The effects of conformation and intermolecular hydrogen bonding on the structure and IR spectra of flutamide; a study based on the matrix isolation technique, ab initio and DFT calculations.

In this study, stable conformers of flutamide referred to as an anticancer drug were searched through a relaxed potential energy surface scan carried out at the B3LYP/6-31G(d) level of theory. This was followed by geometry optimization and thermochemistry calculations performed with the HF-SCF, MP2, B3LYP methods and the 6-31G(d), 6-311++G(d,p), aug-cc-pvTZ basis sets for each of the determined minimum energy conformers. The results revealed that flutamide has at least five stable conformers and two of them provide the major contribution to the observed matrix isolation infrared (IR) spectra of the molecule. The effects of conformational variety and intermolecular hydrogen bonding interactions on the observed IR spectra of flutamide were interpreted in the light of the vibrational spectral data obtained for the most stable monomer and dimer forms of the molecule at the same levels of theory. Pulay's "Scaled Quantum Mechanical-Force Field (SQM-FF)" method was used in the refinement of the calculated harmonic wavenumbers, IR intensities and potential energy distributions. This scaling method which proved its superiority to both anharmonic frequency calculations and other scaling methods helped us to correctly interpret the remarkable differences between the matrix IR spectra of flutamide in argon and the condensed phase IR spectra of the molecule in solvents such as KBr, H2O, D2O, ethanol and methanol.

An investigation on the structure and group vibrations of balenine molecule by matrix isolation IR spectroscopy, DFT and MP2 based calculations.

Stable conformers of neutral balenine were scanned through molecular dynamics simulations and energy minimizations using Allinger's MM2 force field. For each of the found minimum-energy conformers, geometry optimization and thermochemistry calculations were performed by using B3LYP, MP2, G3MP2B3 methods, 6-31G(d), 6-311++G(d,p) and aug-cc-pvTZ basis sets. The calculation results have indicated that balenine has about twenty stable conformers whose relative energies are in the range of 0-9.5 kcal/mol. Three of these are thought to provide the major contribution to matrix isolation IR spectra of the molecule. Our solvent calculations using the polarized continuum model revealed the stable zwitterion structures which are predicted to dominate IR spectra of balenine in water and heavy water (D2O) solvents. Pulay's SQM-FF method was used in scaling of the harmonic force constants and vibrational spectral data calculated for the neutral and zwitterion structures. These refined calculation data together with those obtained from anharmonic frequency calculations enabled us to correctly interpret the matrix isolation IR spectrum of balenine and the tautomerism-based changes observed in its KBr IR and solution (D2O) IR spectra. The results revealed the crucial role of conformation and zwitterionic tautomerism on the structure and vibrational spectral data of the molecule.

The protective effect of lycopene against oxidative kidney damage associated with combined use of isoniazid and rifampicin in rats.

It is known that the combined use of antibiotics, such as isoniazid and rifampicin, in the treatment of tuberculosis causes oxidative kidney damage. The aim of this study was to biochemically and histopathologically investigate the effect of lycopene on oxidative kidney damage due to the administration of isoniazid and rifampicin in albino Wistar male rats. Lycopene at a dose of 5 mg/kg was orally administered to lycopene+isoniazid+rifampicin (LIR) rats, and normal sunflower oil (0.5 mL) was orally administered to isoniazid+rifampicin (IR) and healthy control (HG) rats as vehicle by gavage. One hour after the administration of lycopene and vehicle, 50 mg/kg isoniazid and rifampicin were given orally to the LIR and IR groups. This procedure was performed once a day for 28 days. Rats were sacrificed by a high dose of anesthesia at the end of this period, and oxidant-antioxidant parameters were measured in the removed kidney tissues. Creatinine and blood urea nitrogen (BUN) levels were measured in blood samples, and kidney tissues were also evaluated histopathologically. The combined administration of isoniazid and rifampicin changed the oxidant-antioxidant balance in favor of oxidants, and it increased blood urea nitrogen and creatinine levels, which are indicators of kidney function. Co-administration of isoniazid and rifampicin also caused oxidative kidney damage. Lycopene biochemically and histopathologically decreased oxidative kidney damage induced by isoniazid and rifampicin administration. These results suggested that lycopene may be beneficial in the treatment of nephrotoxicity due to isoniazid and rifampicin administration.

The protective effect of lycopene against oxidative kidney damage associated with combined use of isoniazid and rifampicin in rats

It is known that the combined use of antibiotics, such as isoniazid and rifampicin, in the treatment of tuberculosis causes oxidative kidney damage. The aim of this study was to biochemically and histopathologically investigate the effect of lycopene on oxidative kidney damage due to the administration of isoniazid and rifampicin in albino Wistar male rats. Lycopene at a dose of 5 mg/kg was orally administered to lycopene+isoniazid+rifampicin (LIR) rats, and normal sunflower oil (0.5 mL) was orally administered to isoniazid+rifampicin (IR) and healthy control (HG) rats as vehicle by gavage. One hour after the administration of lycopene and vehicle, 50 mg/kg isoniazid and rifampicin were given orally to the LIR and IR groups. This procedure was performed once a day for 28 days. Rats were sacrificed by a high dose of anesthesia at the end of this period, and oxidant-antioxidant parameters were measured in the removed kidney tissues. Creatinine and blood urea nitrogen (BUN) levels were measured in blood samples, and kidney tissues were also evaluated histopathologically. The combined administration of isoniazid and rifampicin changed the oxidant-antioxidant balance in favor of oxidants, and it increased blood urea nitrogen and creatinine levels, which are indicators of kidney function. Co-administration of isoniazid and rifampicin also caused oxidative kidney damage. Lycopene biochemically and histopathologically decreased oxidative kidney damage induced by isoniazid and rifampicin administration. These results suggested that lycopene may be beneficial in the treatment of nephrotoxicity due to isoniazid and rifampicin administration.

Two-colour chewing gum mixing ability test for evaluating masticatory performance in children with mixed dentition: validity and reliability study.

The unappealing taste of the chewing material and the time-consuming repetitive task in masticatory performance tests using artificial foodstuff may discourage children from performing natural chewing movements. Therefore, the aim was to determine the validity and reliability of a two-colour chewing gum mixing ability test for masticatory performance (MP) assessment in mixed dentition children. Masticatory performance was tested in two groups: systemically healthy fully dentate young adults and children in mixed dentition. Median particle size was assessed using a comminution test, and a two-colour chewing gum mixing ability test was applied for MP analysis. Validity was tested with Pearson correlation, and reliability was tested with intra-class correlation coefficient, Pearson correlation and Bland-Altman plots. Both comminution and two-colour chewing gum mixing ability tests revealed statistically significant MP differences between children (n = 25) and adults (n = 27, both P < 0·01). Pearson correlation between comminution and two-colour chewing gum mixing ability tests was positive and significant (r = 0·418, P = 0·002). Correlations for interobserver reliability and test-retest values were significant (r = 0·990, P = 0·0001 and r = 0·995, P = 0·0001). Although both methods could discriminate MP differences, the comminution test detected these differences generally in a wider range compared to two-colour chewing gum mixing ability test. However, considering the high reliability of the results, the two-colour chewing gum mixing ability test can be used to assess masticatory performance in children, especially at non-clinical settings.

Masticatory parameters of children with and without clinically diagnosed caries in permanent dentition.

AIM: Mastication turns food into a bolus and prepares it for chemical digestion. Any condition affecting tooth structure and position may have an impact on mastication. The aim of this study is to compare masticatory performance (MP) and maximum bite force (MBF) between children with and without clinically visible caries in permanent first molars. MATERIALS AND METHODS: The study was conducted with 50 children in good general condition aged 12-14 years (25 girls, 25 boys) with no orthodontic/skeletal anomalies and no missing teeth due to dental trauma or extraction. Maximum bite force was measured bilaterally using strain gauge sensors. Masticatory performance was evaluated by silicone tablet comminution test. RESULTS: Masticatory performance was superior in caries-free children when compared to children with caries. Maximum bite force values in children with and without caries were not statistically different. CONCLUSIONS: Caries reduces masticatory performance. Therefore, treatment is crucial for masticatory efficiency.

Investigation of the N-terminal coding region of MUC7 alterations in dentistry students with and without caries.

Human low-molecular weight salivary mucin (MUC7) is a small, secreted glycoprotein coded by MUC7. In the oral cavity, they inhibit the colonization of oral bacteria, including cariogenic ones, by masking their surface adhesions, thus helping saliva to avoid dental caries. The N-terminal domain is important for low-molecular weight (MG2) mucins to contact with oral microorganisms. In this study, we aimed to identify the N-terminal coding region of the MUC7 gene between individuals with and without caries. Forty-four healthy dental students were enrolled in this study; 24 of them were classified to have caries [decayed, missing, filled-teeth (DMFT) = 5.6] according to the World Health Organization (WHO) criteria, and 20 of them were caries-free (DMFT = 0). Simplified oral hygiene index (OHI-S) and gingival index (GI) were used to determine the oral hygiene and gingival conditions. Total protein levels and salivary total protein levels and salivary buffer capacity (SBC) were determined by Lowry and Ericsson methods. DNA was extracted from peripheral blood cells of all the participants and genotyping was carried out by a polymerase chain reaction (PCR)-sequencing method. No statistical differences were found between two groups in the terms of salivary parameters, oral hygiene and gingival conditions. We detected one common single nucleotide polymorphism (SNP) that leads to a change of asparagine to lysine at codon 80. This substitution was found in 29.0 and 40.0%, respectively, of the groups with and without caries. No other sequence variations were detected. The SNP found in this study may be a specific polymorphism affecting the Turkish population. Further studies with extended numbers are necessary in order to clarify this finding.

A vibrational spectroscopy study on anserine and its aqueous solutions.

In this study based on vibrational spectroscopic measurements and Density Functional Theory (DFT), we aimed for a reliable interpretation of the IR and Raman spectra recorded for anserine in the solid phase and water (H2O) and heavy water (D2O) solutions. Initial DFT calculations at the B3LYP/6-31G(d) searched possible conformers of the anserine zwitterion using a systematic conformational search. The corresponding equilibrium geometrical parameters and vibrational spectral data were determined for each of the stable conformers (in water) by the geometry optimization and hessian calculations performed at the same level of theory using the polarized continuum model (PCM). The same calculations were repeated to determine the most energetically preferred dimer structure for the molecule and the associated geometry, force field and vibrational spectral data. The harmonic force constants obtained from these calculations were scaled by the Scaled Quantum Mechanical Force Field (SQM) method and then used in the calculation of the refined wavenumbers, potential energy distributions, IR and Raman intensities. These refined theoretical data, which confirm the zwitterion structure for anserine in the solid phase or aqueous solvents, revealed the remarkable effects of intermolecular hydrogen bonding on the structural properties and observed IR and Raman spectra of this molecule.

Echo-guided pericardiocentesis in patients with clinically significant pericardial effusion. Outcomes over a 10-year period.

BACKGROUND: The purpose of the present study is to evaluate current echocardiographically (echo)-guided pericardiocentesis practice with regard to procedural success, complication rate, etiological causes, and outcomes of patients with clinically significant pericardial effusion. PATIENTS AND METHODS: Patients who underwent echo-guided pericardiocentesis between January 2004 and February 2014 were identified using an institutional code for the procedure. Other complementary data were obtained by interviewing patients or their relatives (directly or by telephone) and by searching the social security death index. RESULTS: A total of 301 patients were identified. The pericardium was approached via the subcostal (85 %) or apical (15 %) route under echo guidance in all procedures. The success rate was 97 %, with an intervention-requiring complication rate of 1.3 %. No patient died from complications. The most common etiology was malignancy (n = 84, 28 %). Patients were followed-up for a median of 35 months. Median survival for patients with malignant effusion was 5.9 months compared with 54 months for those with nonmalignant effusion. CONCLUSIONS: Echo-guided pericardiocentesis has a high success and low complication rate in current practice. Among etiologies, malignancy remains the most common cause of clinically significant pericardial effusion and is associated with a poor prognosis.

Evaluation of vitamin D receptor (VDR) gene polymorphisms (FokI, TaqI and ApaI) in a family with dentinogenesis imperfecta.

Dentinogenesis imperfecta Type II (DGI-II) is a condition inherited as an autosomal dominant trait and characterized by abnormal dentine structure affecting both the primary and secondary dentitions. The genetic etiology of the disease still remains unclear, suggesting a genetically heterogeneous background. The aim of this study is to manifest briefly DGI-II and to investigate the association between BsmI, TaqI and FokI polymorphisms of Vitamin D receptor (VDR) gene and dentinogenesis imperfecta type II in a Turkish family by PCR-RFLP methodology. The affected mother and her two affected daughters were bb for BsmI polymorphism, whereas her unaffected son and her husband were Bb for the same polymorphism. One of the affected children was tt, the rest of the family were Tt for TaqI polymorphism, and all of the enrolled subjects were FF for FokI polymorphism. As a conclusion, BsmI polymorphism bb seems to be associated with (DGI-II), but should be examined in larger numbers in order to be considered as a risk factor.

Papillorenal syndrome with de novo reciprocal translocation t(2;15) (q31; q26).

Renal hypoplasia is a congenital anomaly, the etiology of which is not yet fully known. Genetic studies have shown that certain genes, in utero environmental factors and molecular mechanisms have a role in the identification ofnephron formation and kidney size. The coexistence of bilateral renal hypoplasia and optic disc coloboma is observed in papillorenal syndrome, which caused by the mutation of the PAX2 gene. In the case presented in this article, bilateral renal hypoplasia and optic disc coloboma have been detected to coexist. The analysis of the PAX2 gene, which was carried out with an eye to the papillorenal syndrome, did not reveal any mutations. However, de novo t(2;15) (q31; q26) (reciprocal translocation) was detected in chromosome analysis. As far as we know, there are not any publications focusing on the clinical importance of this type of translocation. In cases with renal hypoplasia and optic disc coloboma, the possibility of a de novo translocation between chromosomes 2 and 15 should be considered.

Raman micro-spectroscopic analysis of cultured HCT116 colon cancer cells in the presence of roscovitine.

Raman micro-spectroscopic analysis of cultured HCT116 colon cancer cells in the presence of roscovitine, [seliciclib, 2-(1-ethyl-2-hydroxy-ethylamino)-6-benzylamino-9-isopropylpurine], a promising drug candidate in cancer therapy, has been performed for the first time. The aim of this study was to investigate modulations in colon cancer cells induced by roscovitine. Raman spectra of the cultured HCT116 colon cancer cells treated with roscovitine at different concentrations (0, 5, 10, 25 and 50 µM) were recorded in the range 400-1850 cm(-1). It was shown that the second derivative profile of the experimental spectrum gives valuable information about the wavenumbers and band widths of the vibrational modes of cell components, and it eliminates the appearance of false peaks arising from incorrect baseline corrections. In samples containing roscovitine, significant spectral changes were observed in the intensities of characteristic protein and DNA bands, which indicate roscovitine-induced apoptosis. Roscovitine-induced apoptosis was also assessed by flow cytometry analysis, and analysis of propidium iodide staining. We observed some modifications in amide I and III bands, which arise from alterations in the secondary structure of cell proteins caused by the presence of roscovitine.

Salivary lipid peroxidation and total sialic acid levels during healthy gestation and postpartum: a longitudinal study.

OBJECTIVES: This study investigated salivary lipid peroxidation (LPO) as an oxidative stress marker and salivary total sialic acid (TSA) as an inflammatory response during gestation and postpartum. DESIGN AND METHODS: Salivary LPO and TSA levels, using the Ledwozyw and Warren methods respectively, were obtained in healthy pregnant women followed up during gestation and 6-8 weeks postpartum, and in healthy non-pregnant controls. All were with good oral health. RESULTS: LPO was significantly higher than controls during all trimesters and postpartum and in the second trimester than in the third trimester and postpartum. TSA in the second trimester was significantly higher than in any other group. First trimester levels were significantly higher than postpartum . Oral health indices remained within normal levels for the duration. CONCLUSION: The salivary LPO profile followed plasma gestation and postpartum profiles in the literature but the salivary TSA differed in that after the 2nd trimester, rather than persisting, it decreased.

Association between dental-oral health in young adults and salivary glutathione, lipid peroxidation and sialic acid levels and carbonic anhydrase activity.

The aim of the present study was to evaluate the relationship between salivary oxidative stress and dental-oral health. Healthy young adults, matched for gender and age, with (N = 21, 10 men, mean age: 20.3 +/- 1 years) and without (N = 16, 8 men, mean age: 21.2 +/- 1.8 years) caries were included in this study. The World Health Organization (WHO) caries diagnostic criteria were used for determining the decayed, missing, filled teeth (DMFT) index. The oral hygiene and gingival status were assessed using the simplified oral hygiene index and gingival index, respectively. Unstimulated salivary total protein, glutathione (GSH), lipid peroxidation and total sialic acid levels, carbonic anhydrase activity, and salivary buffering capacity were determined by standard methods. Furthermore, salivary pH was measured with pH paper and salivary flow rate was calculated. Simplified oral hygiene index and gingival index were not significantly different between groups but DMFT scores were significant (P < 0.01). Only, GSH values were significantly different (P < 0.05) between groups (2.2 and 1.6 mg/g protein in young adults without caries and with caries, respectively). There was a significant negative correlation between DMFT and GSH (r = -0.391; P < 0.05; Pearson's correlation coefficient). Our results suggest that there is an association between caries history and salivary GSH levels.

Association between dental-oral health in young adults and salivary glutathione, lipid peroxidation and sialic acid levels and carbonic anhydrase activity

The aim of the present study was to evaluate the relationship between salivary oxidative stress and dental-oral health. Healthy young adults, matched for gender and age, with (N = 21, 10 men, mean age: 20.3 ± 1 years) and without (N = 16, 8 men, mean age: 21.2 ± 1.8 years) caries were included in this study. The World Health Organization (WHO) caries diagnostic criteria were used for determining the decayed, missing, filled teeth (DMFT) index. The oral hygiene and gingival status were assessed using the simplified oral hygiene index and gingival index, respectively. Unstimulated salivary total protein, glutathione (GSH), lipid peroxidation and total sialic acid levels, carbonic anhydrase activity, and salivary buffering capacity were determined by standard methods. Furthermore, salivary pH was measured with pH paper and salivary flow rate was calculated. Simplified oral hygiene index and gingival index were not significantly different between groups but DMFT scores were significant (P < 0.01). Only, GSH values were significantly different (P < 0.05) between groups (2.2 and 1.6 mg/g protein in young adults without caries and with caries, respectively). There was a significant negative correlation between DMFT and GSH (r = -0.391; P < 0.05; Pearson's correlation coefficient). Our results suggest that there is an association between caries history and salivary GSH levels.

Salivary thromboplastic activity in diabetics and healthy controls.

Coagulative function of saliva derives from the thromboplastin found in saliva. It may establish hemostasis in the mouth. Salivary disfunction and changes in salivary composition and are frequent complications of diabetes. This study investigated the influence of some local etiologic and systemic factors on salivary thromboplastic activity (STA) in diabetics. In this study, cytological smears and biochemical tests were used. STA was measured by Quick's one stage method, serum glucose by the glucose oxidase method, and salivary protein by the method of Lowry. STA was almost the same in the diabetic and control groups. The only statistically significant difference within the diabetic group was found to be due to antibiotic usage. STA, i.e. clotting time, was 30% longer (114 s) ( p<0.05) and salivary protein (4.07 mg ml(-1)) ( p<0.1) was lower in diabetics not taking antibiotics than in those taking them. No such differences were observed in the healthy controls. Significant linear correlations ( p<0.05) with respect to STA were with salivary protein in the control group (r=0.61) and in the diabetic group (r=0.51) and with antibiotic usage (r=0.29), with leukocyte cell count (r=0.27) in the diabetic group. It can be concluded that salivary cells, proteins and antibiotic usage are important for STA.

Mycological and cytological examination of oral candidal carriage in diabetic patients and non-diabetic control subjects: thorough analysis of local aetiologic and systemic factors.

In this study, 55 diabetic patients and 45 non-diabetic control subjects were examined to determine oral candidal carriage state. The influence of some local aetiologic and systemic factors such as: salivary flow rate and pH, heredity, alcohol drinking, smoking habits, antimicrobial therapy, wearing of denture, burning sensation, dry mouth, taste alteration and tooth brushing habit on candidal carriage rate were investigated. Imprint culture, cytological smears and biochemical tests were used. Oral carrier rate and density of Candida species were non-significantly higher in the diabetic patients than in the non-diabetic control subjects. This increase was confirmed cytologically too. In both groups, Candida albicans was found to be a predominant species on tongue dorsum. Cigarette and alcohol habits of men were higher while tooth brushing habit was less than in women in diabetic and control groups. Salivary flow rate and pH values of diabetic patients were significantly lower while serum glucose values were significantly higher than of non-diabetic controls. The rate of diabetic patients suffering from dry mouth and having diabetic heredity in the family were significantly higher than control subjects. The candidal colonization was higher and keratinization was lower while diabetic treatment tended from diet and oral antidiabetic towards insulin. The decrease in salivary pH, the increase in serum glucose and wearing denture were correlated with the increased rate and density of C. albicans in both groups. Keratinization was also accompanied with the increase in leucocytes. In diabetic group, positive correlations were found between antimicrobial therapy and C. glabrata carriage; the increase in leucocytes and C. albicans carriage; the increase in keratinization and alcohol habit; serum glucose and smoking habit; dry mouth complaint and antimicrobial therapy. There was a negative correlation between salivary flow rate and C. albicans carriage. In control group a positive correlation was found between antimicrobial therapy and keratinization.

Salivary sialic acid, protein, salivary flow rate, pH, buffering capacity and caries indices in subjects with Down's syndrome.

OBJECTIVES: The aim of this study was to compare salivary sialic acid, protein, salivary flow rate, pH and buffering capacity and caries indices between subjects with Down's Syndrome and healthy controls. METHODS: Unstimulated mixed saliva was collected from 26 Down's syndrome subjects and 25 healthy subjects of age range 6-24 years. Total protein was determined by the method of Lowry and total sialic acid using Ehrlich reagent. Laemmli SDS-polyacrylamide gel electrophoresis was also carried out. RESULTS: Buffering capacity and pH were quite similar for both groups. For permanent dentition subjects pH was significantly higher (P = 0.03) in the Down's syndrome group. The salivary flow rate of the Down's syndrome subjects was significantly lower (P < 0.01) than that of healthy controls and the Down's syndrome subjects' salivary protein and sialic acid levels were significantly higher (P < 0.001). The ratios of total sialic acid to total protein were significantly higher (P < 0.001) in the Down's syndrome group. However, salivary sialic acid expectoration rates, a means of compensating for flow rate differences, were significantly lower (P = 0.01) in the Down's syndrome subjects than in controls. Electrophoresis revealed no significant differences between the protein bands of the groups. There were no significant differences in caries indices between groups, even when compensated for age, nor in the salivary parameters within groups between sexes. CONCLUSIONS: Total salivary sialic acid in Down's syndrome subjects, higher in terms of levels but lower in terms of expectoration rates, was significantly different from that of controls of similar caries indices.

Hemifacial microsomia: oral, clinical, genetic and dermatoglyphic findings.

Oral, clinical, genetic and dermatoglyphic findings of a female patient with hemifacial microsomia are described and compared with those cited in the literature.

Dental caries and Cariostat test in preschool children.

The aim of this study was to investigate the caries status and susceptibility of children in preschool age. Sixty one children ages between 3 to 5 years (mean age 4.38 +/- 0.71) participated in this study. Caries status was assessed according to WHO criteria, and caries susceptibility by using the Cariostat test. The mean df-t was found to be 2.28 +/- 0.71 (df-s 6.26 +/- 11.92) and 31 children were caries-free. Cariostat scores were 1.75, 2.00, 2.16 in the 3, 4, and 5 year age groups respectively. There were no significant differences in caries status or Cariostat scores between boys and girls. The df-t for the 5 year age group was significantly higher than that for the 3 year age groups (p < 0.05). The test found 77% of the children to have a high caries risk (Cariostat score > 2.0).