Comparative study of the structural and vibroelectronic properties of porphyrin and its derivatives.

Density functional theory (DFT and time-dependent-DFT (TD-DFT) were employed to investigate the vibroelectronic structural properties of porphyrin and some derivatives: unsubstituted porphyrin (TPyr), meso-tetraphenylporphyrin (TPP), meso-tetrakis(p-sulfonatophenyl)porphyrin (TSPP), protonated-TPyr (H2TPyr), deuterated-H2TPyr (D4TPyr), protonated-TPP (H2TPP) and deuterated-H2TPP (D4TPP), protonated TSPP (H2TSPP), deuterated-H2TSPP (D4TSPP), dicationic TSPP (H6TSPP) and deuterated-H6TSPP (D8TSPP). The possible internal conversion (IC) and intersystem crossing (ISC) processes of these compounds were investigated. Finally, the relaxed ground state potential energy surface (PES) (S0), and singlet (Sn, n = 1-24) and triplet (Tn) excited state PESs of the TSPP molecule were calculated as function of the dihedral angle (Cα-Cm-Cϕ-C(ph)) rotation. The results of the calculations indicated that while the meso-substitutions caused a significant shift in frequencies when the meso-carbons within the parent-porphine (or TPyr) are involved in the vibrational motion of molecules; the protonation of the N atoms at the porphine/porphyrin core causes a significant blue shift when the H on the N atoms within the pyrroline are dominantly involved in the vibrational motions. The deuteration of N atoms not only caused a red-shift in the frequencies of the corresponding peaks below 1600 cm(-1), but also produced new vibrational modes of frequencies in the 2565-2595 cm(-1) range caused by the N-D bond stretching. Similarly, the deuteration of O atoms within the sulfonato groups (-SO3(-)) exhibited a new peak at around 2642 cm(-1) due to O-D bond stretching. The measured Raman spectrum of the H2TSPP is assigned based on the predicted Raman spectra of the compounds studied here and measured Raman spectrum of the TPP (from our previous work). The IR spectrum is assigned based on our calculations and measured IR spectra obtained from the literature. The results of the TD-DFT calculations did not only indicate that the meso-substitution and protonation of the porphyrin bring about a significant read shift in the electronic transitions; but also provided a strong evidence for the IC from the Soret band to Q-bands beside possibility of the ISC process; its existence depend on the other excited state process such as much faster vibrational relaxation; the IC and etc. The ground state PES curve (S0) of the ionic TSPP exhibited two minima at the dihedral angle (Cα-Cm-Cϕ-C) of about 66° (corresponds to the lowest ground state) and 110° (corresponds to next energetically stable state or the local minima). The energy deference between these two minima is 0.0132 eV (or 106 cm(-1)) and the highest potential energy barrier when undergoing from the lowest ground state to this local state is only 0.0219 eV (177 cm(-1); which is compatible with the thermal energy (kT) at 298 K is 207.2 cm(-1).

Effect of preserving the hepatic vagal nerve during laparoscopic Nissen fundoplication on postoperative biliary functions.

BACKGROUND: Cutting the hepatic branch of the anterior vagus nerve (HB-AVn) technically facilitates the laparoscopic Nissen fundoplication. The aim of this study was to investigate the effects of preserving or sacrificing this branch on postoperative gallbladder functions. METHODS: The patients (n = 40) were prospectively randomized into two groups. The HB-AVn was preserved during the dissection of the lesser omentum in the first group. The nerve was cut in the second group. Postoperative fasting gallbladder volumes were calculated by ultrasonography. Postoperative gallbladder ejection fraction (GEF) and gallbladder emptying time (GET) were determined by calculating intestinal transit time scintigraphically. RESULTS: Fasting gallbladder volumes and GEF values were not different between the groups. On the other hand, in patients with HB-AVn preserved, GET measurements were found to be significantly shorter than those with HB-AVn sacrificed. CONCLUSIONS: Sacrificing the hepatic branch causes prolongation in the GET. This change in the motor functions of the gallbladder does not cause any symptomatic effect during the early postoperative period. However, the delay in the GET may increase the risk of gallbladder stone formation in the long term.

The hemostatic effect of calcium alginate in experimental splenic injury model.

BACKGROUND: We evaluated the effect of calcium alginate as a hemostatic agent in a splenic injury model. METHODS: Experimental rats (Wistar albino) were divided into four groups. Group I: Laparotomy was not performed. Group II: After laparotomy, the abdomen was closed without any splenic injury. Group III: After laparotomy, splenic injury about 0.5 cm in depth and 0.3 cm in length was created by standard Rochester pean forceps. Physiological serum treated gauze dressing, about 2x2 cm in size, was applied to the injured splenic tissue for 3 minutes. Group IV: After laparotomy, standard splenic injury about 0.5 cm in length and 0.3 cm in depth was created. Calcium alginate wound dressing, 1x1 cm in size, was applied to the splenic wound. In all groups, blood samples for bleeding time and hemogram were taken. Peroperative blood loss, pre- and post-operative hemoglobin and hematocrit values were calculated. RESULTS: Comparing hematocrit values and peroperative bleeding in Groups III and IV, Group IV had a lower decline in hematocrit values and lower peroperative bleeding. CONCLUSION: Calcium alginate has hemostatic capacity. It may be used in splenic injuries, especially for Grades I and II.

Density functional theory and Raman spectroscopy applied to structure and vibrational mode analysis of 1,1',3,3'-tetraethyl-5,5',6,6'-tetrachloro- benzimidazolocarbocyanine iodide and its aggregate.

We have measured electronic and Raman scattering spectra of 1,1',3,3'-tetraethyl-5,5',6,6'-tetrachloro-benzimidazolocarbocyanine iodide (TTBC) in various environments, and we have calculated the ground state geometric and spectroscopic properties of the TTBC cation in the gas and solution phases (e.g., bond distances, bond angles, charge distributions, and Raman vibrational frequencies) using density functional theory. Our structure calculations have shown that the ground state equilibrium structure of a cis-conformer lies ∼200 cm(-1) above that of a trans-conformer and both conformers have C(2) symmetry. Calculated electronic transitions indicate that the difference between the first transitions of the two conformers is about 130 cm(-1). Raman spectral assignments of monomeric- and aggregated-TTBC cations have been aided by density functional calculations at the same level of the theory. Vibrational mode analyses of the calculated Raman spectra reveal that the observed Raman bands above 700 cm(-1) are mainly associated with the in-plane deformation of the benzimidazolo moieties, while bands below 700 cm(-1) are associated with out-of-plane deformations of the benzimidazolo moieties. We have also found that for the nonresonance excited experimental Raman spectrum of aggregated-TTBC cation, the Raman bands in the higher-frequency region are enhanced compared with those in the nonresonance spectrum of the monomeric cation. For the experimental Raman spectrum of the aggregate under resonance excitation, however, we find new Raman features below 600 cm(-1), in addition to a significantly enhanced Raman peak at 671 cm(-1) that are associated with out-of-plane distortions. Also, time-dependent density functional theory calculations suggest that the experimentally observed electronic transition at ∼515 nm (i.e., 2.41 eV) in the absorption spectrum of the monomeric-TTBC cation predominantly results from the π → π∗ transition. Calculations are further interpreted as indicating that the observed shoulder in the absorption spectrum of TTBC in methanol at 494 nm (i.e., 2.51 eV) likely results from the ν(") = 0 → ν' = 1 transition and is not due to another electronic transition of the trans-conformer-despite the fact that measured and calculated NMR results (not provided here) support the prospect that the shoulder might be attributable to the 0-0 band of the cis-conformer.

Biliary tract reconstruction with autologous rectus sheath graft--an experimental study.

BACKGROUND/AIMS: Common bile duct injuries which cause significant morbidity and mortality are one of the most serious complications of cholecystectomies. They can be repaired by various approaches. METHODOLOGY: We used an autologous graft obtained from the posterior sheath of the rectus muscle in biliary tract reconstruction for common bile duct defect. This experimental study was carried out on six dogs. A tissue fragment was excised from the posterior sheath of the rectus muscle together with the fascia transversalis and peritoneum. A channel from the fascial graft was formed around a T-tube. The autologous rectus sheath graft was sutured to the common bile duct as a segmental conduit graft. Afterwards, blood biochemistry values and liver histopathology were investigated. Dogs were studied by T-tube cholangiography 4 months postoperatively just prior to removing the T-tube and again 2 months later at relaparotomy. The hepatic parenchyma, intra- and extrahepatic bile ducts were detected by ultrasonography during the last 2 months, one time in fifteen days. RESULTS: There was no anastomotic insufficiency. The fascial graft gained an appearance similar to bile duct in dogs. Postoperatively, no change in blood biochemical parameters was observed, and in the preoperative and postoperative periods no histopathological change in the liver was found. CONCLUSIONS: These findings indicate that the use of an autologous fascial graft to repair common bile duct injuries as a conduit graft for segmental bile duct loss may be a feasible and alternative method of treatment.

[The role of peritoneal aspiration cytology diagnosis of acute appendicitis]. / Akut apandisit tanisinda peritoneal aspirasyon sitolojisinin yeri.

BACKGROUND: The purpose of this study is to search the role of peritoneal aspiration cytology in acute appendicitis. METHODS: Peritoneal aspiration cytology was (PAC) conducted for fifty suspected acute appendicitis patients before their operations. PAC findings was compared with histopathologic results. RESULTS: Negative appendicectomy rate according to clinical diagnosis was 20%. PAC was positive in 32 and negative in 18 patients. 93.75% PAC (+) patients had acute appendicitis, 44.4% PAC (-) patients had normal appendices. The false positive rate was 6.2% and the false negative rate was 55.6%. The sensitivity, the specificity, the positive predictive value, the negative predictive value of PAC for the diagnosis of acute appendicitis were 75%, 80%, 93.8%, 44.4%, respectively and the accuracy was 76%. CONCLUSION: PAC positive results support the diagnosis of acute appendicitis strongly. However, PAC (-) results don't exclude the diagnosis of acute appendicitis.

Effects of cruroraphy and laparoscopic Nissen fundoplication procedures on pulmonary function tests in gastroesophageal reflux patients.

Gastroesophageal reflux disease plays a role in the etiology of asthma, chronic bronchitis, aspiration pneumonia, bronchiectasis and interstitial lung fibrosis by affecting the upper respiratory system. To investigate the changes in pulmonary function tests in patients who underwent cruroraphy and laparoscopic Nissen fundoplication for gastroesophageal reflux disease. Between January and October of 2012, cruroraphy and laparoscopic Nissen fundoplication have been carried out on 40 patients with gastroesophageal reflux disease in the Department of General Surgery, Faculty of Medicine, Duzce University. Patients had pulmonary function tests were measured preoperatively and on postoperative day 20. Increases in forced vital capacity, forced expiratory volume in 1 second/forced vital capacity and forced expiratory flow between 25-75% of vital capacity were observed postoperatively in all patients and these increases were found to be statistically significant (p=0.001). Change in the forced expiratory volume in 1 second was not statistically significant (p=0.182). We conclude that treatment of reflux in early stages by surgical procedures could prevent development of chronic lung disease by safeguarding the pulmonary system functions.

Dermoid cyst of the pancreas: a report of an unusual case and a review of the literature.

Pancreatic dermoid cysts are a rare entity. Preoperative diagnosis is difficult. The diagnosis is generally taking intraoperative. A 20-year-old female presented with epigastric pain without nausea, vomiting, diarrhea, fever, jaundice, and weight loss of one-month duration. Ultrasonography and computed tomography showed a smooth borders, solid, hyperechoic tumor within midline abdomen, without any connection to the stomach or spleen. At surgery, the entire mass was excised off of the head and inferior part of pancreas. Histopathologic evaluation revealed the rare diagnosis of a dermoid cyst. The diagnosis is difficult preoperatively in evaluating cystic pancreatic lesions by imaging. Therefore, we want to summarize the literature on this rare entity knowledge.

The early anti-inflammatory effect of Kefir in experimental corrosive esophagitis.

AIM: Corrosive esophageal burns are still an important problem. The aim of this study was to evaluate the effect of kefir in an experimental corrosive esophagitis model. MATERIAL AND METHOD: Twenty-four male wistar albino rats were used in this experimental study. The rats were randomized into three groups according to the procedure and treatment type (each group has eight rats). Group I: (Control group), Group II: (Induction of corrosive esophagitis with 5 % NaOH without any treatment) and Group III: (Corrosive esophagitis treated with kefir). The rats were sacrificed on the first and seventh days. Mediastinum and abdominal cavity of rats were explorated. Approximately 1.5 cm of esophagus was removed for histopathological examination. Inflammation, injury in the muscularis mucosa and collagen deposition were evaluated. RESULTS: Histopathological results on the first day after caustic injury; inflammation was detected in three rats in Group II and there were no inflammation in rats in Group III. This difference was statistically significant (p<0.05). Injury in muscularis mucosa was detected in three rats in Group II and in one rat in Group III. Histopathological results on the seventh days after caustic injury; Inflammation was positive in four rats in Group II and three rats in Group III. Injury in muscularis mucosa was equal in two groups (three rats each). Collagen deposition with high grade (Grade 2) was detected in two rats in Group II and in four rats in Group III (p<0.05). CONCLUSION: Kefir has anti-inflammatory effect specially in early phase of caustic injury. It has also some beneficial effect in wound healing.

Gastroscopic removal of a migrated adjustable gastric band: a case report.

Laparoscopic gastric banding is a popular method for treating morbid obesity. Band migration is a well-known late complication and the treatment is usually reoperation. In this case report, we show that a band penetrating the gastric wall can be treated by gastroscopic operation with the Gastric Band Cutter device without complication. It seems that this technique is simpler than reoperation and is beneficial even when the intraluminal migration is partial.