Synthesis, spectroscopic, dielectric, molecular docking and DFT studies of (3E)-3-(4-methylbenzylidene)-3,4-dihydro-2H-chromen-2-one: an anticancer agent.

BACKGROUND: Coumarin (2H-chromen-2-one) and its derivatives have a wide range of biological and pharmaceutical activities. They possess antitumor, anti-HIV, anticoagulant, antimicrobial, antioxidant, and anti-inflammatory activities. Synthesis and isolation of coumarins from different species have attracted the attention of medicinal chemists. Herein, we report the synthesis, molecular structure, dielectric, anticancer activity and docking studies with the potential target protein tankyrase. RESULTS: Molecular structure of (3E)-3-(4-methylbenzylidene)-3,4-dihydro-2H-chromen-2-one (MBDC) is derived from quantum chemical calculations and compared with the experimental results. Intramolecular interactions, stabilization energies, and charge delocalization are calculated by NBO analysis. NLO property and dielectric quantities have also been determined. It indicates the formation of a hydrogen bonding between -OH group of alcohol and C=O of coumarin. The relaxation time increases with the increase of bond length confirming the degree of cooperation and depends upon the shape and size of the molecules. The molecule under study has shown good anticancer activity against MCF-7 and HT-29 cell lines. Molecular docking studies indicate that the MBDC binds with protein. CONCLUSIONS: In this study, the compound (3E)-3-(4-methylbenzylidene)-3,4-dihydro-2H-chromen-2-one was synthesized and characterized by spectroscopic studies. The computed and experimental results of NMR study are tabulated. The dielectric relaxation studies show the existence of molecular interactions between MBDC and alcohol. Theoretical results of MBDC molecules provide the way to predict various binding sites through molecular modeling and these results also support that the chromen substitution is more active in the entire molecule. Molecular docking study shows that MBDC binds well in the active site of tankyrase and interact with the amino acid residues. These results are compared with the anti cancer drug molecule warfarin derivative. The results suggest that both molecules have comparable interactions and better docking scores. The results of the antiproliferative activity of MBDC and Warfarin derivative against MCF-7 breast cancer and HT-29 colon cancer cell lines at different concentrations exhibited significant cytotoxicity. The estimated half maximal inhibitory concentration (IC 50) value for MBDC and Warfarin derivative was 15.6 and 31.2 µg/ml, respectively. This enhanced cytotoxicity of MBDC in MCF-7 breast cancer and HT-29 colon cancer cell lines may be due to their efficient targeted binding and eventual uptake by the cells. Hence the compound MBDC may be considered as a drug molecule for cancer.Graphical abstractThe binding mode of the ligand MBDC at active site of protein and the graphical representation of cell inhibition for MCF-7 and HT-29 cell lines.

Neonatal septic arthritis in a tertiary care hospital: a descriptive study.

PURPOSE: The study was conducted to evaluate clinical and microbiological profile of neonates with septic arthritis and also to assess changing epidemiology in the microbial etiology. METHODS: Twenty-nine neonates (1-28 days of life) presenting to the Department of Orthopaedics with acute septic arthritis were included in the study. This was a descriptive study, and the data were collected during the time of hospital admission. History and clinical examination of the neonates were taken, and diagnosis was made based on clinical and laboratory parameters. Emergency arthrotomy was performed to prevent catastrophic sequelae in all the cases given antibiotics as per the culture results. RESULTS: Female children predominated in our study. The children were brought to the OPD with an average of 2.7 days of fever. Thirty-four joints were involved in 29 neonates, out of whom five had more than one joint involvement. Joint effusion or subperiosteal abscess was found in 22 patients by USG. All children had leukocytosis with neutrophilic predominance. Twenty-one of twenty-nine patients had hip-joint involvement followed by knee in seven patients. Gram-negative organisms had grown more commonly, among which Klebsiella pneumonia was grown in nine patients. CONCLUSION: Prematurity and anemia still appear to be important risk factors for neonatal septic arthritis. As there is changing trend toward gram-negative infections, attention has to be given toward preventing nosocomial and community-acquired infections. This is very important in premature infants who are susceptible for infection when they are kept in resuscitative units in hospitals.

A retrospective analysis of osteochondroma of scapula following excision biopsy.

Scapula is an uncommon site for osteochondroma. There is a paucity of information regarding postoperative complications, recurrence of osteochondroma, functional improvement. A retrospective analysis of 9 patients treated for osteochondroma scapula over a period of 4 years was undertaken to assess postoperative complications, recurrence, and functional improvement following excision biopsy for osteochondroma scapula. All patients of any age group who were diagnosed with osteochondroma scapula and treated with excision biopsy in the past 6 years were included in the study. Patients were followed up for recurrence, postoperative complications and functional assessment using modified UCLA shoulder rating scale. The mean age at presentation was 13.7 years. Boys were more commonly affected than girls with a male to female ratio of 7:2. There was no incidence of recurrence of osteochondroma, postoperative wound complications or functional limitation following excision biopsy of osteochondroma scapula. We conclude that preoperative functional restriction in osteochondroma of scapula is mainly due to location of tumour especially when present over ventral or ventromedial aspect scapula. After complete excision they do not cause any functional limitations.

Molecular structure, spectroscopic (FT-IR, FT-Raman), NBO analysis of N,N'-diphenyl-6-piperidin-1-yl-[1,3,5]-triazine-2,4-diamine.

In the present work, we have synthesized and reported a combined experimental and theoretical study on the molecular structure, vibrational spectra and HOMO-LUMO analysis of N,N'-diphenyl-6-piperidin-1-yl-[1,3,5]-triazine-2,4-diamine (C20N6H22). The FT-IR and FT-Raman spectra of N,N'-diphenyl-6-piperidin-1-yl-[1,3,5]-triazine-2,4-diamine were recorded. The molecular geometry, harmonic vibrational wavenumbers and bonding features of the title molecule in the ground-state have been calculated by using the density functional B3LYP method with 6-31G(d) as basis set. Non-linear optical (NLO) behavior of the N,N'-diphenyl-6-piperidin-1-yl-[1,3,5]-triazine-2,4-diamine was investigated by determining the electric dipole moment µ, polarizability α, and hyperpolarizability ß using the above mentioned basis set. The molecular properties such as ionization potential, electro-negativity, chemical potential, electrophilicity have been deduced from HOMO-LUMO analysis employing the same basis set. The calculated HOMO and LUMO energies showed that charge transfer occurs within the molecule. Stability of the molecule arising from hyper conjugative interaction and charge delocalization has been analyzed using natural bond orbital (NBO) analysis. Finally, the calculation results were applied to simulate infrared and Raman spectra of the title compound which showed good agreement with the observed spectra.

Comparative vibrational spectroscopic studies, HOMO-LUMO, NBO analyses and thermodynamic functions of p-cresol and 2-methyl-p-cresol based on DFT calculations.

In the present study structural properties of p-cresol, and 2-methoxy-p-cresol have been studied by using B3LYP/cc-pvdz and B3PW91/cc-pvdz of Density Functional Theory (DFT) utilizing Becke three exchange functional and Lee Yang Paar correlation functional. The Fourier transform infrared and Fourier transform Raman spectra of title molecules were recorded (solid phase). Optimized geometry, harmonic vibrational frequencies and various thermodynamic parameters of the title compounds were calculated with B3LYP/cc-pvdz, and B3PW91/cc-pvdz basis sets. Non-linear optical (NLO) behavior of the p-cresol and 2-methoxy-p-cresol were investigated by determining of electric dipole moment, polarizability α, and hyperpolarizability ß using the above mentioned basis sets. The molecular properties such as ionization potential, electronegativity, chemical potential, electrophilicity have been deduced from HOMO-LUMO analysis employing the same basis sets. A detailed interpretation of the infrared and Raman spectra of title molecules were reported. UV spectrum was measured in different solvent. The energy and oscillator strength are calculated by Time Dependant Density Functional Theory (TD-DFT) results. The calculated HOMO and LUMO energies also confirm that charge transfer occurs within the molecule. The complete assignments were performed on the basis of the potential energy distribution (PED) of vibrational modes, calculated with scaled quantum mechanics (SQM) method. Finally the theoretical FT-IR, FT-Raman, and UV spectra of the title molecules have also been constructed.

Quantum chemical determination of molecular geometries, interpretation of FT-IR, FT-Raman spectra and charge transfer properties for N-(2-cyanoethyl)-N-methylaniline.

FT-Raman and FT-IR spectra were recorded for N-(2-cyanoethyl)-N-methylaniline sample in solid state. The equilibrium geometries, harmonic vibrational frequencies, infrared and Raman scattering activities were computed using DFT method. Results obtained at this level of theory were used for a detailed interpretation of the infrared and Raman spectra, based on the potential energy distribution (PED) of the normal modes. Molecular parameters such as bond length, and bond angle were calculated with the same method. The intra-molecular charge transfer was calculated by means of natural bond orbital analysis (NBO). Hyperconjugative interaction energy was more during the π-π(*) transition. Energy gap of the molecule was found using HOMO and LUMO calculation, hence the less band gap, which seems to be more stable. Atomic charges of various atoms of title molecule and other thermo-dynamical parameters were calculated using same levels of calculation. The correlation equations between heat capacity, entropy, Gibb's free energies changes with temperatures were fitted by quadratic formula. UV-VIS spectral analyses of title molecule have been researched by theoretical calculations. In order to understand electronic transitions of the compound, TD-DFT calculations on electronic absorption spectra in gas phase and solvent were performed. The calculated frontier orbital energies, absorption wavelengths (λ), oscillator strengths (f) and excitation energies (E) for gas phase in different solvent are also illustrated.

Theoretical investigations on molecular structure, vibrational spectra, HOMO, LUMO, NBO analysis and hyperpolarizability calculations of thiophene-2-carbohydrazide.

The Fourier-Transform infrared and Fourier-Transform Raman spectra of thiophene-2-carbohydrazide (TCH) was recorded in the region 4000-400 cm(-1) and 3500-100 cm(-1). Quantum chemical calculations of energies, geometrical structure and vibrational wavenumbers of TCH were carried out by DFT (B3LYP) method with 6-311++G(d,p) as basis set. The difference between the observed and scaled wavenumber values of most of the fundamentals is very small. Stability of the molecule arising from hyper conjugative interaction and charge delocalization has been analyzed using natural bond orbital (NBO) analysis. UV spectrum was measured in different solvent. The energy and oscillator strength are calculated by Time Dependant Density Functional Theory (TD-DFT) results. The calculated HOMO and LUMO energies also confirm that charge transfer occurs within the molecule. The complete assignments were performed on the basis of the potential energy distribution (PED) of vibrational modes, calculated with scaled quantum mechanics (SQM) method. Finally the theoretical FT-IR, FT-Raman, and UV spectra of the title molecule have also been constructed.

Vibrational (FT-IR and FT-Raman) spectra, NBO, HOMO-LUMO, Molecular electrostatic potential surface and computational analysis of 4-(trifluoromethyl)benzylbromide.

In this work, the vibrational characteristics of 4-(trifluoromethyl) benzylbromide (TFMBB) have been investigated and both the experimental and theoretical vibrational data indicate the presence of functional groups in the title molecule. The density functional theoretical (DFT) computations were performed at the B3LYP/6-311+G (d,p) levels to derive the optimized geometry, vibrational wavenumbers with IR and Raman intensities. Furthermore, the molecular orbital calculations such as natural bond orbitals (NBOs), HOMO-LUMO energy gap and Mapped molecular electrostatic potential (MEP) surfaces were also performed with the same level of DFT. The thermal flexibility of molecule in associated with vibrational temperature was also illustrated on the basis of correlation graphs. The detailed interpretation of the vibrational spectra has been carried out with the aid of potential energy distribution (PED) results obtained from MOLVIB program. The delocalization of electron density of various constituents of the molecule has been discussed with the aid of NBO analysis.

Calcific myonecrosis of the leg treated by debridement and limited access dressing.

Calcific myonecrosis is a rare late complication of limb trauma characterized by liquefaction and dystrophic calcification of muscles in the single compartment, usually in the leg. This occurs many years after the trauma and is probably due to chronic compartment syndrome. We report 2 cases of calcific myonecrosis involving the anterior compartment of the leg that presented to us in an advanced stage of multiple sinuses discharging calcific material. Incision and drainage had been attempted at a local hospital prior to presentation at our hospital resulting in a non healing wound. Both patients had a history of antecedent trauma to the leg a few years ago. Patients were treated by thorough debridement of the involved muscles in the anterior compartment. Limited access dressing (LAD) was used to manage the dead space left after debridement. After application of the LAD, the wound was covered with split skin grafting. In both patients, healing of the cavity following debridement was facilitated by application of limited access dressing. While the wound completely healed, the disability due to extensive debridement of anterior compartment of the leg persisted. At the latest follow-up, the patients were asymptomatic without any recurrence. Thorough debridement of the compartment involved and application of LAD may be another option of treating calcific myonecrosis of the leg, which was initially considered a "do not touch" lesion. Morbidity due to surgery and need of repeated surgeries for recurrences should be kept in mind and regular follow-up should be considered.

Vibrational (FT-IR and FT-Raman) spectra and quantum chemical studies on the molecular orbital calculations, chemical reactivity and thermodynamic parameters of 2-chloro-5-(trifluoromethyl) aniline.

In this work, the vibrational characteristics of 2-chloro-5-(trifluoromethyl) aniline have been investigated and both the experimental and theoretical vibrational data indicate the presence of various functional groups within the title molecule. The influence of chlorine substituent on the vibrational wavenumbers of a molecule in comparison with aniline and trifluoromethyl aniline has been discussed in detail. The density functional theoretical (DFT) computations were performed at the B3LYP/6-31++G(3df,3pd)/6-31G(3df,3pd) levels to derive the optimized geometry, vibrational wavenumbers with IR and Raman intensities. Furthermore, the molecular orbital calculations such as; natural bond orbitals (NBOs) and HOMO-LUMO energy gap and mapped molecular electrostatic potential (MEP) surfaces were also performed with the same level of DFT. The temperature dependence thermodynamic parameters of a molecule were illustrated on the basis of their correlation graphs. The detailed interpretation of the vibrational spectra has been carried out with the aid of potential energy distribution (PED) results obtained from MOLVIB program. The delocalization of electron density in various constituents of the molecule has been discussed with the aid of NBO and HOMO-LUMO energy gap analysis.

Acute hematogenous septic arthritis of the knee in adults.

PURPOSE OF STUDY: To evaluate the factors associated with acute hematogenous septic arthritis of the knee in adults and to assess the outcome after open knee arthrotomy. METHODS: We performed a prospective evaluation of 26 adult patients with acute nongonococcal septic arthritis of the knee presenting within 7 days. All patients underwent open knee arthrotomy, and final evaluation by means of Knee society score of the affected knee was compared with the contra lateral normal knee. RESULTS: The average duration of symptoms at the time of presentation was 3.9 days. Staphylococcus aureus was the commonest bacteria isolated in 17 (65.4 %) patients. The average duration of follow-up in our study was 18.5 months. In our study, Knee society score decreases as the age of the patient advances (P < 0.05) and also it was found to be low (P < 0.05) in the affected knee as compared to contra lateral normal knee. CONCLUSION: Our study shows that age of the patient at presentation is critical as it shows significant reduction in knee score. This explains that the septic arthritis may contribute to the progression of age-related degeneration of the knee joint. There appears to be no definite contributing factors or conditions associated with acute hematogenous septic arthritis of the knee in adults, although further study may be warranted regarding this matter.

Heterotopic ossification of the elbow after closed reduction and retrograde intramedullary nailing for radial neck fracture treated by anconeus interposition.

Heterotopic ossification around the elbow can lead to considerable functional disability. We describe a case of a 42-year-old man who developed heterotopic ossification of his elbow after closed reduction of the elbow dislocation and radial neck fracture and retrograde intramedullary nailing for radial neck fracture. During the follow-up after initial surgery, movements of the elbow were gradually deteriorated and diagnosed as heterotopic ossification of the elbow. Implant removal, radial head excision along with heterotopic mass, and also interposition of the anconeus muscle resulted in improvement of his elbow mobility. At 18 months of follow-up, patient had elbow flexion arc of 15°-110°, 70° of supination, and 50° of pronation without recurrence of heterotopic ossification. The uniqueness of this case lies in the treatment of heterotopic ossification of the elbow to prevent its recurrence, which was developed after retrograde intramedullary nailing for radial neck fracture following closed reduction.

Molecular structure, spectroscopic (FT-IR, FT-Raman) studies and first-order molecular hyperpolarizabilities, HOMO-LUMO, NBO analysis of 2-hydroxy-p-toluic acid.

FT-Raman and FT-IR spectra for 2-hydroxy-p-toluic acid molecule had been recorded in the regions 3500-100 cm(-1) and 4000-400 cm(-1), respectively. Vibrational frequencies have been calculated in optimum state by employing density functional theory (DFT) and Hartree Fock (HF) methods with 6-311++G(d,p) basis set in monomeric form. SQM force fields have also been used to calculate potential energy distributions in order to make conspicuous vibrational assignments. Optimized geometries of the molecule had been interpreted and compared. The electric dipole moment and first hyperpolarizability values of the investigated molecule were computed using ab initio and DFT calculations. The calculated HOMO and LUMO energies show that charge transfer occurs within the molecule. Stability of the molecule arising from hyper conjugative interactions, charge delocalization has been analyzed using natural bond analysis. The results show that charge in electron density (ED) in the σ(*) antibonding orbitals and E((2)) energies confirms the occurrence of ICT within the molecule.

Vibrational spectroscopic studies, molecular orbital calculations and chemical reactivity of 6-nitro-m-toluic acid.

The potential energy surface scan for the selected dihedral angle of 6-nitro-m-toluic acid (NTA) has been performed to identify stable conformer. The optimized structure parameters and vibrational wavenumbers of stable conformer have been predicted by density functional B3LYP method with 6-311++G(d,p) basis set. The formation of dimer species through carboxylic acid group of the title molecule has also been discussed. The theoretical dimer geometries have been compared with that of monomer and the variations of bond lengths and bond angles upon dimerization were also discussed. Natural bond orbital (NBO) analysis has been performed on both monomer and dimer geometries. The significant changes in occupancies and the energies of bonding and anti-bonding orbitals upon dimerization have been explained in detail. The predicted frontier molecular orbital energies at B3LYP/6-311++G(d,p) method set show that charge transfer occurs within the molecule. The nucleophilic and electrophilic sites obtained from the molecular electrostatic potential (MEP) surface were compared with their derived fitting point charges. The vibrational wavenumbers of NTA affected profusely by the nitro group substitution in comparison to the toluic acid have been interpreted in this work.

Radiolunate coalition: a case report and literature review.

Radiolunate coalition is a very rare entity and was never reported before. we herein describe a case of congenital non-syndromic radiolunate coalition in a 30 year old male with a brief review of literature. we have also suggested a modification to Minaar's classification for carpal coalition.

Synchronous symmetrical atypical osteoid osteoma of tibia: a case report.

We report a case of synchronous symmetrical osteoid osteoma of tibia which was atypical in its appearance on imaging. Our patient was a 30-year-old woman presented with 2 years history of bilateral leg pain more on the right side. The pain was more during night and relieved on taking salicylates. Laboratory investigations were within normal limits. Radiographs and computed tomography revealed bilateral focal irregular cortical sclerosis with narrowing of medullary canal of mid tibia. The lesion on right side was excised enbloc followed by the lesion on left side 3 months later and histologically confirmed as osteoid osteoma. Initially, we thought it was stress fracture or subacute osteomyelitis but it was in fact histopathology which showed osteoid osteoma. Patient was completely asymptomatic postoperatively.

Late septic hip dislocation with multifocal osteomyelitis and malaria: a case report.

A 9-year-old boy presented with high-grade fever associated with pain and swelling in right hip and left leg of 1-week duration. Pus was found on diagnostic aspiration of the right hip joint. Emergency arthrotomy was performed through anterior approach with drill holes in proximal femur and culture showed MRSA. Intravenous antibiotics were given for 4 weeks. Patient symptomatically improved in immediate postoperative period and in bed hip mobilization was started. On eighth postoperative day, child developed high-grade intermittent fever with chills and rigors and diagnosed as plasmodium falciparum malaria. Fever subsided with antimalarial treatment. On twenty-first day, patient complained pain in right hip and X-ray showed posterior hip dislocation with osteomyelitis of proximal femur. Closed reduction and hip spica application was done under general anesthesia. At follow-up, the clinical result was fair with resolution of infection and stiff hip.

Parental consanguinity and associated factors in congenital talipes equinovarus.

BACKGROUND: The cause of congenital talipes equinovarus (CTEV) is multifactorial and, consanguinity could be one of the causative factors in its development. The purpose of this study was, to determine the prevalence of parental consanguinity in CTEV and other factors like associated, congenital anomalies, maternal and fetal factors and also the severity of CTEV in these patients. METHODS: The above factors were studied in 54 patients of less than 1 month of age with parental, consanguinity and 91 feet were evaluated for its severity using Dimeglio classification at the time of presentation. RESULTS: Out of 174 children presented to our department with CTEV, 54 (31%) children were born out, of consanguineous marriage. Thirty seven (68.5%) patients had bilateral CTEV. Twenty five (46.3%), patients had associated congenital anomalies and myelomeningocele being the commonest anomaly, associated. Out of 91 feet 61 (67%) were of grade 4 severity. CONCLUSION: High grade of severity observed in both idiopathic and non idiopathic CTEV suggests the, probable role of consanguinity as an etiological factor in the development of CTEV especially in our, part of the world.