Thermal analysis of renal stones

The chemical composition of 200 renal stones, collected from Taxila, Rawalpindi and Islamabad regions in Pakistan, was determined by thermogravimetric (TG) and differential thermal analysis (DTA) techniques. The thermal curves show weight losses at various temperatures indicating dehydration and decomposition phenomena of renal stones. Results were compared with qualitative data obtained by IR analysis which confirmed the chemical composition of various stones in the solid state. The thermal curves helped in the differentiation of various kinds of water held by stones and their chemical composition was obtained by weight loss during pyrolysis. It was found that 26.5% of the stones were pure whewellite, 3% weddellite, 13% uric acid anhydrous, 7.5% struvite, 2.5% ammonium acid urate, 0.5% cystine and 47% stones had mixed composition. In the mixed state the most frequent combinations were those of calcium oxalate with uric acid (14.5%) and with phosphates (27.5%).

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Zusammenfassung Mittels TG und DTA wurde die chemische Zusammensetzung von 200 Nierensteinen untersucht, die in den Gebieten Taxila, Rawalpindi und Islamabad in Indien gesammelt wurden. Die Thermogramme zeigen Masseverluste bei verschiedenen Temperaturen, die auf Dehydratation und Zersetzung der Nierensteine hinweisen. Die Ergebnisse wurden mit den qualitativen Resultaten aus der IR-Analyse verglichen, welche die chemische Zusammensetzung der verschiedenen Steine im festen Zustand bekräftigte. Die Thermogramme halfen bei der Unterscheidung von verschieden gebundenem Wasser, ihre chemische Zusammensetzung wurde durch Gewichtsverlust bei der Pyrolyse bestimmt. Man fand, daß 26.5 % der Steine aus reinem Whewellit bestanden, 3 % aus Weddellit, 13 % aus anhydrierter Harnsäure, 7.5 % aus Struvit, 2.5 % aus Ammmoniumhydrogenurat, 0.5 % aus Cystin und 47 % der Steine hatten eine gemischte Zusammensetzung. Die häufigsten Kombinationen der Mischzusammensetzungen waren Calciumoxalat mit Harnsäure (14.5 %) und mit Phosphaten (27.5 %).

     

An electrolytic device for preparation of hydrogen and oxygen from water for isotopic analysis

An electrolytic device for decomposition of water has been developed which readily gives hydrogen and oxygen for isotopic measurement with a mass spectrometer. A 20-mul sample can be decomposed quantitatively in 10 min with good reproducibility. The results produced are comparable with those obtained by reduction with uranium.     

Microbial Transformation of Sesquiterpenes, (−)‐Ambrox® and (+)‐Sclareolide

The microbial transformation of (?)‐Ambrox^® ( 1 ), a perfumery sesquiterpene, by a number of fungi, by means of standard two‐stage‐fermentation technique, afforded ambrox‐1α‐ol ( 2 ), ambrox‐1α,11α‐diol ( 3 ), ambrox‐1α,6α‐diol ( 4 ), ambrox‐1α,6α,11α‐triol ( 5 ), ambrox‐3‐one ( 6 ), ambrox‐3β‐ol ( 7 ), ambrox‐3β,6β‐diol ( 8 ), 13,14,15,16‐tetranorlabdane‐3,8,12‐triol ( 9 ), and sclareolide ( 10 ) (Schemes 1 and 2). Further incubation of compound 10 with Cunninghamella elegans afforded 3‐oxosclareolide ( 11 ), 3β‐hydroxysclareolide ( 12 ), 2α‐hydroxysclareolide ( 13 ), 2α,3β‐dihydroxysclareolide ( 14 ), 1α,3β‐dihydroxysclareolide ( 15 ), and 3β‐hydroxy‐8‐episclareolide ( 16 ) (Scheme 3). Metabolites 2 – 5, 12, 13 , and 16 were found to be new compounds. The major transformations include a reaction path involving hydroxylation, ether‐bond cleavage and inversion of configuration. Metabolites 11 – 16 of sclareolide showed significant phytotoxicity (Table 1). The structures of the metabolites were characterized on the basis of spectroscopic techniques.     

Synthesis of a novel cis-proline-derived cyclic type VI beta-turn mimic via ring-closing metathesis

A cis-proline derived cyclic mimic of a type VI beta-turn is synthesized via a ring-closing metathesis reaction. The solution NMR conformational study indicates that the major conformer of the cyclic peptide adopts a type VIa beta-turn in CDCl(3) and a type VIb beta-turn in DMSO-d(6).     

Palladium(0)-catalyzed regioselective synthesis of alpha-dehydro-beta-amino esters from amines and allyl acetates: synthesis of a alpha-dehydro-beta-amino acid derived cyclic peptide as a constrained beta-turn mimic

Acetates derived from the adducts of the Baylis-Hillman reaction can be reacted in a regioselective manner with amines in the presence of palladium(0) catalyst to afford alpha-dehydro-beta-amino esters (2 and 3) in good yields. The regioselectivity of the reaction can be controlled by temperature and reaction medium leading to the synthesis of regioisomers 2 or 3. The alpha-dehydro-beta-amino acid 3 is a turn inducer, and the dipeptides 6 derived from it show the presence of an eight-membered intramolecular hydrogen bond. Also, cobalt(II) chloride catalyzes the cleavage of epoxy peptides with alpha-dehydro-beta-amino acid derivative 3b to afford the corresponding dipeptide derivatives 8, which exhibit an intramolecular hydrogen bond and thus mimic a beta-turn. This intramolecular hydrogen bonding preorganizes the corresponding diallylated peptide 8c for cyclization via ring-closing metathesis to afford the cyclic peptide 9 as a constrained mimic of a beta-turn.     

Reverse turn induced pi-facial selectivity during polyaniline-supported cobalt(II) salen catalyzed aerobic epoxidation of N-cinnamoyl L-proline derived peptides

A novel chemo- and diastereoselective aerobic epoxidation of the N-cinnamoyl peptides catalyzed by polyaniline-supported cobalt(II) salen (PASCOS) is described. The N-cinnamoyl proline derived peptides 1 show a high pi-facial selectivity during these epoxidations. The origin of this diastereoselectivity in 1 has been attributed to (i) the propensity of the N-cinnamoyl proline amide to exist predominantly as trans rotamer in CDCl3, DMSO-d6, and CH3CN medium and (ii) existence of these peptides as organized structures (gamma- and beta-turns) due to the presence of intramolecular hydrogen bonds. An extensive solution NMR and MD simulation study on 1d and 1f indicates that the origin of the high pi-facial selectivity is due to the well-defined gamma- and beta-turns which result in the hindrance of one face of the cinnamoyl double bond in the transition state of the epoxidation reaction.     

A study of simultaneous photolysis and photoaddition reactions of riboflavin in aqueous solution

The photodegradation reactions of riboflavin (RF) in the presence of 0.05-2.00 M phosphate (pH 7.0) have been studied using a specific multicomponent spectrophotometric method. The reactions involve simultaneous photolysis (intramolecular photoreduction) and photoaddition (intramolecular photoaddition) leading to lumichrome (LC) and cyclodehydroriboflavin (CDRF), respectively, as major products. The contribution of each reaction in the overall photodegradation depends upon the phosphate concentration, i.e., higher the phosphate concentration higher the extent of photoaddition. The apparent first-order rate constants for the photodegradation of RF and for the formation of LC and CDRF at 0.25-2.00 M phosphate concentration range from 0.65 to 3.03 x 10(-2), and from 0.41 to 0.99 x 10(-2) and 0.12 to 1.63 x 10(-2) min(-1), respectively. The second-order rate constants for the phosphate catalysed photodegradation of RF and for the formation of LC and CDRF are 2.12 x 10(-4) and 0.61 x 10(-4) and 1.41 x 10(-4) M(-1)s (-1), respectively. Since the formation of CDRF by photoaddition is catalysed by HPO(4)(2-) ions, it is suggested that H(2)PO(4)(-) ions may be involved in the formation of LC by photolysis. Thus, both H(2)PO(4)(-) and HPO(4)(2-) ions may catalyse the two major reaction pathways of riboflavin photodegradation, respectively.     

Depolymerization Study of Pakistani Lignite Coal Influence of Pre‐treatments on Product Slate

Influence of pretreatments, i.e., demineralization and pre‐soaking in some solvents on the yields of liquefied products obtained from hydro‐depolymerization of Pakistani coal in a pool of hydrogen has been discussed. Results of hydrogenation experiments demonstrated that demineralizing the coal sample prior to liquefaction caused the yields to decrease compared with the virgin coal samples. The contribution of mineral matter of coal has been evaluated by comparing the yields of liquid products of virgin and leached samples. Increase in the yields obtained from the hydrogenation experiments of swollen coal samples was not satisfactorily significant.