Isolation and structural elucidation of antioxidant peptides from oyster (Saccostrea cucullata) protein hydrolysate.

Protein derived from the oyster (Saccostrea cucullata) was hydrolyzed using protease from Bacillus cereus SU12 for isolation of antioxidant peptides. The oyster hydrolysate exhibited a strong antioxidant potential in DPPH (85.7±0.37%) followed by Hydrogen peroxide radical scavenging activity (81.6±0.3%), Hydroxyl radical-scavenging activity (79.32±0.6%), Reducing power assay (2.63±0.2 OD at 700nm). Due to the high antioxidant potential, hydrolysate was fractionated in Sephadex G-25 gel filtration chromatography. The active peptide fraction was further purified by UPLC-MS. Totally 7 antioxidant peptides were collected. Among 7 peptides (SCAP 1-7), 3 peptides (SCAP 1, 3 and 7) had highest scavenging ability on DPPH radicals. The amino acid sequence and molecular mass of purified antioxidant peptides (SCAP1, SCAP3 and SCAP7) were determined by Q-TOF ESI mass spectroscopy and structures of the peptides were Leu-Ala-Asn-Ala-Lys (MW=515.29Da), Pro-Ser-Leu-Val-Gly-Arg-Pro-Pro-Val-Gly-Lys-Leu-Thr-Leu (MW=1432.89Da) and Val-Lys-Val-Leu-Leu-Glu-His-Pro-Val-Leu (MW=1145.75Da), respectively. The unique amino acid composition and sequence in the peptides might play an important role in expression of their antioxidant activity. The results of this study suggest that oyster protein hydrolysate is good source of natural antioxidants.

Synthesis and conformational studies of newly synthesized cis-2r,6c-distyryltetrahydro thiopyran-4-one and its oxime: comparison of experimental and theoretical NMR spectral data.

The cis-2r,6c-distyryltetrahydro thiopyran-4-one (4) was synthesized by the reaction of dicinnamylacetone with hydrogen sulphide. cis-2r,6c-distyryltetrahydro thiopyran-4-one oxime (5) was synthesized via oximination of 4. The synthesized compounds were characterized by IR, NMR spectral studies and elemental analysis. The proton and carbon chemical shift values were unambiguously assigned using two dimensional NMR (1H1H COSY, HSQC, HMBC, NOESY) spectra. 1H NMR and 13C NMR chemical shifts of 4 were also obtained by the density functional theory (DFT) using 6-311++G(d,p) basis sets and the theoretical values were compared with experimental values.

Hematological changes following early ligation of splenic artery during splenectomy in shunt surgery for portal hypertension.

OBJECTIVE AND BACKGROUND DATA: Reduction in cellular elements of blood, secondary to hypersplenism is an established component of non-cirrhotic portal hypertension. Prior transfusion of blood or blood components is frequently required for safe surgical intervention. Due to thrombocytopenia, epidural catheter insertion for effective and durable analgesia is not possible. The aim of the present study was to objectively demonstrate the gain in blood components following early ligation of splenic artery for splenectomy in shunt surgery. METHODS: From Jan 2008 to July 2010, 30 patients underwent elective proximal spleno renal shunt for portal hypertension, for various indications and were analyzed prospectively. We followed the standard protocol of ligating the splenic artery in situ, first in the lesser sac. Proximal spleno shunt was done. After the surgical procedure and before extubation, an epidural catheter was placed for effective and durable analgesia. 5ml of venous blood was drawn in the following order of sequence: prior to induction of anesthesia, immediately after the ligation of splenic artery, 30 minutes after ligation of splenic artery and 30 minutes after splenectomy. Samples were sent for complete hemogram and values were analyzed in respective order. Patients requiring transfusion of blood or blood components during surgery were excluded from the study. RESULTS: 30 patients (M - 9, F- 21) with mean age of 29.4 years (11-60 years) were analyzed (NCPF- 20, EHPVO- 9, cirrhosis- 1). We objectively demonstrated a significant gain in RBCs (p = 0.016) and platelets (p = 0.000) using this standard protocol. As there were no intrinsic abnormalities in RBCs, red blood cell indices (MCV, MCH, MCHC) showed no changes as expected (p-0.9). CONCLUSION: By following this standard protocol, in addition to reduction in blood loss there was a significant gain in RBCs and platelets. This gain allows the surgeon to perform the surgical procedure safely and the anesthetist to secure an epidural catheter immediately after surgery for effective and durable analgesia without prior transfusion.

Effects of protonation and co-anion on the 1H and 13C chemical shifts of 2r,6c- diphenylpiperidin-4-ones: evidence for the formation of ion pair.

(1)H and (13)C NMR spectra have been recorded for 2r,6c-diphenylpiperidin-4-one (1a), 3t-alkyl-2r,6c-diphenylpiperidin-4-ones 1b-d, 3t-alkyl-2r,6c-diphenyl-4-oxopiperidinium nitrates 2b and 2d, 3t-alkyl-2r,6c-diphenylpiperidin-4-one hydrochlorides 3a-c and 3t-methyl-2r,6c-diphenyl-4-oxopiperidinium picrate 4b in DMSO-d(6). For 1b, 2b and 3b, (1)H and (13)C NMR spectra have been recorded in CH(3)OD also. For 1b, 1d, 2b, 2d, 3b and 4b, 2D spectra have also been recorded. In DMSO-d(6) the protons of the piperidine ring and the ortho protons of the phenyl groups are markedly deshielded due to protonation. Protonation shields all the carbons of the piperidine ring and the ipso carbons of the phenyl groups markedly but deshields the other aromatic carbons slightly. The deshieldings on H-3a, H-5a and the ortho protons of the phenyl groups are less in the nitrate and picrate than in the corresponding hydrochloride. The effects on (13)C chemical shifts are not influenced by the co-anion. These observations suggest that the nitrates and pictrate exist as ion pairs in DMSO-d(6) and the nitrate and picrate ions shield, H-3a, H-5a and the ortho protons by magnetic anistropic effect. In CH(3)OD for 2b and 3b in addition to the ion-pair containing free ions two ion-pairs containing solvated ions are also present. The effects of protonation in the ion pairs containing the solvated ions are significantly different from those in the ion-pair containing free ions.

Vibrational, NMR spectral studies of 2-furoic hydrazide by DFT and ab initio HF methods.

The Fourier transform infrared spectra, 1H NMR and 13C NMR spectra of 2-furoic hydrazide have been recorded. Optimized geometry, frequency and intensity of the vibrational bands of 2-furoic hydrazide were obtained by the density functional theory (DFT) and ab initio levels of theory and also 1H NMR, 13C NMR chemical shifts were calculated using 6-31G+(d,p) basis sets. The theoretical values were compared with experimental values.

1-Acetyl-2-r,6-c-bis-(4-chloro-phen-yl)-3-methyl-1,2,5,6-tetra-hydro-pyridin-4-yl acetate.

In the title compound, C(22)H(21)Cl(2)NO(3), the pyridine ring adopts a half-chair conformation and the 4-chloro-phenyl groups occupy axial positions. The 4-chloro-phenyl groups are almost perpendicular to the plane of the tetra-hydro-pyridine ring forming dihedral angles 84.62 (6) and 85.55 (5)°; the dihedral angle between the two 4-chloro-phenyl rings is 12.16 (4)°. The crystal structure is stabilized by inter-molecular C-H⋯O inter-actions.

Peri-operative outcomes for pancreatoduodenectomy in India: a multi-centric study.

BACKGROUND: There have been an increasing number of reports world-wide relating improved outcomes after pancreatic resections to high volumes thereby supporting the idea of centralization of pancreatic resectional surgery. To date there has been no collective attempt from India at addressing this issue. This cohort study analysed peri-operative outcomes after pancreatoduodenectomy (PD) at seven major Indian centres. MATERIALS AND METHODS: Between January 2005 and December 2007, retrospective data on PDs, including intra-operative and post-operative factors, were obtained from seven major centres for pancreatic surgery in India. RESULTS: Between January 2005 and December 2007, a total of 718 PDs were performed in India at the seven centres. The median number of PDs performed per year was 34 (range 9-54). The median number of PDs per surgeon per year was 16 (range 7-38). Ninety-four per cent of surgeries were performed for suspected malignancy in the pancreatic head and periampullary region. The median mortality rate per centre was four (range 2-5%). Wound infections were the commonest complication with a median incidence per centre of 18% (range 9.3-32.2%), and the median post-operative duration of hospital stay was 16 days (range 4-100 days). CONCLUSIONS: This is the first multi-centric report of peri-operative outcomes of PD from India. The results from these specialist centers are very acceptable, and appear to support the thrust towards centralization.

Post pancreaticoduodenectomy haemorrhage: outcome prediction based on new ISGPS Clinical severity grading.

UNLABELLED: OBJECTIVE & BACKGROUND DATA: Mortality following pancreatoduodenectomy (PD) has fallen below 5%, yet morbidity remains between 30 and 50%. Major haemorrhage following PD makes a significant contribution to this ongoing morbidity and mortality. The aim of the present study was to validate the new International Study Group of Pancreatic Surgery (ISGPS) Clinical grading system in predicting the outcome of post pancreaticoduodenectomy haemorrhage (PPH). MATERIAL AND METHODS: Between January 1998 and December 2007 a total of 458 patients who underwent Whipple's pancreaticoduodenectomy in our department were analysed with regard to haemorrhagic complications. The onset, location and severity of haemorrhage were classified according to the new criteria developed by an ISGPS. Risk factors for haemorrhage, management and outcome were analysed. RESULTS: Severe PPH occurred in 14 patients (3.1%). Early haemorrhage (<24 hours) was recorded in five (36%) patients, and late haemorrhage (>24 hours) in nine (64%) patients. As per Clinical grading of ISGPS 7 (50%) belongs to Grade C and 7 (50%) belongs to Grade B. Haemostasis was attempted by surgery in 10 (71%) patients; angioembolisation was successful in two (14%) and endotherapy in one (7%) patient. The overall mortality is 29%(n=4). Age >60 years (p=0.02), sentinel bleeding (p=0.04), pancreatic leak (p=0.04) and ISGPS Clinical grade C (p=0.02) were associated with increased mortality. CONCLUSION: Early haemorrhage was mostly managed surgically with better outcome when endoscopy is not feasible. Late haemorrhage is associated with high mortality due to pancreatic leak and sepsis. ISGPS Clinical grading of PPH is useful in predicting the outcome.

Role of retrograde dilatation in the management of pharyngo-esophageal corrosive strictures.

Pharyngo-esophageal corrosive stricture is a complex clinical scenario. If an esophageal opening cannot be found orally through endoscopy, a retrograde approach with a mini-laparotomy and gastrostomy should be attempted. This study primarily aimed at defining the role of preoperative retrograde dilatation of pharyngo-esophageal corrosive strictures. A retrospective analysis of 51 cases of pharyngo-esophageal corrosive strictures identified between 1997-2005 was performed. The demographic details were analyzed. The details of the injury to the pharynx either in isolation or in combination were noted and the management details were recorded. In 21 patients preoperative retrograde dilatation was considered and the technique was successful in 14 (Group I). In seven the technique failed (Group II) and these patients underwent transhiatal resection and gastric pull-through and/or retrosternal pharyngocoloplasty. In Group I patients the postoperative stay was significantly less than in Group II (12 +/- 2.03 days vs. 18 +/- 4.32 days; p = 0.001) Recurrent aspiration, respiratory tract infections, choking sensation and the need for tracheostomy were less frequent in Group I. The overall functional assessment was good in Group I. For treatment of pharyngo-esophageal obstruction, if antegrade dilatation is not possible due to technical reasons, retrograde dilatation is a viable option before opting for organ replacement/bypass procedures. There is no best replacement of the native organ to maintain quality of life.