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Background: Osteoarthritis (OA) is characterized by cartilage and synovial inflammation as well as anomalous lower extremity leading to joint pain, and impairment in lifestyle and epidemic of obesity. This study aimed to use the Jumpstart Nutrition® supplement (JNS) for achieving symmetry of aberrant lower extremity and improving the outcome measures in the management of OA., Methods: This week-twelve registry included 108 patients treated with JNS mainly comprised of calcium, phosphorus, magnesium, vitamin-K 2 , coenzyme-Q 10 , vitamin-C, boswellic acids, and curcumin mixed with soy and whey proteins (experimental group) and 72 were treated with symptomatic slow-acting drugs (control group) for chronic OA confirmed with radiological images. The outcome measures (Visual analogue scale, Western Ontario and McMaster Universities Osteoarthritis Index, Knee-injury Osteoarthritis Outcomes Scale, and Body mass index), and anomalous lower extremity included bilateral: knee gaps between biceps femoris-short head and surface of the bed, diameters of muscles at the calf, the thigh, 4cm above and below the patella, angles of straight leg raising, knee- flexion and-extension in supine were evaluated with appropriate protocol at week-0 and at week-12 for both the groups., Results: After week-12, risk ratios of studied lower extremity, and mean ±standard deviation of all outcome measures were significantly improved (p<0.0001), and Kellgren-Lawrence scale (KLS) was upgraded to ≥2 in experimental group compared to control., Conclusions: This registry study indicates that JNS can be used to achieve symmetry of studied lower extremity and to improve the outcome measures safely as an effective management of OA patients confirmed with radiological images correlated with KLS., Competing Interests: The author declares that there are no conflicts of interest regarding the present study., (© The Author(s).)

Relativistic restricted active space (RAS) second-order multireference perturbation theory (MRPT2) methods, incorporating spin-orbit (SO) coupling perturbatively via state interaction (SO-MRPT2/RASSCF), were used to reproduce the absorption spectra of parent metalloporphyrins containing the Mg 2+ , Zn 2+ , Co 2+ , Ni 2+ , Cu 2+ , or FeCl 2+ ions in the 12,500-40,000 cm -1 region. Particular attention was paid to the interaction between the porphyrin ring and the metal 3 d electrons in states of different multiplicities (we used metal 3 d and double d -shell or 3 d ' orbitals). For this class of compounds, the N -electron valence state perturbation theory (NEVPT2) method is superior to the complete active space perturbation theory (CASPT2) and successfully reproduces the energies of all four characteristic transitions ( Q , B , N , and L ) of closed-shell metalloporphyrins. Inclusion of SO coupling was found to have very little effect on excitation energies and oscillator strengths. For FeCl 2+ porphyrin, we treated ligand-to-metal charge-transfer (LMCT; π ,d ), metal ligand field ( d,d ), and metal-to-ligand charge-transfer (MLCT; d ,π*) transitions within the same framework. The broad and intense spectral features associated with its B (Soret) band are attributed to multiconfigurational LMCT ( d ,π*) bands involving strong metal-ligand orbital mixing.

The period of the year from spring to fall, when clocks in most parts of the United States are set one hour ahead of standard time, is called daylight saving time, and its beginning and ending dates and times are set by federal law. The human biological clock is regulated by the timing of light and darkness, which then dictates sleep and wake rhythms. In daily life, the timing of exposure to light is generally linked to the social clock. When the solar clock is misaligned with the social clock, desynchronization occurs between the internal circadian rhythm and the social clock. The yearly change between standard time and daylight saving time introduces this misalignment, which has been associated with risks to physical and mental health and safety, as well as risks to public health. In 2020, the American Academy of Sleep Medicine (AASM) published a position statement advocating for the elimination of seasonal time changes, suggesting that evidence best supports the adoption of year-round standard time. This updated statement cites new evidence and support for permanent standard time. It is the position of the AASM that the United States should eliminate seasonal time changes in favor of permanent standard time, which aligns best with human circadian biology. Evidence supports the distinct benefits of standard time for health and safety, while also underscoring the potential harms that result from seasonal time changes to and from daylight saving time., Citation: Rishi MA, Cheng JY, Strang AR, et al. Permanent standard time is the optimal choice for health and safety: an American Academy of Sleep Medicine position statement. J Clin Sleep Med . 2024;20(1):121-125., (© 2024 American Academy of Sleep Medicine.)

Cancer during pregnancy, affecting 1 in 1000 pregnancies, is rising in incidence due to delayed childbearing and improved detection. Common types include breast cancer, melanoma and cervical cancer and Hodgkin's Lymphoma. There are several physiological changes that occur during pregnancy that make its management a challenge to clinicians. Managing it requires multidisciplinary approaches and cautious test interpretation due to overlapping symptoms. To minimize fetal radiation exposure, non-ionizing imaging is preferred, and the interpretation of tumor markers is challenging due to inflammation and pregnancy effects. In terms of treatment, chemotherapy is avoided in the first trimester but may be considered later. Immunotherapy's safety is under investigation, and surgery depends on gestational age and cancer type. Ethical and legal concerns are growing, especially with changes in U.S. abortion laws. Access to abortion for medical reasons is vital for pregnant cancer patients needing urgent treatment. Maternal outcomes may depend on the type of cancer as well as chemotherapy received but, in general, they are similar to the non-pregnant population. Fetal outcomes are usually the same as the general population with treatment exposure from the second trimester onwards. Fertility preservation may be an important component of the treatment discussion depending on the patient's wishes, age and type of treatment. This article addresses the complicated nature of a diagnosis of cancer in pregnancy, touching upon the known medical literature as well as the ethical-legal implications of such a diagnosis, whose importance has increased in the light of recent judicial developments.

Background: This study aimed to investigate the efficacy of Jumpstart Nutrition® dietary supplement (JNDS) for enhancing the skeletal muscle metabolism and function of older adults with knee osteoarthritis (KOA) by evaluating the biomarkers of aberrant levels of serum tumor necrosis factor-alpha (TNF-α), interleukin-10 (IL-10), C-reactive protein (CRP), creatine kinase-muscle (CK-MM), and aldolase-A (Aldo-A)., Methods: This twelve-week registry included 54 patients treated with JNDS mainly comprised of calcium, phosphorus, vitamin-K 2 , coenzyme-Q 10 , boswellic acid, and curcumin mixed with soy and whey protein (experimental group) and 51 patients treated with symptomatic slow-acting drugs for osteoarthritis (SYSADOA) (control group) for KOA confirmed with radiological images. At week 0 and week 12 for both the groups evaluated, the non-fasting serum levels of TNF-α, IL-10, CRP, CK-MM, and Aldo-A by using appropriate kits., Results: At week-twelve, the respective values of area under the ROC curves of the studied biomarkers for pooled experimental cohorts were 0.928, 0.907, 0.908, 0.927, and 0.988 having the significance of accuracy (R-square):66.28%, 47.25%, 70.39%, 65.13%, and 68.00%, indicating a satisfactory treatment policy, their mean± SD, and risk ratio, all exhibited highly significant differences (p<0.0001) and KOA-gradation was upgraded between≥2 and ≥3 from≥4 as per the Kellgren-Lawrence scale compared to the control. Fewer patients had to use emergency medications (p<0.05)., Conclusions: Results suggest that JNDS may be effectively used to strengthen the skeletal muscle metabolism and function of elderly patients with KOA confirmed with the stabilization of studied biomarkers as an alternative to the treatment of SYSAD correlated with ROC curves and the Kellgren-Lawrence scale., Competing Interests: The author declares that there are no conflicts of interest regarding the present study.

As the world grapples with global warming, it becomes imperative to carefully examine the sustainable energy technology choices. Solar is the fastest growing clean energy source but today it contributes little to the electricity generated, so future installations will dwarf the existing installed base. There is a factor of 2-4 decrease in the energy payback time from the dominant crystalline silicon technology to thin film technologies. Essential criteria like use of abundant materials and simple but mature production technology point to amorphous silicon (a-Si) technology. Here we delve into the primary issue impeding adoption of a-Si technology-the Staebler Wronski Effect (SWE), that generates metastable, light induced defects which reduce the performance of a-Si based solar cells. We demonstrate that a simple change leads to a significant reduction in SWE power loss and define a clear path to elimination of SWE, allowing the technology to be widely adopted., (© 2023. The Author(s).)

Charcot-Marie-Tooth (CMT) disease is mainly a disease of peripheral nervous system and patients typically present with features of demyelinating neuropathy or axonal neuropathy or both. Rarely patients present with features of central nervous system involvement. Parkinsonism, aphemia and familial epilepsy syndrome have previously come up as case reports in association with CMT type 4 J.We hereby describe a family with 3 siblings affected with CMT4J with homozygous FIG4 mutation who presented with global developmental delay, epilepsy and spastic quadriparesis.

Background: Coronavirus disease 2019 (CoVID-19), primarily thought of as a respiratory system disease is actually a multi-system disease with immunological implications. CNS involvement in COVID has been explained in recent literature mainly for stroke, encephalopathy, encephalitis, acute disseminated encephalomyelitis and myelopathy. There are few studies characterizing clinical spectrum of COVID autoimmune encephalitis. We present a unique case of post-COVID autoimmune encephalitis in a diabetic male presenting with language dysfunction and novel radiologic findings., Case Presentation: Patient admitted to inpatient department of a tertiary care hospital of India was evaluated by bedside clinical examination, routine blood tests, CSF study with intrathecal SARS-Cov-2 antibody detection, commercially available tests for autoimmune encephalitis, neuroviral panel with HSV PCR, EEG, 3-Tesla MRI and PET scan. Patient was found to have personality change and transcortical sensory aphasia in the outset of COVID encephalitis. MRI findings like temporal involvement and insular ribboning are also being reported. The patient was treated with IV immunoglobulin and is on an improving course., Conclusions: This case reports dysphasia due to COVID-mediated injury to the language networks, with novel radiologic findings. Role of parainfectious versus immune etiology is also discussed. Further studies are needed to elucidate the mechanism and clinical spectrum of post-COVID autoimmune encephalitis., Competing Interests: Competing interestsThe authors declare that they have no conflict of interest., (© The Author(s) 2022.)

5f covalency in [U(C 7 H 7 ) 2 ] - was probed with carbon K-edge X-ray absorption spectroscopy (XAS) and electronic structure theory. The results revealed U 5f orbital participation in δ-bonding in both the ground- and core-excited states; additional 5f ϕ-mixing is observed in the core-excited states. Comparisons with U(C 8 H 8 ) 2 show greater δ-covalency for [U(C 7 H 7 ) 2 ] - .

Cyclobutadiene (CBD) is the paradigmatic antiaromatic molecule but is known to form highly stable aromatic complexes, e.g. CBD-Fe(CO)3. This intriguing reversal of aromaticity from antiaromatic to aromatic terrain during the complexation process cannot be appropriately handled with single-reference-based theoretical techniques. We explore this aromaticity reversal, for the first time, by a detailed aromaticity analysis using magnetically induced current densities (MICD) and nucleus independent chemical shifts (NICS) using genuine ab initio multi-reference wavefunction-based theory. We trace the dramatic change of aromaticity for a prototypical cyclobutadiene complex, CBD-CH+ (CH+Fe(CO)3), considering a 3D potential energy surface for two independent parameters, namely the approach of CH+ and the automerization cross-section of cyclobutadiene. The 3D potential energy surfaces indicate the presence of a conical intersection/avoided crossing between the ground and the first excited state. The plot of aromaticity indices and the corresponding numerical values show that the change of aromaticity indices is drastic around the conical intersection/avoided crossing and automerization of cyclobutadiene plays a crucial role in the formation of cyclobutadiene complexes. Computations on analogous CBD-Be and CBD-CO systems (Be/COFe(CO)3) emphasize the generality of the conclusions drawn from the CBD-CH+ system.

Myelin oligodendrocyte glycoprotein antibody (MOG-Ab) is involved in the pathogenesis of central nervous system (CNS) demyelination disorders. We aimed to explore the spectrum of MOG-Ab-associated diseases in eastern India. A single-center, prospective observational study was done over a period of 2 years in a tertiary care hospital of eastern India. Patients with CNS demyelination disorders who tested positive for MOG-Ab using live cell-based assay were included in the study; while, those with age less than 1 year, documented preexisting CNS structural lesions, developmental delays or diagnosed multiple sclerosis were excluded. Demographic profile, clinical spectrum, disease course, radiological features as well as response to treatment were analyzed among included patients. Twenty MOG-Ab-positive patients were included (M:F 1:1.85). The median age of symptom onset was 10.5 years. The median follow-up of patients was 13 months. Acute disseminated encephalomyelitis (ADEM) was the commonest presentation at first attack (55%), followed by optic neuritis (ON) (45%). Patients with ADEM had a significantly lower age at first attack (p = 0.025). Monophasic and relapsing disease courses were seen in 45% and 55% patients, respectively. While all patients with only ADEM had a monophasic course, 77.8% with ON had a relapsing course. Among patients who presented with isolated transverse myelitis, 75% had a monophasic course and all had disease confined to the spinal cord. Good response to corticosteroids was seen in majority of participants. Second-line drugs were needed in 55% patients, rituximab being the commonest second-line agent used. 35% patients had significant disability (EDSS > 4) at last follow-up. MOG-Ab-associated diseases have diverse clinical phenotypes characterized by age-dependent pattern-specific courses., (© 2020. Belgian Neurological Society.)

C-term magnetic circular dichroism (MCD) spectroscopy is a powerful method for probing d-d and f-f transitions in paramagnetic metal complexes. However, this technique remains underdeveloped both experimentally and theoretically for studies of U(v) complexes of Oh symmetry, which have been of longstanding interest for probing electronic structure, bonding, and covalency in 5f systems. In this study, C-term NIR MCD of the Laporte forbidden f-f transitions of [UCl6]- and [UF6]- are reported, demonstrating the significant fine structure resolution possible with this technique including for the low energy Γ7 → Γ8 transitions in [UF6]-. The experimental NIR MCD studies were further extended to [U(OC6F5)6]-, [U(CH2SiMe3)6]-, and [U(NC(tBu)(Ph))6]- to evaluate the effects of ligand-type on the f-f MCD fine structure features. Theoretical calculations were conducted to determine the Laporte forbidden f-f transitions and their MCD intensity experimentally observed in the NIR spectra of the U(v) hexahalide complexes, via the inclusion of vibronic coupling, to better understand the underlying spectral fine structure features for these complexes. These spectra and simulations provide an important platform for the application of MCD spectroscopy to this widely studied class of U(v) complexes and identify areas for continued theoretical development.

A 5-year-old male child of consanguineous parentage, without any adverse perinatal history, presented with progressive cognitive regression predominantly in the language and attention domains, for 2 years. He had simultaneous pyramidal and extrapyramidal involvement, frequent generalised tonic-clonic seizures and recurrent respiratory tract infections. Examination was significant for vertical supranuclear gaze palsy, coarse facial features and splenomegaly. Given the clinical features, in the background of consanguinity and mother's history of spontaneous pregnancy losses, inborn errors of metabolism were suspected. Following relevant investigations including tailored genetic study, Niemann-Pick disease type C (NPC) was diagnosed. Interestingly, MRI brain showed bilateral T2/fluid-attenuated inversion recovery claustrum hyperintensities, which are more commonly associated with autoimmune encephalitis and febrile infection-related epilepsy syndrome and not reported previously in NPC. Additionally, language regression as a presenting manifestation in NPC as opposed to classical dysarthria makes this case truly unique., Competing Interests: Competing interests: None declared., (© BMJ Publishing Group Limited 2021. No commercial re-use. See rights and permissions. Published by BMJ.)

The absorption spectra of the octahedral [UX 6 ] n - (X = Cl, Br; n = 1, 2) complexes in the near-infrared (NIR) and UV-vis spectral regions were studied theoretically, using a relativistic restricted active space second-order perturbation theory (RASPT2) wavefunction framework, with the spin-orbit (SO) coupling treated by state interaction, in conjunction with Kohn-Sham density functional theory calculations for determining the vibrational normal modes. The electric-dipole-allowed ligand-to-metal charge-transfer (LMCT) and 5f-to-6d transitions, and the electric-dipole-forbidden 5f-to-5f ligand field (LF) transitions, are thereby obtained within the same theoretical framework. For the 5f-to-5f LF transitions, the observed absorption intensity is mostly due to vibronic coupling with low-energy electric-dipole-allowed transitions, but in some cases, the magnetic dipole intensity of the purely electronic transition has comparable intensity to the vibronic transitions. Experimental LF spectra of 5f 2 open-shell systems have been reported decades back, but ab initio calculations of their vibronic intensity have not yet been reported in the literature. Although the LF spectra for the 5f 2 systems can be assigned in detail, based on the calculations, the spectra are very complex and the underlying electronic states are strongly multiconfigurational. Therefore, the usefulness of the LF spectra beyond serving as a "fingerprint" of the LF and the metal oxidation state appears to be limited.

Background and Aims: To study the clinical profile of genetically proven Huntington's disease (HD) patients from eastern India., Methods: This cross sectional study selected patients of HD after genetic confirmation of expanded CAG repeats in Huntingtin ( HTT ) gene. We performed detail clinical evaluation including cognitive and neuropsychological assessment, and imaging of brain., Results: This study included 75 patients (male: 57.3%; female: 42.7%). Mean age at onset was 37.12 (range 16-62) years; juvenile variety (onset below 20 years) was detected in 5.3%. Paternal transmission was commoner. Manifestations at onset were motor in 81.3% patients, behavioral in 10.7% and cognitive impairment in 8%. After chorea, next common movement disorder was dystonia. Frontal lobe dysfunction was found in 77.3% patients. Behavioral disturbances were observed in 77.3% patients and commonly manifested as depression, irritable behavior and anxiety. Among the three onset groups (motor/behavioral/cognitive), there was no significant difference regarding age at onset, gender distribution, pattern of inheritance (paternal/maternal), and at the time of evaluation, all groups had essentially similar pattern of clinical features. Mean CAG repeat of the patients was 48.25 (range 40-79). Our study showed some differing clinical characteristics compared to previous studies from the Indian subcontinent., Conclusion: Clinical features in our study showed differences from previous studies from the Indian subcontinent. We had more cognitive-onset patients. However, behavioral onset was lower in our study. Motor, behavioral and cognitive onset groups of HD were comparable regarding demographics, family history, CAG repeat lengths and major clinical features at the time of evaluation., Competing Interests: There are no conflicts of interest., (Copyright: © 2020 Annals of Indian Academy of Neurology.)

Relativistic multireference ab initio wave function calculations with the restricted active space second-order perturbation theory (RASPT2) were performed on thorocene and uranocene to determine the actinide N 4,5 -edge and carbon K-edge X-ray absorption near-edge structure (XANES) intensities and the metal-ligand orbital mixing in the ground state and core-excited states. Calculated spectral intensities show very good agreement with the experiments and therefore allow detailed and unambiguous assignment of the observed spectral features. φ-type covalent bonding or antibonding interactions are observed for thorocene in the core-excited states, though not in the ground state. This is because the molecular orbital of φ symmetry, which is the in-phase combination of the ligand L φ and the Th 5f φ orbitals, can be populated with electrons in core-excited states, whereas it is essentially unoccupied in the ground state. For uranocene, the XANES spectra do not reveal much information beyond multiplet broadening, despite the presence of distinct peaks in the spectra. Every core-excited peak is best characterized by its own set of bond orbitals, as the excited state covalency is clearly different from the ground state covalency., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The aim of this study was to determine a cost-effective diagnostic method for lumbar herniated disc with knee osteoarthritis (LHD-KOA) based on aberrant outcome measures, levels of biomarkers, and examination of the lower-extremity. Data were separately analyzed for each cohort suffering with LHD-KOA ( n =108; 59.82±7.15years) and without LHD-KOA ( n =108; 58.81±7.61years), and findings were confirmed with radiological images. The aberrant-leg-features (bilateral: knee gaps between the short head of biceps femoris and the surface of the bed, diameters of calves and thighs, angles of straight leg raising, knee-flexion and -extension in a supine position) and biochemical parameters (Interleukin-10, Tumor necrosis factor-alpha, C-reactive protein, creatine kinase-muscle, and Aldolase-A), and outcome measures, Western Ontario and McMaster Universities osteoarthritis index (WOMAC), knee-injury osteoarthritis outcomes scale (KOOS), Oswestry disability index (ODI), and body mass index (BMI)for participants with and without LHD-KOA were evaluated with appropriate techniques. All the subjects underwent standardized physical examination and completed a questionnaire. The risk ratios and mean± standard deviations of biomarkers, anatomical features, and outcome measures of the experimental subjects were highly significant compared to controls (p<0.0001). Results suggest that monitoring the studied aberrant outcome measures, biomarkers, and lower-anatomical features may be a cost-effective diagnostic tool for LHD-KOA. Further research is recommended for an alternative treatment protocol for LHD-KOA.

The cytotoxicity of dopamine on cultured cells of neural origin has been used as a tool to explore the mechanisms of dopaminergic neurodegeneration in Parkinson's disease. In the current study, we have shown that dopamine induces a dose-dependent (10-40 μM) and time-dependent (up to 96 h) loss of cell viability associated with mitochondrial dysfunction and increased intra-cellular accumulation of α-synuclein in cultured SH-SY5Y cells. Dopamine-induced mitochondrial dysfunction and the loss of cell viability under our experimental conditions could be prevented by cyclosporine, a blocker of mitochondrial permeability transition pore, as well as the antioxidant N-acetylcysteine. Interestingly, the dopamine effects on cell viability and mitochondrial functions were significantly prevented by knocking down α-synuclein expression by specific siRNA. Our results suggest that dopamine cytotoxicity is mediated by α-synuclein acting on the mitochondria and impairing its bioenergetic functions.

A mononuclear iron(II) complex [Fe II (N4Py Me2 )(OTf)](OTf)(1), supported by a new pentadentate ligand, bis(6-methylpyridin-2-yl)- N, N-bis((pyridin-2-yl)methyl)methanamine (N4Py Me2 ), has been isolated and characterized. Introduction of methyl groups in the 6-position of two pyridine rings makes the N4Py Me2 a weaker field ligand compared to the parent N4Py ligand. Complex 1 is high-spin in the solid state and converts to [Fe II (N4Py Me2 )(CH 3 CN)](OTf) 2 (1a) in acetonitrile solution. The iron(II) complex in acetonitrile displays temperature-dependent spin-crossover behavior over a wide range of temperature. In its reaction with m-CPBA or oxone in acetonitrile at -10 °C, the iron(II) complex converts to an iron(IV)-oxo species, [Fe IV (O)(N4Py Me2 )] 2+ (2). Complex 2 exhibits the Mössbauer parameters δ = 0.05 mm/s and Δ E Q = 0.62 mm/s, typical of N-ligated S = 1 iron(IV)-oxo species. The iron(IV)-oxo complex has a half-life of only 14 min at 25 °C and is reactive toward oxygen-atom-transfer and hydrogen-atom-transfer (HAT) reactions. Compared to the parent complex [Fe IV (O)(N4Py)] 2+ , 2 is more reactive in oxidizing thioanisole and oxygenates the C-H bonds of aliphatic substrates including that of cyclohexane. The enhanced reactivity of 2 toward cyclohexane results from the involvement of the S = 2 transition state in the HAT pathway and a lower triplet-quintet splitting compared to [Fe IV (O)(N4Py)] 2+ , as supported by DFT calculations. The second-order rate constants for HAT by 2 is well correlated with the C-H bond dissociation energies of aliphatic substrates. Surprisingly, the slope of this correlation is different from that of [Fe IV (O)(N4Py)] 2+ , and 2 is more reactive only in the case of strong C-H bonds (>86 kcal/mol), but less reactive in the case of weaker C-H bonds. Using oxone as the oxidant, the iron(II) complex displays catalytic oxidations of substrates with low activity but with good selectivity.

The aging of brain in the absence of neurodegenerative diseases, usually called non-pathological brain aging or normal cognitive aging, is characterized by an impairment of memory and cognitive functions. The underlying cellular and molecular changes in the aging brain that include oxidative damage, mitochondrial impairment, changes in glucose-energy metabolism and neuroinflammation have been reported widely from animal experiments and human studies. The cognitive deficit of non-pathological brain aging is the resultant of such inter-dependent and reinforcing molecular pathologies which have striking similarities with those operating in Alzheimer's disease which causes progressive, irreversible and a devastating form of dementia and cognitive decline in the elderly people. Further, this article has described elaborately how nutraceuticals present in a wide variety of plants, fruits and seeds, natural vitamins or their analogues, synthetic antioxidants and other compounds taken with the diet can ameliorate the cognitive decline of brain aging by correcting the biochemical alterations at multiple levels. The clinical usefulness of such dietary supplements should be examined both for normal brain aging and Alzheimer's disease through randomized controlled trials., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Understanding the oxidation mechanism and positions of twistacenes and twistheteroacenes under ambient conditions is very important because such knowledge can guide us to design and synthesize novel, larger stable analogues. Herein, we demonstrated for the first time that a twisted isoquinolinone can decompose under oxygen and light at room temperature. The as-decomposed product 1 was fully characterized through conventional methods as well as single-crystal structure analysis. Moreover, the physical properties of the as-obtained product were carefully investigated and the possible formation mechanism was proposed., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Molecular solar thermal storage (MOST) systems have been largely limited to three classes of molecular motifs: azo-benzene, norbornadiene, and transition metal based fulvalene-tetracarbonyl systems. Photodimerization of anthracene has been known for a century; however, this photoprocess has not been successfully exploited for MOST purposes due to its poor energy storage. Using well-calibrated theoretical methods on a series of [n.n](9,10)bis-anthracene cyclophanes, we have exposed that they can store solar energy into chemical bonds and can release in the form of heat energy on demand under mild conditions. The storage is mainly attributed to the strain in the rings formed by the alkyl linkers upon photoexcitation. Our results demonstrate that the gravimetric energy storage density for longer alkyl-chain linkers (n > 3) are comparable to those for the best-known candidates; however, it lacks some of the deleterious attributes of known systems, thus making the proposed molecules desirable targets for MOST applications.

Here, we present our recent progress on the synthesis, crystal structure, physical properties and DFT calculations of a novel large pyrene-fused N-heteroacene (15RINGS) with 15 aromatic six-membered rings linearly fused in one row. The long conjugated backbone (more than 35 Å) of 15RINGS possesses a dual-bending feature (the bending angle is about 13.2°).

Peripheral neuropathy (PN) is a common disorder and presents as diagnostic and therapeutic challenge to physicians and neurologists. In epidemiological studies from India from various regions the overall prevalence of PN varied from 5 to 2400 per 10,000 population in various community studies. India is composed of a multiethnic, multicultural population who are exposed to different adverse environmental factors such as arsenic and lead. Use of different chemotherapeutic agents with propensity to affect peripheral nerves, increasing methods of diagnosis of connective tissue disorders and use of immunomodulating drugs, growing aging population is expected to change the spectrum and burden of peripheral neuropathy in the community. The other important aspect of peripheral neuropathies is in terms of the geographical and occupational distribution especially of toxic neuropathies like arsenic which is common in eastern belt; lead, mercury and organo-phosphorous compounds where occupational exposures are major sources. Inflammatory neuropathies either due to vasculitis or G B Syndrome, chronic inflammatory polyradiculopathies are another major group of neuropathies which is increasing due to increase longevity of Indian subjects and immunological impairment, also adds to morbidity of the patients and are potentially treatable. Leprous neuropathy is common in India and although its frequency is significantly decreasing because of national control program yet pure neuritic form still remains a cause of concern and similar is the case with another infective cause like diptheric neurpathy. Thus this article is an attempt to cover major categories and also highlight the areas where further studies are needed., Competing Interests: There are no conflicts of interest.

Alzheimer's disease and Parkinson's disease are two common neurodegenerative diseases of the elderly people that have devastating effects in terms of morbidity and mortality. The predominant form of the disease in either case is sporadic with uncertain etiology. The clinical features of Parkinson's disease are primarily motor deficits, while the patients of Alzheimer's disease present with dementia and cognitive impairment. Though neuronal death is a common element in both the disorders, the postmortem histopathology of the brain is very characteristic in each case and different from each other. In terms of molecular pathogenesis, however, both the diseases have a significant commonality, and proteinopathy (abnormal accumulation of misfolded proteins), mitochondrial dysfunction and oxidative stress are the cardinal features in either case. These three damage mechanisms work in concert, reinforcing each other to drive the pathology in the aging brain for both the diseases; very interestingly, the nature of interactions among these three damage mechanisms is very similar in both the diseases, and this review attempts to highlight these aspects. In the case of Alzheimer's disease, the peptide amyloid beta (Aβ) is responsible for the proteinopathy, while α-synuclein plays a similar role in Parkinson's disease. The expression levels of these two proteins and their aggregation processes are modulated by reactive oxygen radicals and transition metal ions in a similar manner. In turn, these proteins - as oligomers or in aggregated forms - cause mitochondrial impairment by apparently following similar mechanisms. Understanding the common nature of these interactions may, therefore, help us to identify putative neuroprotective strategies that would be beneficial in both the clinical conditions., Competing Interests: Disclosure The authors report no conflicts of interest in this work.

The breaking of bonds by catalytic electrons has gained prominence very recently but has been limited to cases where electrons from external sources have been used. Here, we show that upon photoexcitation, an electron of intramolecular origin is transferred from one part of a molecule to another followed by bond cleavage and then returns to its original moiety on completion of its catalytic function. By a proper assessment of the dramatic changes in aromaticity in excited-state intermediates along the photoreaction coordinate captured by the magnetically induced current density (MICD) technique, we show that in 5-phenyltetrazole, an excited electron, which migrates from the phenyl ring to the tetrazole ring, induces bond cleavage catalytically. Using the MICD technique, we establish for the first time a link between the phenomenon of excited-state electron/charge transfer among aromatic rings and the intricate interplay of aromatic, antiaromatic and non-aromatic states.

Introduction: Spinocerebellar ataxias (SCAs) are hereditary, autosomal dominant progressive neurodegenerative disorders showing clinical and genetic heterogeneity. They are usually manifested clinically in the third to fifth decade of life although there is a wide variability in the age of onset. More than 36 different types of SCAs have been reported so far and about half of them are caused by pathological expansion of the trinucleotide, Cytosine Alanine Guanine (CAG) repeat. The global prevalence of SCA is 0.3-2 per 100,000 population, SCA3 being the commonest variety worldwide, accounting for 20-50 per cent of all cases, though SCA 2 is generally considered as the commonest one in India. However, SCA6 has not been addressed adequately from India though it is common in the eastern Asian countries like, Japan, Korea and Thailand., Objective: The present study was undertaken to identify the prevalence of SCA6 in the city of Kolkata and the eastern part of India., Materials and Methods: 83 consecutive patients were recruited for the study of possible SCAs and their clinical features and genotype were investigated., Results: 6 of the 83 subjects turned out positive for SCA6, constituting therefore, 13.33% of the patient pool., Discussion: SCA6 is prevalent in the eastern part of India, though not as frequent as the other common varieties., Conclusions: Further community based studies are required in order to understand the magnitude of SCA6 in the eastern part, as well as in other regions of India.

Using well calibrated DFT studies we predict that experimentally synthesized B24 N24 fullerene can serve as a potential reversible chemical hydrogen storage material with hydrogen-gas storage capacity up to 5.13 wt %. Our theoretical studies show that hydrogenation and dehydrogenation of the fullerene framework can be achieved at reasonable rates using existing metal-free hydrogenating agents and base metal-containing dehydrogenation catalysts., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Neuromyelitis optica spectrum disorder (NMOSD) is a diverse condition which not only encompasses isolated longitudinally extensive transverse myelitis (LETM) and optic neuritis but also includes area postrema syndrome, acute brainstem syndrome, symptomatic narcolepsy or acute diencephalic clinical syndrome, and symptomatic cerebral syndrome. Imaging may reveal periependymal lesions surrounding the ventricular system or involvement of corticospinal tracts, area postrema, diencephalon, and corpus callosum. Rarely, there may be hemispheric tumefactive lesions that enhance in a "Cloud-like" fashion on gadolinium injection unlike in tumefactive multiple sclerosis where there is incomplete ring enhancement. Here, we present a case of aquaporin-4 positive relapsing NMOSD who presented to us with recurrent episodes of paraparesis with LETM and tumefactive lesions of brain on imaging, which enhanced in an incomplete ring like pattern resembling multiple sclerosis.

Oxidation by dioxygen has a rich repertoire of mechanistic intricacies. Herein, we report a hitherto unknown paradigm of dioxygen activation reaction which propagates through a four center two electron (4c-2e) bound species. Using static DFT and ab initio quantum chemical techniques we have unraveled the oxidation pathway for hydrazine and its methylated analogues by dioxygen which involves formation of this unconventional 4c-2e bonded species en route to the oxidation products. Inconvertible evidence in favor of such an unprecedented dioxygen activation route is provided by capturing the events of formation of the 4c-2e species in aqueous phase for hydrazine and its congeners and the experimentally observed products from the respective 4c-2e species, like H2O2 and N2H2 , diazene in the case of hydrazine using Car-Parrinello molecular dynamics simulations., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Aim: Neurocognitive dysfunction continues to be the bane of open heart surgery despite vast improvements in surgical, anesthetic, and postoperative management. This observational cohort study was carried out to evaluate the efficacy of intraoperative CO2 insufflation by the field flooding technique in reducing postoperative neurocognitive dysfunction., Methods: Three hundred randomly selected patients undergoing open heart surgery were observed: 150 (group A) were exposed to CO2 insufflation, and the other 150 (group B) were not exposed to CO2. Anesthetic, cardiopulmonary bypass, and myocardial protection techniques were standardized and similar in both groups. Neurocognitive function tests were performed preoperatively, 1 week postoperatively, and after 1 month., Results: The analysis revealed that neurocognitive dysfunction occurred in 8 of 150 patients in group A (incidence p1 = 0.053) and 27 of 150 in group B (incidence p2 = 0.18). The relative risk of neurocognitive dysfunction was 0.30 (p = 0.001, 95% confidence interval 0.14-0.63), implying that CO2 insufflation is protective against neurocognitive dysfunction. The risk difference was 0.13 (p2-p1); this implies that 13% of patients can be prevented from developing neurocognitive dysfunction if exposed to CO2., Conclusion: This study confirms the known advantage of the relatively underutilized practice of CO2 insufflation. We recommend that CO2 insufflation be performed in all open heart surgery cases to bring down the incidence of neurocognitive dysfunction. This technique is simple to use without any major paraphernalia or additional cost., (© The Author(s) 2015.)

Megalencephalic leukoencephalopathy with subcortical cysts (MLC), or Van der Knaap disease, is a rare autosomal recessive disorder. It is characterised by macrocephaly that either presents at birth or develops during infancy. It occurs more commonly in some ethnicities where consanguinity is common, such as in the Agrawal community in India. This disease typically presents with a history of delayed motor milestones in affected children. MRI findings including leukodystrophy and subcortical cysts are hallmarks of the disease and yield the diagnostic clue in most cases. Several cases of Van der Knaap disease with classical features have been reported in the literature. We present a case of Van der Knaap disease with classical MRI features, including a few distinctly atypical characteristics in its epidemiological, clinical and electrophysiological attributes., (2015 BMJ Publishing Group Ltd.)

Background: Progressive cerebellar ataxia inherited by autosomal dominant transmission is known as Spino Cerebellar Ataxia (SCA)., Aims and Objectives: To look for various clinical profile and molecular genetics of patients with SCAs and their phenotype-genotype correlation of patients with SCAs., Materials and Methods: This was a cross-sectional study conducted at Bangur Institute of Neurosciences, Kolkata from June 2010 to April 2013. We selected patients from the neurogenetic clinic of our institute and performed genetic test for SCA 1, 2, 3, 6 and 12. The diagnosis was based on suggestive clinical features and positive genetic study, done by polymerase chain reaction., Results: 83 patients were tested for trineucleotide repeats and turned out 45 positive for the mentioned SCAs. We found 13(28.9%) SCA-1, 18(40%) SCA-2, 7(15.6%) SCA-3, 6(13.3) SCA-6 and 1(2.2%) SCA-12 patients. Half of the remaining 38 patients had positive family history. The mean age of onset were 38.46 years in SCA-1, 29.55 years in SCA-2, 38.43 years in SCA-3, 47.33 years in SCA-6. Slow saccades were observed in 7(53.8%) SCA-1, 17(94.4%) SCA-2, 4(57.1%) SCA-3, 3(50%) SCA-6 patients. Hyporeflexia was noticed in 5(27.8%) SCA-2 patients. Pyramidal tract involvement was found in 8(61.5%) SCA-1, 4(22.2%) SCA-2, 4(57.1%) SCA-3 and 1(16.7%) SCA-6 patients., Conclusion: Our study showed SCA-2 is the most common variety of SCA and genotypic-phenotypic correlation was observed in SCA-1,2,6 and 12 patients.

HCN is clearly associated with the prebiotic chemical evolution of life. It has been known for decades that the radiolysis of HCN solutions produces sugars, amino acids and nucleobases. Remarkably, recent experimental studies have shown that the photolytic reduction of aqueous HCN by a photoredox reagent [Cu(CN)3](2-) specifically yields sugars, which are the essential building blocks of RNA. Although a mechanistic understanding of such reductions with solvated electrons is poor, the general consensus is that they involve neutral free radicals. We show herein through the use of electronic structure studies and molecular simulations that the reduction of the nitrile bond of HCN is initiated through the formation of a molecular dipole-bound anion from the photoredox reagent. Our theoretical studies show how HCN binds to the photoexcited reagent and then extracts an electron from the reagent and is ultimately detached as a dipole-bound anion. The dipole-bound anionic form of [HCN](-) can easily convert into a solvated valence-bound form of [HCN](-). After the formation of solvated [HCN](-), an extraordinary chemical event ensues through a counter-intuitive coupling of two valence-bound anions to form a solvated molecular dianionic intermediate, [HCN]2(2-). Finally, a proton-coupled electron transfer occurs within the dianionic entity to complete the reduction. This mechanistic scenario is applicable to the reduction of other prebiotic nitrile species and avoids neutral radical-based pathways, thereby preventing the proliferation of reactive species and preserving chemical selectivity. Furthermore, we show how such similar nitrile reduction pathways operate to yield the sugar precursors., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A new hexaprismane Co(II)6(μ3-OH)6 cluster-based three-dimensional coordination polymer ({Co(μ3-OH)(HCOO)0.72(CH3COO)0.28}n, Co6-CP) was successfully synthesized and characterized with single-crystal XRD, IR spectra, TGA spectra and elemental analysis. Co6-CP was used as an effective heterogeneous catalyst for the aerobic epoxidation of various alkenes. For the catalytic epoxidation of trans-stilbene, the conversion and selectivity towards the epoxide reached 98.6 and 98.0%, respectively. Also, an average TOF of 22 h(-1) was obtained for the reaction. The results indicated that Co6-CP displayed excellent aerobic epoxidation activity among the reported coordination polymer materials, even rivaling the traditional heterogeneous cobalt catalysts. The influence of the reaction parameters such as temperature and oxygen flow rate for the epoxidation of the trans-stilbene were also studied in detail.

Aim: To devise a simple, cheap and effective improvised method of treating deep sternal wound infections (DSWI) by negative pressure obviating high cost of patented systems., Method: Records of ten post CABG patients operated via median sternotomy approach over a two and half year period and treated for DSWI were analysed. Sterile foam with drain was placed in the wound, which was covered with Ioban (Steridrape), the drain being connected to a suction unit maintaining 100mmHg pressure (<$12 cost)., Results: Ten (10) patients of DSWI were managed with this therapy. Mean age was 60.4 years. Pseudomonas found in 1 (10%), Acinetobacter and Pseudomonas in 1 (10%) with Escherichia coli in 1 (10%). Five (50%) patients had diabetes mellitus. Mean hospitalisation period was 43 days. Seven (70%) patients underwent secondary suturing. Two (22%) patients had relapse, which was managed with dressings and secondary intention suturing. One patient who underwent a muscle flap cover had major recurrence with multiple sinuses. Excellent wound healing in 9 (90%) patients with no (0%) 90-day mortality. Improvised components can be safely employed to provide effective negative pressure therapy for DSWI with excellent results., (Copyright © 2012 Australian and New Zealand Society of Cardiac and Thoracic Surgeons (ANZSCTS) and the Cardiac Society of Australia and New Zealand (CSANZ). Published by Elsevier B.V. All rights reserved.)

Pulmonary artery aneurysm presenting with dissection and hemopericardium is extremely rare, and we came across one such case in our center. The patient was a 22-year-old man who presented with dyspnoea, tachypnoea, and pallor. On evaluation, he was found to have a leaking pulmonary artery aneurysm with dissection and hemopericardium, and a patent ductus arteriosus. He underwent pericardiocentesis followed by successful closure of the ductus, aneurysmectomy, and reconstruction of the pulmonary artery.

From atomic level to understand the cluster-size-dependant behavior of dye-sensitized photocatalysts is very important and helpful to design new photocatalytic materials. Although the relationship between the photocatalytic behaviors and particles' size/shape has been widely investigated by theoretical scientists, the experimental evidences are much less. In this manuscript, we successfully synthesized three new ruthenium dye-sensitized polyoxometalates (POM-n, n relate to different size clusters) with different-sized POM clusters. Under visible-light illumination, all three complexes show the stable O2 evolution with the efficient order POM-3 > POM-2 > POM-1. This cluster-size-dependent catalytic behavior could be explained by the different numbers of M = Ot (terminal oxygen) bonds in each individual cluster because it is well-known that Mo = Ot groups are the catalytically active sites for photooxidation reaction. The proposed mechanism of water oxidation for the dye-sensitized POMs is radical reaction process. This research could open up new perspectives for developing new POM-based WOCs.

Introduction: Exploding head syndrome (EHS) is a rare parasomnia in which affected individuals awaken from sleep with the sensation of a loud bang. The etiology is unknown, but other conditions including primary and secondary headache disorders and nocturnal seizures need to be excluded., Case Presentation: A 57-year-old Indian male presented with four separate episodes of awakening from sleep at night after hearing a flashing sound on the right side of his head over the last 2 years. These events were described 'as if there are explosions in my head'. A neurologic examination, imaging studies, and a polysomnogram ensued, and the results led to the diagnosis of EHS., Conclusion: EHS is a benign, uncommon, predominately nocturnal disorder that is self-limited. No treatment is generally required. Reassurance to the patient is often all that is needed.

Coordination of a tetratopic nitrogen-rich linker with Zn(2+) under solvothermal conditions afforded a Zn-based metal organic framework (MOF), where the Zn(II) ions could be exchanged by Cu(II) ions in a single-crystal-to-single-crystal fashion leading to a new Cu-based MOF. Such transformation induces a significant enhancement in gas sorption along with a high selectivity towards CO(2) over N(2) and CH(4).