A 500 kV, 10 kA, 40 ns coaxial Marx generator pulser for cable fed flash x-ray system.

Flash x-ray (FXR) systems are used for dynamic radiography. Depending on the speed of the object, these systems typically require a very short pulse duration (∼25 ns) for image acquisition without motion blur. The conventional Marx generators with zigzag discharge paths result in higher inductance; hence, they do not meet the requirement of shorter pulse duration (30-40 ns) and low impedance (40-60 Ω) simultaneously. A coaxial Marx generator has been designed and developed, which is capable of generating 500 kV peak voltages and 10 kA peak current within a 40 ns pulse duration. The CST simulation of the coaxial Marx generator has been carried out to validate the design parameters. The FXR electron beam diode is powered by this Marx generator. Experiments were carried out to measure the x-ray parameters like pulse width, source size, x-ray energy spectrum, penetration depth, and cone angle. The maximum measured x-ray dose was 62 mR at 1 m distance from the source window. The x-ray radiograph demonstrates a penetration depth of 32 mm in steel kept at 2.5 m distance from the source for 500 kV diode voltages.

Design, simulation, and development of bipolar pulse forming network based Marx generator for S band backward wave oscillator.

Pulse power systems have a wide range of applications, one of which is microwave generation. Microwave emission is associated with a certain time delay between the application of a high voltage pulse and the generation of the microwave signal. This time delay is known as microwave delay time, and it depends on the time period of the microwave signal being generated. As the time period of the microwave signal increases, the required input electrical pulse duration also goes up. To achieve this, a pulse forming network (PFN) based Marx generator is proposed. The Bipolar Marx generator is preferred over the uni-polar Marx generator to obtain the high voltage high current pulse. This also helps in maintaining the impedance requirement for Backward Wave Oscillator (BWO) devices that generate the microwave pulse. To the best of our knowledge, PFN based Marx generators have been developed up to 400 kV. Here, a bipolar Marx generator has been designed with ratings of 800 kV peak voltage, 10 kA peak current, and 150 ns flattop pulse duration. The design includes analytical calculations and numerical analysis by electromagnetic simulation. The triggering method to get a wide triggering range has also been discussed. The design values have also been experimentally verified, and the resulting parameters were applied to a BWO to simulate the microwave power that it can produce. A peak microwave power of ∼1 GW has been observed in the particle-in-cell simulation.

Contrasting Association Between COVID-19 Vaccine Hesitancy and Mental Health Status in India and Saudi Arabia-A Preliminary Evidence Collected During the Second Wave of COVID-19 Pandemic.

Background: Vaccine hesitancy is a global public health threat. Understanding the role of psychological factors in vaccine hesitancy is often neglected and relatively less explored. Aim and Objectives: To analyze the relationship between mental health and COVID-19 vaccine hesitancy before and after the advent of COVID-19 vaccines (AC19V) in the general population of India and Saudi Arabia (KSA) which vary in severity of the pandemic and vaccine mandates. Materials and Methods: A total of 677 adult participants from India and KSA participated in this cross-sectional online web-based survey. Sociodemographic details and current COVID-19 status pertaining to infection and vaccination were collected. Depression, anxiety, post-traumatic stress disorder (PTSD) symptoms, and perceptive need for mental health support (MHS) were assessed before and after AC19V. A newly constructed and validated COVID19 vaccine hesitancy scale-12 (COVID19-VHS12) scale was used to evaluate the COVID-19 vaccine hesitancy. Results: Prevalence and levels of depression and anxiety symptoms decreased significantly in Saudis but not in Indians after AC19V. PTSD symptoms showed a significant reduction in both India and KSA. Anxiety symptoms were higher in KSA than India before AC19V while PTSD was higher in India before and after AC19V. Except for the place of residence and employment status, the subgroups of sociodemographic variables which were at higher risk of negative mental health before AC19V showed improvement in their mental health after AC19V. The prevalence of COVID-19 vaccine hesitancy in India and KSA was 50.8% (95% CI 45.73-55.89%) and 55.7% (95% CI 50.16-61.31%), respectively. A bidirectional association between vaccine hesitancy and mental health was observed in KSA but not in India. Higher vaccine hesitancy favored higher levels of depression, anxiety, and perceptive need for MHS and vice versa in KSA. None of the mental health parameters predicted vaccine hesitancy in India, while higher vaccine hesitancy increased the risk of anxiety. Conclusion: Vaccine hesitancy has a negative impact on mental health and vice versa over and above the impact of sociodemographic factors and COVID-19 vaccination and infection status which shows variations between India and KSA.

Quantitative profiling of Marek's Disease Virus in vaccinated layer chicken.

The present study was undertaken to quantify the Marek's Disease Virus (MDV) serotypes in vaccinated commercial layer flocks at 7, 14, 21, 28, 35 and 60-90 days post vaccination (dpv) and to correlate the pathogenic Gallid herpesvirus 2 (GaHV-2, MDV1) load with vaccine viral load of Gallid herpesvirus 3 (GaHV-3, MDV2) and Meleagridis herpesvirus 1 (MeHV-1, MDV3). A total of 25 commercial layer flocks were selected in and around Namakkal district of Tamil nadu, India and the feather pulp (FP) and blood samples were collected. Out of 25 flocks, 14 were revaccinated with bivalent vaccine, six were revaccinated with monovalent vaccine apart from the initial bivalent vaccination done at hatchery and five flocks were not revaccinated. SYBR green based real time PCR was used for absolute quantification of MDV serotypes. The pathogenic MDV1 load had shown an increasing trend until 21 dpv followed by a dip and again had shown a constant uptick between 60 and 90 dpv in the flocks that went on to develop MD outbreak. The flocks which had not encountered any Marek's Disease outbreak had shown increasing trend of MDV2 and 3 load until 21 dpv followed by a slight decrease but maintained a higher load when compared to MDV 1 which had marked a sharp decline between 60 and 90 dpv. Outbreak of MD was observed in seven (28%) out of 25 flocks between 18 and 27 weeks of age. It includes, two out of fourteen farms (14%) revaccinated with bivalent vaccine, two out of six farms (33%) revaccinated with MDV3 vaccine and three out of five farms (60%) without revaccination. The overall mean of vaccine viral load at various stages of dpv was constantly low where as pathogenic MDV 1 load was constantly high between 60 and 90 dpv in the flocks that went on to develop Marek's Disease during later part of life.

Rare histologic presentation of pleomorphic adenoma: A diagnostic dilemma.

Pleomorphic adenoma is the most common benign salivary gland tumor deriving its name from varied morphological patterns in histopathology. The presence of chondromyxoid stroma in histopathology is characteristic of pleomorphic adenoma. Cellular variants without characteristic chondromyxoid stroma are rare and often pose a diagnostic challenge. We report a case of pleomorphic adenoma involving minor salivary glands of the palate presenting with a predominantly cellular histopathology. Immunohistochemical workup was pivotal in the diagnosis of this challenging case.

Molecular characterisation of lineage IV peste des petits ruminants virus using multi gene sequence data.

Peste des petits ruminants is responsible for an economically important plague of small ruminants that is endemic across much of the developing world. Here we describe the detection and characterisation of a PPR virus from a recent outbreak in Tamil Nadu, India. We demonstrate the isolation of PPR virus from rectal swab and highlight the potential spread of disease to in-contact animals through faecal materials and use of faecal material as non-invasive method of sampling for susceptible wild ruminants. Finally we have performed a comprehensive 'multi-gene' assessment of lineage IV isolates of PPRV utilising sequence data from our study and publically available partial N, partial F and partial H gene data. We describe the effects of grouping PPRV isolates utilising different gene loci and conclude that the variable part of N gene at C terminus gives the best phylogenetic assessment of PPRV isolates with isolates generally clustering according to geographical isolation. This assessment highlights the importance of careful gene targeting with RT-PCR to enable thorough phylogenetic analysis.

Compact inductive energy storage pulse power system.

An inductive energy storage pulse power system is being developed in BARC, India. Simple, compact, and robust opening switches, capable of generating hundreds of kV, are key elements in the development of inductive energy storage pulsed power sources. It employs an inductive energy storage and opening switch power conditioning techniques with high energy density capacitors as the primary energy store. The energy stored in the capacitor bank is transferred to an air cored storage inductor in 5.5 µs through wire fuses. By optimizing the exploding wire parameters, a compact, robust, high voltage pulse power system, capable of generating reproducibly 240 kV, is developed. This paper presents the full details of the system along with the experimental data.

Regulation of insulin-like growth factors and their binding proteins by thyroid stimulating hormone in human osteoblast-like (SaOS2) cells.

Thyroid stimulating hormone (TSH) is shown to have definite anabolic effects on skeletal metabolism. Previous studies have demonstrated that Insulin-like growth factors (IGF-I and IGF-II) and their six high affinity binding proteins (IGFBPs 1-6) regulate proliferation and differentiation of bone-forming osteoblasts. The current study was intended to determine whether the anabolic effects of TSH on human osteoblastic (SaOS2) cells are mediated through insulin-like growth factor system components. TSH given at 0.01 ng to 10 ng/ml dose levels for 24 and 48 h significantly increased human osteoblastic (SaOS2) cell proliferation and alkaline phosphatase activity, the differentiation marker. TSH significantly increased IGFs (IGF-I and IGF-II) mRNA expression after 6 and 24 h and their protein levels after 24 and 48 h of treatment, respectively. Unlike the IGFs, the IGFBPs responded differently to TSH treatment. Though there were some inconsistencies in the regulation of stimulatory IGF binding protein-3 and -5 by TSH treatment, there was an overall increase at the mRNA abundance and protein levels. Again, the inconsistency persisted at the regulation of the inhibitory IGFBPs 2, 4, and 6 especially at the level of mRNA expression due to TSH treatment, there is an overall decrease in the levels of IGFBP-2, 4, and 6 in the conditioned media (CM) of SaOS2 cell cultures. The IGFBP proteases which control the availability of IGFs are also regulated by hormones. Pregnancy-Associated Plasma Protein-A (PAPP-A) is responsible for the proteolysis of IGFBP-4. TSH treatment significantly unregulated the expression of PAPP-A both at mRNA and protein levels. In conclusion, TSH promotes human osteoblastic (SaOS2) cell proliferation and differentiation by upregulating IGFs and their stimulatory IGF binding proteins and down regulating the inhibitory IGF binding proteins.

Tunable one-, two-, and three-dimensional self-assemblies from an acceptor-donor fullerene-N,N-dimethylaminoazobenzene dyad: interfacial geometry and temporal evolution.

Controllable fabrication of spontaneously ordered and varied geometry fullerene C(60) based molecular architecture was achieved upon hierarchical self-assembly of the fullerene-N,N-dimethylaminoazobenzene acceptor-donor hybrid (DPNME). Simple preparation techniques, such as Langmuir-Blodgett (LB), solution-cast, and immersion at the liquid-air and solid-air interfaces, were used without templates as a function of DPNME concentration, media pH, time, and supporting substrate characteristics. The resulting structures depending upon the preparation methods were investigated with field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), and molecular modeling, which revealed a delicate role of intermolecular donor-acceptor, π-π, and van der Waals interactions between the electron deficient fullerene core and the N,N-dimethylaminoazobenzene electron donor under neutral conditions. Upon protonation, the electrostatics associated with the charged DPNME moiety and the dominant intermolecular fullerene-fullerene interactions guided the self-assembly process. Increased time scales led the molecular subunits to grow by maximizing the most favored orientations and yielded one-dimensional (1D) and two-dimensional (2D) structures in neutral and acidic conditions, respectively, which upon solvent evaporation formed the final multipods or stacked squares upon oriented attachment. For the protonated DPNME, 2D lamellar sheets formed from the bilayers gained cohesive energy, forming ultimately rectangular sheets. Interestingly, the Si(100) supported multilayer DPNME Langmuir films as a function of surface pressure and pH yielded a uniform and directional structure pattern in comparison with the geometry obtained from drop casting methods. This controllable structure architecture of the fullerene-azobenzene hybrid opens up a new alley in fullerene C(60) based self-assembly.

Growth and characterization of organic material 2-methylamino-5-chlorobenzophenone single crystal by modified vertical Bridgman technique.

The organic material 2-methylamino-5-chlorobenzophenone single crystal has been grown by modified vertical Bridgman technique using the single wall ampoule with nano translation. The grown crystal was confirmed by single crystal and powder X-ray diffraction analyses. Fourier transform infrared analysis was used to identify the functional groups present in the grown crystal. High resolution X-ray diffraction studies show the crystalline perfection of the grown crystal. The optical property of the grown crystal was analyzed by UV-vis-NIR and photoluminescence spectral studies. The thermal behavior of the grown crystal was analyzed by thermogravimetric and differential thermal analyses. The dielectric measurements of the grown crystal were carried out with different frequencies and temperatures and the results indicate an increase in dielectric and conductivity parameters with the increase of temperature at all frequencies. The microhardness measurements were performed to analyze the mechanical property of the grown crystal.

Solvent-polarity-tunable dimeric association of a fullerene (C60)-N,N-dimethylaminoazobenzene dyad: modulated electronic coupling of the azo chromophore with a substituted 3D fullerene.

The tunable self-assembly of a fullerene (C(60))-N,N-dimethylaminoazobenzene (DPNME) molecular system as a function of solvent polarity in THF/water binary solvent is reported. Gradual increase of the volume fraction of the nonsolvent water in a 1×10(-5) M THF solution of DPNME at a mixed dielectric constant ε(mix)≈42 resulted in initial redshifting of the (1)(π→π(*)) absorption band, which signified the 1D head-to-tail or J-type arrangement of the DPNME molecular system. Further increase in the solvent polarity to ε(mix)≈66 evidenced formation of an antiparallel head-to-tail or H-type molecular arrangement in conjunction with the J-aggregates, thereby establishing a solvent-polarity-dependent dynamic equilibrium between the monomer ↔ J-aggregate ↔ H-aggregate. The controlled aggregation was governed by the synergetic effect of intermolecular donor-acceptor interaction between the electron-deficient fullerene ring and the electron-rich N,N-dimethylamino-substituted aromatic ring; typically, van der Waals and π-π interactions between the molecules constituting a pair of dimers were envisaged. An agreement between the semiempirically calculated drastically reduced oscillator strength of the DPNME H-dimer in the antiparallel configuration (0.69 vs. 1.29 in the monomeric DPNME) and the experimental electronic absorption spectra beyond ε(mix)=66 further strengthened this assignment to the hitherto forbidden antiparallel H-dimer. Complementing the above, the periodicity of molecular self-assembly dictated a monoclinic unit cell in the single-crystal XRD packing pattern with a C2/c space group; the molecules packed laterally with mutual interdigitation with the donor (E)-N,N-dimethyl-4-(p-tolyldiazenyl)aniline (AZNME) parts in an antiparallel fashion (contrary to the usual expectation for H-aggregates) with strong inter- and intrapair van der Waals and π-π interactions between the constituent fullerene moieties. Unlike those of porphyrin/phthalocyanine bowl-like donor-initiated architectures, a rare class of DPNME dyadic supramolecular self-assemblies was realized with π-extended 2D fullerene networks, in which the linear geometry of the AZNME donor and the conformational rigidity of the fullerene acceptor played crucial roles.

Role of povidone iodine in periapical surgeries: Hemostyptic and anti-inflammatory?

INTRODUCTION: Periapical surgery needs asepsis, a bloodless field for ensuring success of the treatment. Efficacy of Povidone Iodine (PVI) in the elimination of pathogen causing periapical lesions is well established. PVI is also widely used as a disinfectant, sclerosing agent, styptic as well as an anti-odematous agent. MATERIALS AND METHODS: This prospective pilot study done on 20 males between 20-40 years age group with periapical lesions in single rooted maxillary anterior tooth of 1-2 cm in diameter. The bleeding time, clotting time, bleeding time at the apex, drugs used and visual analogue scale of oedema on postoperative days were obtained. Descriptive statistics, paired t test and independent t-test were used. RESULTS AND CONCLUSION: Results show a statistically significant reduction in the time required to achieve a bloodless field and a marked decrease in oedema in the first and second postoperative days resulting in lesser consumption of NSAIDs. In conclusion, the effect of PVI in periapical surgery seems to reduce the bleeding time at apex, total dose of NSAIDs used, oedema on first two postoperative days with high statistical significance. Hence the routine use of saline in periapical surgeries may be effectively substituted with PVI. The finding of this pilot study has to be evaluated using wider samples for effective clinical translations.

Tunable electronic properties of a proton-responsive N,N-dimethylaminoazobenzene fullerene (C60) dyad.

A basic N,N-dimethylaminoazobenzene-fullerene (C(60)) dyad molecular skeleton is modelled and synthesized. In spite of the myriad use of azobenzene as a photo- and electrochromic moiety, the idea presented herein is to adopt a conceptually different path by using it as a bridge in a donor-bridge-acceptor single-molecular skeleton, connecting the electron acceptor N-methylfulleropyrrolidine with an electron donor N,N-dimethylaniline. Addition of trifluoroacetic acid (TFA) results in a drastic colour change of the dyad from yellow to pink in dichloromethane (DCM). The structure of the protonated species are established from electronic spectroscopy and time-dependent density functional theory (TD-DFT) calculations. UV/Vis spectroscopic investigations reveal the disappearance of the 409 nm (1)(π→π*) transition with appearance of new features at 520 and 540 nm, attributed to protonated ß and α nitrogens, respectively, along with a finite weight of the C(60) pyrrolidinic nitrogen. Calculations reveal intermixing of n((N=N))→π*((N=N)) and charge transfer (CT) transitions in the neutral dyad, whereas, the n((N=N))→π*((N=N)) transition in the protonated dyad is buried under the dominant (1)(π →π*) feature and is red-shifted upon Gaussian deconvolution. The experimental binding constants involved in the protonation of N,N-dimethylanilineazobenzene and the dyad imply an almost equal probability of existence of both α- and ß-protonated forms. Larger binding constants for the protonated dyads imply more stable dyad complexes than for the donor counterparts. One of the most significant findings upon protonation resulted in frontier molecular orbital (FMO) switching with the dyad LUMO located on the donor part, evidenced from electrochemical investigations. The appearance of a new peak, prior to the first reduction potential of N-methylfulleropyrrolidine, clearly indicates location of the first incoming electron on the donor-centred LUMO of the dyad, corroborated by unrestricted DFT calculations performed on the monoanions of the protonated dyad. The protonation of the basic azo nitrogens thus enables a rational control over the energetics and location of the FMOs, indispensable for electron transport across molecular junctions in realizing futuristic current switching devices.

Preventive effect of caffeic acid on lysosomal dysfunction in isoproterenol-induced myocardial infarcted rats.

We evaluated the preventive effect of caffeic acid (CA) on lysosomal enzymes in isoproterenol (ISO)-treated myocardial infarcted rats. Male albino Wistar rats were pretreated with CA (15 mg/kg) daily for a period of 10 days. After the pretreatment period, ISO (100 mg/kg) was subcutaneously injected to rats twice at an interval of 24 h. The activity of serum creatine kinase-MB and lactate dehydrogenase was increased significantly (P < 0.05) in ISO-induced myocardial infarcted rats. The levels of plasma thiobarbituric acid reactive substances and lipid hydroperoxides were significantly (P < 0.05) increased, and the level of plasma-reduced glutathione was significantly (P < 0.05) decreased in ISO-induced myocardial infarcted rats. The activities of lysosomal enzymes (beta-glucuronidase, beta-N-acetylglucosaminidase, beta-galactosidase, cathepsin-B and cathepsin-D) were increased significantly (P < 0.05) in the serum and heart of ISO-induced myocardial infarcted rats. ISO induction also resulted in decreased stability of membranes, which was reflected by lowered activities of beta-glucuronidase and cathepsin-D in different fractions except cytosol. Pretreatment with CA (15 mg/kg) to ISO-treated rats significantly (P < 0.05) prevented the changes in the activities of cardiac marker enzymes, the levels of lipid peroxidation products, reduced glutathione and the activities of lysosomal enzymes in the serum, heart, and subcellular fractions. Oral treatment with CA (15 mg/kg) to normal control rats did not show any significant effect. Thus, the results of our study showed that CA prevented the lysosomal membrane damage against ISO-induced myocardial infarction. The observed effects of CA are due to membrane-stabilizing, antilipo peroxidative, and antioxidant effects.

Community reintegration of spinal cord-injured patients in rural south India.

STUDY DESIGN: Cross sectional follow-sup survey. OBJECTIVE: To ascertain the factors influencing community reintegration, of individuals with spinal cord injury living in rural environment, and to suggest measures to enhance community participation. SETTING: Bangalore, Karnataka, India. METHODS: Thirty-five individuals who were admitted under Physical Medicine and Rehabilitation Department of St Johns Medical College Hospital and rehabilitated to their functional level based on their level of injury; individuals living in rural environment were included in the study. The study was conducted by means of a standardized questionnaire and environmental and home assessments carried out during follow-up home visits after 12 months of discharge from the hospital. The main outcome measures were Craig Handicap Assessment and Reporting Technique (CHART) and Craig Hospital Inventory of Environmental Factors (CHIEF). The home visits and assessments were carried out by a rehabilitation team, which consisted of community-based rehabilitation worker, medico-social worker, physiotherapist and occupational therapist, and headed by a physiatrist. RESULTS: The findings of the study indicate a general decline in community re integration in terms of physical independence, mobility, occupation and social integration. Mobility issues were the greatest perceived barrier and economic issues also significantly influenced the community participation. CONCLUSION: Our study showed significant decline in community reintegration in subjects living in rural south India. Architectural and environmental barriers, poor socio-economic status and comorbidities significantly affected the level of community participation.

Protective effect of caffeic acid on cardiac markers and lipid peroxide metabolism in cardiotoxic rats: an in vivo and in vitro study.

Myocardial infarction affects a large population in the world. Lipid peroxide metabolism plays an important role in the pathology of myocardial infarction. This study aims to evaluate the preventive effect of caffeic acid on lipid peroxides, antioxidants, cardiac marker enzymes, and histopathological findings in isoproterenol (ISO)-induced myocardial-infarcted male Wistar rats. Myocardial infarction was induced in rats by subcutaneous injection of ISO (100 mg/kg) at an interval of 24 hours for 2 days. The ISO-induced rats showed significant increase in the levels of thiobarbituric acid reactive substances, lipid hydroperoxides in the heart, plasma uric acid, and serum cardiac marker enzymes, and significant decrease in the activities of heart superoxide dismutase, catalase, glutathione peroxidase, glutathione reductase, glutathione-S-transferase, and the levels of reduced glutathione, vitamin E, and vitamin C in the plasma and heart. Oral pretreatment with caffeic acid (15 mg/kg) daily for 10 days showed significant decrease in the levels of serum cardiac marker enzymes, heart lipid peroxidation products and plasma uric acid and significant increase in the levels of antioxidant system. Histopathology of myocardium also confirmed the protective effect of caffeic acid in myocardial-infarcted rats. In vitro study on total antioxidant activity (2,2'-azinobis-[3-ethylbenzothiazoline-6-sulfonic acid](+) assay) confirmed the strong antioxidant action of caffeic acid. Thus, the present study revealed that caffeic acid ameliorates cardiac damage in ISO-induced myocardial infarction by maintaining lipid peroxide metabolism due to its free radical scavenging and antioxidant effects. A diet containing caffeic acid may be beneficial to myocardial infarction.

Intramolecular electronic communication in a dimethylaminoazobenzene-fullerene C60 dyad: an experimental and TD-DFT study.

An electronically push-pull type dimethylaminoazobenzene-fullerene C(60) hybrid was designed and synthesized by tailoring N,N-dimethylaniline as an electron donating auxochrome that intensified charge density on the beta-azonitrogen, and on N-methylfulleropyrrolidine (NMFP) as an electron acceptor at the 4 and 4' positions of the azobenzene moiety, respectively. The absorption and charge transfer behavior of the hybrid donor-bridge-acceptor dyad were studied experimentally and by performing TD-DFT calculations. The TD-DFT predicted charge transfer interactions of the dyad ranging from 747 to 601 nm were experimentally observed in the UV-vis spectra at 721 nm in toluene and dichloromethane. A 149 mV anodic shift in the first reduction potential of the N=N group of the dyad in comparison with the model aminoazobenzene derivative further supported the phenomenon. Analysis of the charge transfer band through the orbital picture revealed charge displacement from the n((N=N)) (nonbonding) and pi ((N=N)) type orbitals centered on the donor part to the purely fullerene centered LUMOs and LUMO+n orbitals, delocalized over the entire molecule. The imposed electronic perturbations on the aminoazobenzene moiety upon coupling it with C(60) were analyzed by comparing the TD-DFT predicted and experimentally observed electronic transition energies of the dyad with the model compounds, NMFP and (E)-N,N-dimethyl-4-(p-tolyldiazenyl)aniline (AZNME). The n((N=N)) --> pi*((N=N)) and pi((N=N)) --> pi*((N=N)) transitions of the dyad were bathochromically shifted with a significant charge transfer character. The shifting of pi((N=N)) --> pi*((N=N)) excitation energy closer to the n --> pi*((N=N)) in comparison with the model aminoazobenzene emphasized the predominant existence of charge separated quinonoid-like ground state electronic structure. Increasing solvent polarity introduced hyperchromic effect in the pi((N=N)) --> pi*((N=N)) electronic transition at the expense of transitions involved with benzenic states, and the extent of intensity borrowing was quantified adopting the Gaussian deconvolution method. On a comparative scale, the predicted excitation energies were in reasonable agreement with the observed values, demonstrating the efficiency of TD-DFT in predicting the localized and the charge transfer nature of transitions involved with large electronically asymmetric molecules with HOMO and LUMO centered on different parts of the molecular framework.

Synthesis and catalytic application of chiral 1,1'-Bi-2-naphthol- and biphenanthrol-based pincer complexes: selective allylation of sulfonimines with allyl stannane and allyl trifluoroborate.

New easily accessible 1,1'-bi-2-naphthol- (BINOL-) and biphenanthrol-based chiral pincer complex catalysts were prepared for selective (up to 85% enantiomeric excess) allylation of sulfonimines. The chiral pincer complexes were prepared by a flexible modular approach allowing an efficient tuning of the selectivity of the catalysts. By employment of the different enantiomeric forms of the catalysts, both enantiomers of the homoallylic amines could be selectively obtained. Both allyl stannanes and allyl trifluoroborates can be employed as allyl sources in the reactions. The biphenanthrol-based complexes gave higher selectivity than the substituted BINOL-based analogues, probably because of the well-shaped chiral pocket generated by employment of the biphenanthrol complexes. The enantioselective allylation of sulfonimines presented in this study has important implications for the mechanism given for the pincer complex-catalyzed allylation reactions, confirming that this process takes place without involvement of palladium(0) species.