445 research outputs found

    Reactions of organo-rhodium complexes with multidentate N,N and N,S-heterocycles and exchange studies by NMR

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    Dihalobridged binuclear complexes Rh(diolefin)(μ-X)2 {diolefin = 1,5-cyclooctadiene (cod), X = Cl or Br; diolefin = norbornadiene (nbd), X = Cl}, undergo halide bridge cleavage reactions with multidentate N,N-heterocycles 1,3,5-tris(benzimidazolyl)benzene (L1H3), 1,3,5-tris(N-methylbenzimidazolyl)benzene (L2H3) and N,S-heterocycle 1,3,5-tris(benzothiazolyl)benzene (L3H3) to yield trinuclear heterocycle bridged complexes {RhX(cod)}3(μ-LH3) and {RhCl(nbd)}3(μ-LH3) (LH3 = L1H3, L2H3, L3H3). 1H NMR exchange measurements have shown resonances for olefinic protons 1â³, 2â³, 5â³ and 6â³ of cod at different chemical shifts, perhaps due to restricted Rh-N bond rotation. The olefinic and aliphatic protons would undergo exchange with each other and also with intermediate species. The exchange mechanism may be visualized to involve Rh-N bond breaking, rotation of the cod ligand of the T-shaped (three-coordinate) intermediate species followed by recomplexation. An alternate mechanism may be Rh-cod bond breaking at olefin positions 5â³ and 6â³, isomerisation of the T-complex such that 5â³/6â³ moves trans to X coupled with rotation of the heterocycle about the Rh-N bond (made easier by the reduced coordination number of the intermediate), followed by recoordination of 1â³/2â³ trans to N, followed by recomplexation. NMR signals from the intermediate species in one dimensional 1H, 13C and 2D NMR spectra have supported the exchange of protons. © 2009 Elsevier Ltd. All rights reserved

    Synthesis of rhodium(III) complexes with tris/tetrakis-benzimidazoles and benzothiazoles - quick identification of cyclometallation by nuclear magnetic resonance spectroscopy

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    Reactions of rhodium(III) halides with multidentate N, S-heterocycles, (LH3) 1,3,5-tris(benzimidazolyl)benzene (L1H3; 1), 1,3,5-tris(N-methylbenzimidazolyl) benzene (L2H3; 2) and 1,3,5-tris(benzothiazolyl)benzene (L3H3; 3), in the molar ratio 1 : 1 in methanol-chloroform produced mononuclear cyclometallated products of the composition RhX2 (LH2)(H2O) (X = Cl, Br, I; LH2 = L1H2, L2H 2, L3H2). When the metal to ligand (1-3 or 1,2,4,5-tetrakis(benzothiazolyl)benzene L4H2; 4) molar ratio was 2 : 1, the reactions yielded binuclear complexes of the compositions Rh2Cl5 (LH2)(H2O) 3 (LH2 = L1H2, L2H2, L 3H2) and Rh2X4 (L 4)(H2O) 2 (X= Cl, Br, I). Elemental analysis, IR and 1H nuclear magnetic resonance (NMR) chemical shifts supported the binuclear nature of the complexes. Cyclometallation was detected by conventional 13C NMR spectra that showed a doublet around �190 ppm. Cyclometallation was also detected by gradient-enhanced heteronuclear multiple bond correlation (g-HMBC) experiment that showed cross-peaks between the cyclometallated carbon and the central benzene ring protons of 1-3. Cyclometallation was substantiated by two-dimensional 1H- 1H correlated experiments (gradiant-correlation spectroscopy and rotating frame Overhauser effect spectroscopy) and 1H-13C single bond correlated two-dimensional NMR experiments (gradient-enhanced heteronuclear single quantum coherence). The 1H-15N g-HMBC experiment suggested the coordination of the heterocycles to the metal ion via tertiary nitrogen. © 2009 John Wiley & Sons, Ltd

    Internal heat generation effect on mixed convection heat and mass transfer over a vertical heated plate with Soret and Dufour effects

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    Study and analysis of internal heat generation effect of two-dimensional, steady, laminar, heat and mass transfer mixed convection flow of a viscous incompressible fluid from a vertical heated plate embedded in a sparsely packed porous medium with variable fluid properties such as permeability, porosity, thermal conductivity and solutal diffusivity with the Soret and Dufour effects are considered and studied numerically. The boundary layer flow in the porous medium is governed by Lapwood-Forcheimer-Brinkman extended Darcy model. Please download the full abstract below

    GREEN SYNTHESIS OF PYRAZOLO [3,4]-PYRIMIDINE-THIONES USING IONIC LIQUID 2-METHYL-IMIDAZOLIUM-OXALATE AS POTENT EHRLICH ASCITES CARCINOMA RECEPTOR ANTAGONISTS

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    Objective: Pyrazolopyrimidines are heterocyclic molecules containing nitrogen as the main composition, and hence, they exhibit pharmacological efficacy. They are analogs of purines so that possessing wide applications in the field of medicinal chemistry. The main objective of this study is to synthesize different derivatives of pyrazole-pyrimidine classes by adopting simple methodology as well as by employing green chemistry. The purpose of the synthesis of these molecules is to study the antitumor activity against Ehrlich ascites carcinoma (EAC) cell lines. Methods: After literature studies, it makes us to involve in the research of synthetic organic chemistry, especially to synthesize new compounds of pyrazolopyrimidines. We are reported solvent-free synthesis of pyrazolo [3,4-d]-pyrimidine-thiones through ethyl acetoacetate, hydrazine hydrate, thiourea, and different benzaldehydes. An ionic liquid 2-methyl-imidazolium-oxalate catalyzed the reactions under ultrasonication bath. Both conventional and ultrasonic methods were employed and comparison studies have been made. It was found that ultrasonic method completed the reaction quicker than the conventional method. All the synthesized compounds were confirmed their structures by 1HNMR, Fourier transform infrared, 13C-NMR, and elemental analysis spectra. The compounds were tested for in vitro anticancer activity against EAC cell lines. Most compounds revealed significant anticancer activity relative to doxorubicin as a positive control with inhibitory concentration (IC50) values. Results: Ultrasonication method is a simple method under which all the reactions were completed at faster time (<7 min) compared to the convention method. Among eight molecules, 8a and 8d completed the reactions at a faster rate. We reported IC50 values of all the molecules, in which 8e and 8g were exhibited excellent potency against EAC cell lines at different concentrations . Conclusions: Ultrasonication method is an excellent method for the organic synthesis. We are herein reported that under this method, all the reactions are completed within 7 min. Hence, it is superior method than the conventional method. All synthesized molecules have shown good inhibitor potency against EAC cell lines. Among them, two molecules 8e and 8g have shown excellent inhibitor potency

    Functional and radiological outcome in distal radius fractures treated with locking compression plate

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    Background: Fractures of distal end of radius are one of the most common skeletal injuries encountered in orthopaedics. There are various modalities for treatment like close reduction and cast application, external fixators, ORIF with plate etc. CR and cast application or K-wire fixation, external fixation is associated with immobilisation, wrist stiffness, loss of reduction postoperatively. So we performed volar plating for distal end radius fractures and calculated its results.Methods: We performed ORIF with plating (Volar approach) in 35 patients (22 male and 13 female) of distal end radius fractures depending on inclusion and exclusion criteria. Fractures were classified according to AO classification. All patients were operated under tourniquet. Results were analysed using Mayo score.Results: Out of 35 patients, 14 had type A, 16 had type B and 5 had type C fractures (AO classification). Average operative time was 45 minutes and blood loss of 50 ml. Average time to clinico-radiological union was 7 weeks. Average follow up time was 8 months. Average time to wrist mobilisation was 8 days. According to Mayo score, 16 patients had excellent results, 15 had well and 4 had satisfactory results.Conclusions: Volar plating for fracture distal end radius reduces chances of wrist joint stiffness and loss of reduction and good results can be obtained. So in our opinion, volar plating for treatment of fracture distal end radius is good method with excellent outcomes

    Predictors of urinary retention in benign prostate hyperplasia

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    Background: Acute urinary retention (AUR) is one of the most significant complications or long-term outcomes of benign prostatic hyperplasia (BPH). Because of the high prevalence of BPH and its effect on the patient's quality of life, additional research is needed to better predict the risk factors of AUR. The study was aimed to find out the incidence and factors responsible for retention of urine in BPH.Methods: It was a prospective study, conducted at a medical college after the approval from IEC. The study included the patients admitted to the surgical wards admitted with the symptoms of lower urinary tract symptom and presented with acute urinary retention. Duration of the study was 2 months. A total 40 patients were studied over this duration. The outcome of the study was analyzed by these factors: Age in years, Symptom severity, Prostate Volume on DRE and USG Grade.Results: The mean age of presentation was 64.87±7.85 with median age of 65 years (range 45-82 years) with mean IPSS score of 17.45and the mean PVR was 110.80 ± 85.52 with median 110 (range 0-500). Maximum number of patients having Grade 3 and 4 enlargements had PSA level 9-12 ng/ml. The PSA levels and the grade of enlargement on USG were statistically significant (p-0.004).Conclusions: Out of the four factors considered to be the independent risk factors, all of them have positive correlation with the symptom of acute urinary retention. None of these four factors i.e. age in years, symptom severity, prostate Volume on DRE and USG grade could establish significant correlation.

    Pattern of diabetic foot - presentation and complications in rural Indian population

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    Background: Foot ulcer is one of the most common and deadest complications of diabetes mellitus. This is also a frequent cause of hospitalization and disability. Most of the patients with diabetic foot ulcers living in developing countries present to healthcare facilities fairly late with advanced foot ulcers because of poor economic status, inadequate knowledge of self-care, sociocultural reasons and poor and inadequate diabetes healthcare.Methods: A prospective study was conducted in the department of Surgery, JNMC Sawangi (Meghe), Wardha of DMIMS (DU) with the aim to evaluate the pattern of distribution of foot ulcers in diabetic foot patients and related complications. We enrolled 30 diabetic patients in the study, of these 21 (70%) were males and 9 (30%) were females with male to female ratio 2.33.  Results: The mean age of presentation was 52.93 ± 14.10 and the mean duration of diabetes was 8.20 ± 10.06. The maximum numbers of lesion was present in the region of second to fifth metatarsal (53.33%), followed by heel (26.66%) and great toe (10%). Maximum patients 9 (30%) had grade II lesions as per Wagner’s classification and 12 (40%) had II B as per University of Texas diabetic wound classification. Associated deformity was present in 36.66%, insensitivity to the 5.07 S-W monofilaments in 56.66%, impaired vibration in 43.33%, and abnor­mal Achilles tendon reflex in 40%. Ankle–brachial index <0.8 was present in 33.33%. Only 13.33% patients were using customized footwear whereas 46.66% were walking barefoot, the difference was statistically significant P = 0.0027.Conclusion: The health education to promote Knowledge, Attitude, Behavior and Practice (KABP) is essential to prevent diabetes associated foot complications.

    Site selection for vascular access creation in hemodialysis in end stage renal disease

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    Background: Chronic kidney failure is characterized with progressive and irreversible diminishing of glomerular filtration rate. AVF has been unanimously considered the gold standard vascular access of choice for hemodialysis. Arterio-venous fistula (AVF) for hemodialysis should be created in patients with endogenous creatinine clearance < 20 mL/min/1,73m2. Aim of current study was to choose the proper site for arteriovenous fistula creation with minimal complications.Methods: It was a prospective study, carried out in the dept. of surgery from April 2008 to August 2013. A total of 140 patients were studied over the period. The fistulae were created using radial artery cephalic vein side to side and brachial artery cephalic vein side to side or end to side anastomosis. Statistical analysis used: Mean, Standard deviation, Standard error.Results: A total 140 patients were studied, out of them 104 were males and 36 were females. The radiocephalic site was used for 82 (58.57%) patients and 58 (41.43%) patients were operated on brachiocephalic site. The mean inner diameter of radial artery, brachial artery and cephalic vein (intima to intima) at elbow and wrist were 21.49001 ± 0.901 (SE - 0.28492), 3.72533 ± 1.06837 (SE - 0.30841) and 0.68079 ± 0.49551 (SE - 0.116790) respectively. The mean flows velocity of brachial and radial artery were 76.10526 ± 4.54477 (SE - 1.04264) and 52.64286 ± 5.5968 (SE - 1.495810) respectively. The success rate of AV fistula on table was 97.85% (137 out of 140). The incidence of complication was 18.57%.Conclusion: The site for fistula creation depends on the quality of the artery and vein. To achieve good success rates preoperative color Doppler is essential to evaluate the vessels. The complication rates can be minimised by following standard operating protocols.
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