments could lead to disturbances in benthic populations and may cause decreases in numbers of organisms that are important in food web and nutrient cycling processes.

Serodiagnostic efficiency of phospholipid associated protein of Mycobacterium tuberculosis H37Rv.

The phospholipid-associated protein (55-67 kDa) fraction of Mycobacterium tuberculosis H37Rv was purified as the DE-V protein fraction. This DE-V fraction was used for diagnosis of tuberculosis by enzyme-linked immunosorbent assay (ELISA), detecting IgG antibody in sera collected from different categories of tuberculosis patients, i.e. with acid fast bacilli (AFB) culture-positive pulmonary tuberculosis, with AFB culture-negative, but radiologically suspected, pulmonary tuberculosis, extrapulmonary tuberculosis, and control groups of patients suffering from diseases other than tuberculosis (asthma and/or rhinitis, lepromatous leprosy) as well as from healthy volunteers. Encouraging operational ELISA validity could be achieved with 93% sensitivity, 100% specificity, 97% efficiency, 100% positive predictivity and 95% negative predictability even among the extrapulmonary and suspected pulmonary tuberculosis patients. The above assay was insensitive but with 100% specificity among control group of patients suffering from diseases other than tuberculosis. The DE-V protein fraction was associated with phosphatidyl inositol and phosphatidyl inositol mannosides. The dissociation of phospholipid-protein complex decreased ELISA specificity. ELISA reactivity of the DE-V fraction appeared to be thermostable; thus, it may have serodiagnostic utility in developing countries.

Calmodulin-like activity in mycobacteria.

Calmodulin-like activity has been reported for the first time in mycobacterial species, namely Mycobacterium tuberculosis BCG and M. smegmatis ATCC 14468. The activity was mainly located in the soluble fraction of the mycobacterial cells, Radioimmunoassay revealed maximum levels of calmodulin in young growing cells (early logarithmic phase of growth). Calmodulin-dependent phosphodiesterase activation assay revealed low activity (22%) of partially purified calmodulin either due to insufficient amount of calmodulin to activate phosphodiesterase or due to the presence of some factors interfering with the assay. Calmodulin antagonists, viz. trifluoperazine and phenothiazine, significantly inhibited the 32Pi incorporation into mycobacterial phospholipids. Similar inhibition was observed when EGTA (which removes calcium) was added to the medium. Significant inhibition of 32Pi incorporation in the presence of calmodulin antagonists suggested the involvement of calmodulin in mycobacterial phospholipid metabolism.

Chronic toxicity of a pure and technical grade pentachlorophenol to Daphnia magna.

Chronic toxicity test procedures (static, with renewal) were used to determine the chronic toxicity of sublethal concentrations of a technical formulation of pentachlorophenol (PCP) and pure pentachlorophenol to Daphnia magna. Test organisms 48 +/- 12 h old were exposed for their entire lifespan (i.e., until death) to 0.01, 0.05, 0.1 and 0.5 mg technical PCP/L and 0.01, 0.087 and 0.1 mg pure PCP/L. Criteria used to assess chronic toxicity were mean time to appearance of the primiparous instar in the brood chamber, mean number of days to release of the first brood, mean number of broods produced per female, mean brood size per female, mean number of reproductive days, mean number of young produced per reproductive day per female and survivorship. Pentachlorophenol differentially affected maturation and reproduction but not survivorship or longevity. Mean number of broods produced per daphnid, length of the reproductive period, longevity and survivorship were insensitive criteria relative to mean time to appearance of the primiparous instar, time to release of first brood, brood size, and number of young produced per daphnid per reproductive day. Generally, there was little difference in toxicity of the three concentrations of pure PCP, for they significantly reduced mean brood size and rate of reproduction of young and significantly but differentially affected maturation. Technical PCP, at the highest concentration of 0.5 mg/L, significantly reduced mean brood size and the rate of production of young, and significantly delayed both time to appearance of the primiparous instar and release of the first brood. When differences in toxicity occurred, generally, pure PCP was more toxic than comparable concentrations of technical PCP. Although enhanced maturation was observed there was no compensatory reproduction.(ABSTRACT TRUNCATED AT 250 WORDS)

Role of ultrasonography in patients with normal oral cholecystogram.

The role of real-time ultrasonography was evaluated in 50 randomly selected cases with a strong clinical suspicion of gallbladder diseases and normal oral cholecystogram. Of these, 13(26%) cases showed abnormalities on ultrasonography.

Comparative study of ultrasonography and oral cholecystography in evaluation of gallbladder and biliary tract diseases.

50 cases, aged between 14-60 years, clinically suspected of gall-bladder and biliary tract diseases were evaluated by ultrasonography and oral cholecystography. Ultrasound with a preliminary radiograph of gallbladder region, proved to be more sensitive and reliable procedure than oral cholecystography. Besides providing ancillary information regarding adjacent anatomic structures, it also guided the surgeon to decide preoperatively about the mode of surgery to be employed. Further, from the present study it can be fairly concluded that ultrasound should be used as the primary screening technique for evaluating gallbladder and biliary tract diseases, after plain skiagram of the gallbladder region, since it is non-invasive, more sensitive than OCG and is devoid of use of contrast media and its toxicity.

Serodiagnosis of tuberculosis using purified mycobacterial proteins.

With a view to detect specific M. tuberculosis infection, mycobacterial proteins were purified initially by ammonium sulphate precipitation followed by ion-exchange chromatography. Out of the three fractions, namely P1, P2 and P3 precipitated with increasing concentrations (0-25%, 26-65% and 66-100% respectively) of ammonium sulphate, P2 fraction was found to be more immunoreactive. P2 fraction proteins were further fractionated into five fractions by salt gradient using DEAE-cellulose DE-52 ion-exchange chromatography. Immunoreactivity against tuberculous patients sera of all the fractions was assessed using ELISA test. The last fraction (DE-V) eluted with high salt concentration was found to have a more specific immunoreactive set of proteins within the range of 55 kD to 67 kD molecular weight. Multiple non-specific proteins were distributed in all the other fractions. ELISA test using P2 fraction proteins against tuberculous patients sera showed significantly higher (p less than 0.01) titre even in the absence of any other bacteriological evidence. DE-V fraction of P2 proteins was found to have a significantly high specificity for detecting M. tuberculosis infection in clinically confirmed and suspected tuberculous patients indicating its application in the diagnosis of the disease.