Doubly Fused Unsymmetrical Calixdicarbahexaphyrins.

Three novel doubly fused unsymmetrical calixdicarbahexaphyrins were synthesized by mild acid-catalyzed (4+2) condensation of dicarbatetrapyrrane with dipyrroethene diol followed by oxidation. The condensation formed doubly fused calixdicarbahexaphyrins instead of π-conjugated dicarbahexaphyrins, due to the unusual fusion of the pyrrole N with the α-carbon of the adjacent pyrrole ring to form a tripentacyclic ring and one usual fusion of the pyrrole N with the adjacent phenylene C to form a fused moiety containing two pentacycles and one hexacycle ring. Both fusions occurred on one side of the macrocycle, making the macrocycles unsymmetric. The crystal structure obtained for one of the macrocycles exhibited a saddle-shaped structure with two benzene rings and four pyrrole rings connected via two ethylene and four methene meso-carbon atoms. The crystal structure also revealed unusual fusions in the macrocyclic framework and the presence of one sp3 carbon that disrupts the π-electron delocalization. 1H, 1H-1H COSY, NOESY, 13C, and HMBC NMR techniques were used to characterize the macrocycles. The absorption spectra of the macrocycles showed one intense sharp band at ∼485 nm along with a shoulder in the lower-energy region, suggesting its non-aromatic nature. Electrochemical studies indicated their electron rich nature, and DFT/TD-DFT studies corroborated the experimental observations.

Electron-phonon superconductivity in C-doped topological nodal-line semimetal Zr5Pt3: a muon spin rotation and relaxation (µSR) study.

In the present work, we demonstrate that C-doped Zr5Pt3is an electron-phonon superconductor (with critical temperatureTC= 3.8 K) with a nonsymmorphic topological Dirac nodal-line semimetal state, which we report here for the first time. The superconducting properties of Zr5Pt3C0.5have been investigated by means of magnetization, resistivity, specific heat, and muon spin rotation and relaxation (µSR) measurements. We find that at low temperatures, the depolarization rate is almost constant and it can be well described by a single-bands-wave model with a superconducting gap of 2Δ(0)/kBTC= 3.84, somewhat higher than the value of BCS theory. From the transverse field µSR analysis, we estimate the London penetration depthλL= 469 nm, superconducting carrier densityns= 1.83 × 1026 m-3, and effective massm* = 1.428me. The zero field µSR confirms the absence of any spontaneous magnetic field in the superconducting ground state. In order to gain additional insights into the electronic ground state of C-doped Zr5Pt3, we also performed first-principles calculations within the framework of density functional theory (DFT). The observed homogenous electronic character of the Fermi surface as well as the mutual decrease ofTCand density of states at the Fermi level are consistent with the experimental findings of this study. However, the band structure reveals the presence of robust, gapless fourfold-degenerate nodal lines protected by 63screw rotations and glide mirror planes. Therefore, Zr5Pt3represents a novel, unprecedented condensed matter system to investigate the intricate interplay between superconductivity and topology.

A Comparative Study between Indigenous Low Cost Negative Pressure Wound Therapy with Added Local Oxygen versus Conventional Negative Pressure Wound Therapy.

INTRODUCTION: The incidence of compound fractures and severe soft tissue loss has increased manifolds due to high speed traffics. Negative Pressure Wound Therapy (NPWT) is a treatment modality for managing soft tissue aspect of such injuries. It reduces the need of flap coverage. However, many patients from developing countries cannot afford a conventional NPWT. We developed an indigenous low cost NPWT for our patients and supplemented it with Topical Pressurised Oxygen Therapy (TPOT). We conducted this study to compare its treatment outcome with the use of conventional NPWT. MATERIALS AND METHODS: The study was conducted from 2018 to 2020 at a tertiary care teaching hospital. A total of 86 patients were treated with NPWT and their results were assessed for various parameters like reduction in wound size, discharge, infection, etc. We included patients with acute traumatic wounds as well as chronic infected wounds, and placed them in three treatment groups to receive either conventional NPWT, Indigenous NPWT and lastly NPWT with supplement TPOT. RESULTS: We observed a significant reduction of wound size, discharge and infection control in all three groups. The efficacy of indigenous NPWT is at par with conventional NPWT. Only six patients who had several comorbidities required flap coverage while in another four patients we could not achieve desired result due to technical limitations. CONCLUSION: Indigenous NPWT with added TPOT is a very potent and cost effective method to control infection and rapid management of severe trauma seen in orthopaedic practice. It also decreases the dependency on plastic surgeons for management of such wounds.

Investigation of superconducting gap structure in HfIrSi using muon spin relaxation/rotation.

We have investigated the superconducting state of HfIrSi using magnetization, specific heat, muon spin rotation and relaxation ([Formula: see text]SR) measurements. Superconductivity was observed at [Formula: see text] K in both specific heat and magnetization measurements. From an analysis of the transverse-field [Formula: see text]SR data, it is clear that the temperature variation of superfluid density is well fitted by an isotropic Bardeen-Cooper-Schrieffer (BCS) type s-wave gap structure. The superconducting carrier density [Formula: see text] m-3, the magnetic penetration depth, [Formula: see text] nm, and the effective mass, [Formula: see text], were calculated from the TF-[Formula: see text]SR data. Zero-field [Formula: see text]SR data for HfIrSi reveal the absence of any spontaneous magnetic moments below [Formula: see text], indicating that time-reversal symmetry (TRS) is preserved in the superconducting state of HfIrSi. Theoretical investigations suggest that the Hf and Ir atoms hybridize strongly along the c-axis, and that this is responsible for the strong three-dimensionality of this system which screens the Coulomb interaction. As a result, despite the presence of d-electrons in HfIrSi, these correlation effects are weakened, making the electron-phonon coupling more important.

A Comparative Study between Indigenous Low Cost Negative Pressure Wound Therapy with Added Local Oxygen versus Conventional Negative Pressure Wound Therapy

@#Introduction: The incidence of compound fractures and severe soft tissue loss has increased manifolds due to high speed traffics. Negative Pressure Wound Therapy (NPWT) is a treatment modality for managing soft tissue aspect of such injuries. It reduces the need of flap coverage. However, many patients from developing countries cannot afford a conventional NPWT. We developed an indigenous low cost NPWT for our patients and supplemented it with Topical Pressurised Oxygen Therapy (TPOT). We conducted this study to compare its treatment outcome with the use of conventional NPWT. Materials and Methods: The study was conducted from 2018 to 2020 at a tertiary care teaching hospital. A total of 86 patients were treated with NPWT and their results were assessed for various parameters like reduction in wound size, discharge, infection, etc. We included patients with acute traumatic wounds as well as chronic infected wounds, and placed them in three treatment groups to receive either conventional NPWT, Indigenous NPWT and lastly NPWT with supplement TPOT. Results: We observed a significant reduction of wound size, discharge and infection control in all three groups. The efficacy of indigenous NPWT is at par with conventional NPWT. Only six patients who had several comorbidities required flap coverage while in another four patients we could not achieve desired result due to technical limitations. Conclusion: Indigenous NPWT with added TPOT is a very potent and cost effective method to control infection and rapid management of severe trauma seen in orthopaedic practice. It also decreases the dependency on plastic surgeons for management of such wounds.

Evidence of a Nodal Line in the Superconducting Gap Symmetry of Noncentrosymmetric ThCoC_{2}.

The newly discovered noncentrosymmetric superconductor ThCoC_{2} exhibits numerous types of unconventional behavior in the field dependent heat capacity data. Here we present the first measurement of the gap symmetry of ThCoC_{2} by muon spin rotation and relaxation (µSR) measurements. The temperature dependence of the magnetic penetration depth measured using the transverse field µSR experiment reveals the evidence of a nodal pairing symmetry. To understand this finding, we carry out calculations of the superconducting pairing eigenvalue and eigenfunction (pairing symmetry) due to the spin-fluctuation mechanism by directly implementing the ab initio band structures. We find that the system possesses a single Fermi surface with considerable three dimensionality and a strong nesting along the k_{z} direction. Such nesting promotes a superconducting state with a cosk_{z}-like pairing symmetry with a prominent nodal line on the k_{z}=±π/2 plane. The result agrees well with the experimental data.

Serial evaluation of retinal vascular changes in infants treated with intravitreal bevacizumab for aggressive posterior retinopathy of prematurity in zone I.

PURPOSE: To evaluate the serial changes in retinal vasculature in infants treated with intravitreal bevacizumab (IVB) for aggressive posterior retinopathy of prematurity (APROP) in zone I. METHODS: Retrospective analysis of serial changes in retinal vasculature after IVB in the seven eyes of four babies with APROP in zone I. RESULTS: The initial regression, following IVB, was dramatic with reduction in vessel caliber and marked thinning and invisibility of the bridging shunts. Resurgent vascular development was very slow radially though there was continued abnormal vascular growth circumferentially. Common findings in all eyes were tangled vasculature and fine saw-toothed shunts. The variable findings were (1) new closely packed multilayered bridging shunts, long arching mature looking vessels, and finally a ridge at the periphery (n=3 eyes) at 52 weeks of postmenstrual age (PMA); (2) status quo at the stage of saw-toothed shunt and ridge in both eyes for a long time (n=2 eyes); and (3) multiple retinal hemorrhages within the vascularized retina and thick preretinal hemorrhage overlying the saw-toothed shunts and ridge that persisted for another 3 weeks and regressed 2 weeks after laser (n=1). The eyes that received bevacizumab alone (3) did not show any abnormal vascularization at 56 weeks of PMA or beyond. CONCLUSIONS: The retinal vascularization following IVB was different than normal in terms of its time, speed, and morphology; few of these changes are first to be reported in the literature (Medline search) and warrants further studies.

Larger and near-term baby retinopathy: a rare case series.

PURPOSE: To report retinopathy in a series of four babies unusually beyond the screening standards reported so far in the literature. METHODS: During routine screening for retinopathy of prematurity, we detected retinopathy in four babies who were surprisingly bigger and older than the screening standards. The gestational age (GA), birth weight (BW), post menstrual age at first examination and significant perinatal events were noted. The retinopathy details imaged by the RetCam were classified as per ICROP revisited standards. RESULT: The GA ranged from 36 to 39 weeks and BW from 2.4 to 3.0 kg. Three of them had retinopathy in zone III that regressed spontaneously and one had marked plus with vascular arcades and shunts in zone II that regressed after laser photocoagulation. All of them had fetal distress and multiple systemic comorbidities in the neonatal period. CONCLUSION: This report makes one aware of the possibility of retinopathy in newborn of older GA and larger BW especially with fetal distress and stormy neonatal course.

Lack of association between SNP rs3914132 of the RELN gene and otosclerosis in India.

Otosclerosis (MIM 166800) is primarily a metabolic bone disorder of the otic capsule, which leads to bony fixation of the stapedial footplate in the oval window; it is among the most common causes of acquired hearing loss. The etiology of this disease is largely unknown, although epidemiological studies suggest the involvement of both genetic and environmental factors. Recently, a reelin gene, SNP rs3914132, located in intron 2, was shown to be associated with otosclerosis in a European population. When we sequenced blood DNA samples of 85 individuals with otosclerosis and 85 controls, four SNPs of this gene: rs3914131 (P = 0.6463), rs3914132 (P = 0.1822), rs9641319 (P = 0.7371), and rs10227303 (P = 0.5669) were not significantly associated with this disease. In one familial case, a novel variant (C/T) at contig position 2923488 was found to be inherited by the proband and affected family members.

Congenital fusion of the jaws: a management protocol.

Congenital fusion of the jaws is the inability to open the mouth at the time of birth. It occurs as a result of fusion of the jaws or fusion of the mandible to zygoma or temporal bone. The authors report four case studies and describe their management protocol.

An efficient highly regioselective synthesis of 2,3,4-trisubstituted pyrroles by cycloaddition of polarized ketene S,S- and N,S-acetals with activated methylene isocyanides.

An efficient route for regioselective synthesis of 2,3,4- substituted pyrroles allowing precise control over the introduction of a number of substituents and functionalities (tosyl, carbalkoxy, aryl, cyano, nitro, acetyl, benzoyl, cyclic amines, etc.) at the three positions of the pyrrole ring has been developed via 1,3-dipolar cycloaddition of readily accessible polarized ketene S,S- and N,S-acetals with carbanions derived from activated methylene isocyanides.

Mass transfer and oxidation kinetics in an in situ ozone generator.

An in situ ozone generator design based on a novel type of corona discharge tube construction was tested to examine enhancements in mass transfer and ozonation efficiency over conventional systems. In this design, the discharge gap is kept juxtaposed to the tubular pathway through which the treatment fluid is passed. A porous inner electrode tube is employed in the discharge tube, and the generated ozone diffuses through this porous tube and dissolves and reacts with the contaminants in the fluid that is being treated. The inner porous ceramic tube is grounded while the outer glass electrode is positively charged for corona discharge. Oxidation studies conducted on Reactive Blue 19 dye indicate that the time required for 90% color removal is about half that of a conventional ozone generation and bubble diffusion system at the same ozone dosage.

Cigarette smoke-induced protein oxidation and proteolysis is exclusively caused by its tar phase: prevention by vitamin C.

We have reported before that whole phase cigarette smoke (CS) contains stable oxidants that cause oxidative damage and increased proteolysis of proteins [Free Radic. Biol. Med. 27 (1999) 1064]. Here, we demonstrate that these oxidants are exclusively present in the tar phase of the CS and not its gas phase and can almost wholly account for the observed whole phase CS-induced oxidation of human plasma proteins as well as extensive oxidative proteolysis of guinea pig lung and heart microsomal proteins in vitro. The mechanism of the tar phase CS-induced proteolysis of microsomal proteins involves two-steps: (i) initial oxidation of the proteins by oxidants present in the tar extract followed by (ii) rapid proteolytic degradation of the oxidized proteins by proteases present in the microsomes. Like the whole phase CS, the oxidative damage of proteins caused by the tar phase CS, as evidenced by the formation of protein carbonyl and bityrosine as well as loss of tryptophan residues and thiol groups, is also almost completely prevented by ascorbic acid and only partially by glutathione. Other antioxidants, including superoxide dismutase, catalase, vitamin E, beta-carotene and mannitol are ineffective. This again leads us to suggest that adequate intake of vitamin C may help smokers to evade the CS-induced degenerative diseases associated with oxidative damage. The revelation of the acute toxicity of the tar phase with respect to CS-induced oxidative damage also urges the necessity of trapping it more effectively by suitable cigarette filters to reduce the health damage caused to smokers.

Evaluation of phytotoxicity and genotoxicity of uranyl nitrate in Allium assay system.

Uranyl nitrate inhibited root growth of Allium cepa at > or = 25 microM concentration. Fluorimetric analysis of metal uptake indicated the entry and accumulation of uranium into the root cell. Uranyl nitrate was neither clastogenic nor aneugenic as it failed to induce micronuclei significantly, but between 25 and 100 microM concentration, it increased significantly the frequency of sister chromatid exchange over that of control, implying its genotoxicity that possibly interfered with DNA replication and/or repair process.

Calmodulin activates intersubunit electron transfer in the neuronal nitric-oxide synthase dimer.

Neuronal nitric oxide synthase (nNOS) is composed of an oxygenase domain that binds heme, (6R)-tetrahydrobiopterin, and Arg, coupled to a reductase domain that binds FAD, FMN, and NADPH. Activity requires dimeric interaction between two oxygenase domains and calmodulin binding between the reductase and oxygenase domains, which triggers electron transfer between flavin and heme groups. We constructed four different nNOS heterodimers to determine the path of calmodulin-induced electron transfer in a nNOS dimer. A predominantly monomeric mutant of rat nNOS (G671A) and its Arg binding mutant (G671A/E592A) were used as full-length subunits, along with oxygenase domain partners that either did or did not contain the E592A mutation. The E592A mutation prevented Arg binding to the oxygenase domain in which it was present. It also prevented NO synthesis when it was located in the oxygenase domain adjacent to the full-length subunit. However, it had no effect when present in the full-length subunit (i.e. the subunit containing the reductase domain). The active heterodimer (G671A/E592A full-length subunit plus wild type oxygenase domain subunit) showed remarkable similarity with wild type homodimeric nNOS in its catalytic responses to five different forms and chimeras of calmodulin. This reveals an active involvement of calmodulin in supporting transelectron transfer between flavin and heme groups on adjacent subunits in nNOS. In summary, we propose that calmodulin functions to properly align adjacent reductase and the oxygenase domains in a nNOS dimer for electron transfer between them, leading to NO synthesis by the heme.

Moustache reconstruction using an extended midline forehead flap.

A new method for reconstruction of the upper lip and moustache is presented. An extended midline forehead flap is described, which is a modification of the classical midline forehead flap in which the flap is extended into the hair-bearing scalp. Simultaneously, a nasal alar defect was reconstructed using the non-hair-bearing forehead skin in a patient with cancrum oris. The flap is reliable, technically easy to raise, does not require any special expertise and causes minimal donor site deformity. However, it is a multistage procedure and hence causes prolonged morbidity.

Vitamin C prevents cigarette smoke-induced oxidative damage in vivo.

Our recent in vitro results [4] indicate that cigarette smoke induces oxidation of human plasma proteins and extensive oxidative degradation of the guinea pig lung, heart, and liver microsomal proteins, which is almost completely prevented by ascorbic acid. In this paper, we substantiate the in vitro results with in vivo observations. We demonstrate that exposure of subclinical or marginal vitamin C-deficient guinea pigs to cigarette smoke causes oxidation of plasma proteins as well as extensive oxidative degradation of the lung microsomal proteins. Cigarette smoke exposure also results in some discernible damage of the heart microsomal proteins. The oxidative damage has been manifested by SDS-PAGE, accumulation of carbonyl and bityrosine, as well as loss of tryptophan and protein thiols. Cigarette smoke exposure also induces peroxidation of microsomal lipids as evidenced by the formation of conjugated dienes, malondialdehyde, and fluorescent pigment. Cigarette smoke-induced oxidative damage of proteins and peroxidation of lipids are accompanied by marked drop in the tissue ascorbate levels. Protein damage and lipid peroxidation are also observed in cigarette smoke-exposed pair-fed guinea pigs receiving 5 mg vitamin C/animal/day. However, complete protection against protein damage and lipid peroxidation occurs when the guinea pigs are fed 15 mg vitamin C/animal/day. Also, the cigarette smoke-induced oxidative damage of proteins and lipid is reversed after discontinuation of cigarette smoke exposure accompanied by ascorbate therapy. The results, if extrapolated to humans, indicate that comparatively large doses of vitamin C may protect the smokers from cigarette smoke-induced oxidative damage and associated degenerative diseases.

Primary angiitis of CNS : neuropathological study of three autopsied cases with brief review of literature.

Primary angiitis of CNS(PACNS) or granulomatous angiitis of CNS is a rare inflammatory disease of small blood vessels mostly confined to the CNS. The clinical and pathological features of 3 autopsied cases are described. Clinically all the three PACNS patients were young males, age ranging from 19 to 31 years. All presented with varied neurological manifestations. There was no evidence of systemic disease in any of the cases. The ESR was normal and CSF analysis showed chronic meningitic pattern. The cerebral angiogram in one case was normal and the CT scan done in another case showed multiple intracerebral haematoma due to vasculitis. Brain biopsy was not done. Diagnosis was made at post-mortem examination. Histology showed characteristic but variable degree of granulomatous and non-granulomatous angiitis of small vessels. Venulitis with parenchymal haemorrhages was the predominant feature and in one case phlebitis with thrombosis was noted. Since the disease responds to steroids and immunosuppressive therapy, establishing antemortem diagnosis is important. In view of the association of angiitis of CNS with bacteria and viral infections, their role in the evolution of the disease needs to be investigated.

ANALYTICAL REVIEW OF: REVIEW MEDICAL BOARDS (RMB) CARRIED OUT DURING 1993-98.

The medical fitness of the candidates selected for officers' training institutes of three wings of Armed Forces is assessed by special medical boards(SMBs) and appeal medical boards (AMBs). The candidates declared unfit at AMBs arc given one more chance to prove their medical fitness, if they so desire, at an another board, designated as review medical board (RMB). RMB is sanctioned by DGAFMS based on merit of the case and as per the provisions of para 482 of RMSAF -1983. The venue of RMB is either at AFMC Pune or at Army Hospital (R&R) Delhi. RMB documents for the period from 1993-98 were analysed. During this period 338 requests for RMB were received, out of which 173 cases were given sanction (51.69%) for RMB. The average percentage of fitness in RMB among the total requests was 25.73%. There was no significant difference in the percentage of fitness between the RMBs held at AFMC Pune and Army Hospital (R&R) Delhi. Thus the paper goes to prove its usefulnesss to the candidates as well as to services and its fairness.

Vitamin C prevents cigarette smoke induced oxidative damage of proteins and increased proteolysis.

Aqueous extract of cigarette smoke (CS) contains some stable oxidants, which oxidize human plasma proteins, bovine serum albumin, amino acid homopolymers, and also cause extensive oxidative degradation of microsomal proteins. Similar observations are made when the aqueous extract of cigarette smoke is replaced by whole phase CS solution or whole phase cigarette smoke. CS-induced microsomal protein degradation is a two step process: (i) oxidation of proteins by the oxidants present in the CS and (ii) rapid proteolytic degradation of the oxidized proteins by proteases present in the microsomes. Using aqueous extract of CS equivalent to that produced from one-twentieth of a cigarette, the observed initial and postcigarette smoke treated values of different parameters of oxidative damage per milligram of microsomal proteins are respectively: 0.24 and 1.74 nmoles for carbonyl formation, 125.4 and 62.8 fluorescence units for tryptophan loss, 10.2 and 33.4 fluorescence units for bityrosine formation, and 58.3 and 12.2 nmoles for loss of protein thiols. When compared with sodium dodecyl sulphate polyacrylamide gel electrophoresis profiles of untreated microsomal proteins, the extent of microsomal protein degradation after treatment with whole phase CS solution or aqueous extract of CS is above 90%. Ascorbate (100 microM) almost completely prevents cigarette smoke-induced protein oxidation and thereby protects the microsomes from subsequent proteolytic degradation. Glutathione is partially effective, but other antioxidants including superoxide dismutase, catalase, vitamin E, probucol, beta-carotene, mannitol, thiourea, and histidine are ineffective. The gas phase cigarette smoke contains unstable reactive oxygen species such as superoxide (O2*-) and hydrogen peroxide (H2O2) that can cause substantial oxidation of pure protein like albumin but is unable to produce significant oxidative damage of microsomal proteins. Gas phase cigarette smoke-induced albumin oxidation is not only inhibited by ascorbate and glutathione but also by superoxide dismutase, catalase and mannitol. The stable oxidants in the cigarette smoke are not present in the tobacco and are apparently produced by the interaction of O2*-/H2O2/OH* of the gas phase with some components of the tar phase during/following the burning of tobacco.