Novel Benzothiadiazole-based Donor-Acceptor Systems: Synthesis, Ultrafast Charge Transfer and Separation Dynamics.

Near-infrared (NIR) absorbing electron donor-acceptor (D-A) chromophores have been at the forefront of current energy research owing to their facile charge transfer (CT) characteristics, which are primitive for photovoltaic applications. Herein, we have designed and developed a new set of benzothiadiazole (BTD)-based tetracyanobutadiene (TCBD)/dicyanoquinodimethane (DCNQ)-embedded multimodular D-A systems (BTD1-BTD6) and investigated their inherent photo-electro-chemical responses for the first time having identical and mixed terminal donors of variable donor-ability. Apart from poor luminescence, the appearance of broad low-lying optical transitions extendable even in the NIR region (> 1000 nm), particularly in the presence of the auxiliary acceptors, are indicative of underlying nonradiative excited state processes leading to strong intramolecular CT and subsequent charge separation (CS) processes in these D-A constructs. The spectral and temporal responses of different photoproducts are obtained from  transient studies. All the systems are found to be susceptible to ultrafast (~ps) CT and CS before carrier recombination to the ground state, which is, however, significantly facilitated after incorporation of the secondary TCBD/DCNQ acceptors, leading to faster and thus efficient CT processes. These findings are likely to expand the horizons of BTD-based multimodular CT systems to revolutionize the realm of solar energy conversion and associated photonic applications.

Near-IR Capturing N-Methylbenzene Sulfonamide-Phenothiazine Incorporating Strong Electron Acceptor Push-Pull Systems: Photochemical Ultrafast Carrier Dynamics.

Unraveling the intriguing aspects of the intramolecular charge transfer (ICT) phenomenon of multi-modular donor-acceptor-based push-pull systems are of paramount importance considering their promising applications, particularly in solar energy harvesting and light-emitting devices. Herein, a series of symmetrical and unsymmetrical donor-acceptor chromophores 1-6, are designed and synthesized by the Corey-Fuchs reaction via Evano's condition followed by [2+2] cycloaddition retroelectrocyclic ring-opening reaction with strong electron acceptors TCNE and TCNQ in good yields (~60-85 %). The photophysical, electrochemical, and computational studies are investigated to explore the effect of incorporation of strong electron acceptors 1,1,4,4-tetracyanobuta-1,3-diene (TCBD) and dicyanoquinodimethane (DCNQ) with phenothiazine (PTZ) donor. An additional low-lying broad absorption band extended towards the near-infrared (NIR) region suggests charge polarization after the introduction of the electron acceptors in both symmetrical and asymmetrical systems, leading to such strong ICT bands. The electrochemical properties reveal that reduction potentials of 3 and 6 are lower than those of 2 and 5, suggesting DCNQ imparts more on the electronic properties and hence largely contributes to the stabilization of LUMO energy levels than TCBD, in line with theoretical observations. Relative positions of the frontier orbitals on geometry-optimized structures further support accessing donor-acceptor sites responsible for the ICT transitions. Eventually, ultrafast carrier dynamics of the photoinduced species are investigated by femtosecond transient absorption studies to identify their spectral characteristics and target analysis further provides information about different excited states photophysical events including ICT and their associated time profiles. The key findings obtained here related to excited state dynamical processes of these newly synthesized systems are believed to be significant in advancing their prospect of utilization in solar energy conversion and related photonic applications.

Pediatric non-galenic pial arteriovenous fistula's characteristics and outcomes: a systematic review.

INTRODUCTION: Pediatric non-galenic pial arteriovenous fistulas (pAVFs) are rare vascular malformations that are characterized by a pial arterial-venous connection without an intervening capillary bed. Outcomes and treatment strategies for pAVFs are highly individualized, owing to the rarity of the disease and lack of large-scale data guiding optimal treatment approaches. METHODS: We performed a systematic review of pediatric patients (< 18 years at diagnosis) diagnosed with a pAVF by digital subtraction angiogram (DSA). The demographics, treatment modalities, and outcomes were documented for each patient and clinical outcome data was collected. Descriptive information stratified by outcome scores were classified as follows: 1 = excellent (no deficit and full premorbid activity), 2 = good (mild deficit and full premorbid activity), 3 = fair (moderate deficit and impaired activity), 4 = poor (severe deficit and dependent on others), 5 = death. RESULTS: A total of 87 studies involving 231 patients were identified. Median age at diagnosis was 3 years (neonates to 18 years). There was slight male preponderance (55.4%), and 150 subjects (81.1%*) experienced excellent outcomes after treatment. Of the 189 patients treated using endovascular approaches, 80.3% experienced excellent outcomes and of the 15 patients surgically treated subjects 75% had an excellent outcome. The highest rate of excellent outcomes was achieved in patients treated with Onyx (95.2%) and other forms of EvOH (100%). High output heart failure and comorbid vascular lesions tended to result in worse outcomes, with only 54.2% and 68% of subjects experiencing an excellent outcome, respectively. *Outcomes were reported in only 185 patients. CONCLUSION: pAVFs are rare lesions, necessitating aggregation of patient data to inform natural history and optimal treatment strategies. This review summarizes the current literature on pAVF in children, where children presenting with heart failure as a result of high flow through the lesion were less likely to experience an excellent outcome. Prospective, large-scale studies would further characterize pediatric pAVFs and enable quantitative analysis of outcomes to inform best treatment practices.

Macromolecular Crowding Significantly Affects the Conformational Features and Carbohydrate Binding Properties of CIA17, a PP2-Type Lectin from Coccinia indica.

The effect of macromolecular crowding on the conformational features and carbohydrate binding properties of CIA17, a PP2-type lectin, was investigated employing polymeric dextrans D6, D40, and D70 (Mr ∼ 6, 40, and 70 kDa, respectively) as crowders. While the secondary structure of CIA17 was significantly affected by D6, with a considerable decrease in the number of ß-sheets and ß-turns with a corresponding increase in the number of unordered structures, relatively smaller changes were induced by D40 and D70. However, differential scanning calorimetry (DSC) studies revealed that the thermal stability of the protein remains unchanged in the presence of crowders. While the larger dextrans, D70 and D40, induced modest quenching (∼10%) of the protein fluorescence by a static pathway, the smaller D6 induced a higher degree of quenching (37%), which involved both static and collisional quenching processes. The results of fluorescence correlation spectroscopy measurements together with DSC studies suggested that CIA17 forms larger oligomers in the presence of D40 and D70 but D6 prevents the formation of higher-order oligomers. The association constant for the CIA17-chitooligosaccharide interaction increased by ∼30% and 160% in the presence of D40 and D70, respectively, but decreased by ∼30% in the presence of D6. The higher binding affinity can be attributed to the excluded volume effect, i.e., an increased effective concentration of the protein in the presence of D40 and D70, whereas D6, being smaller, possibly penetrates into the protein interior, disrupting the water structure around the protein and also inducing conformational changes, resulting in weaker binding. These observations demonstrate that molecular crowding significantly affects the carbohydrate binding characteristics of lectins, which can modulate their physiological function.

Adoption of the Transradial Approach for Neurointerventions: A National Survey of Current Practitioners.

OBJECTIVES: The transradial approach (TRA) is technically feasible for both diagnostic and therapeutic neurointerventions. It improves patient comfort and is not associated with increased procedural complications when compared to the transfemoral approach (TFA). To date, no studies have looked at barriers to adoption of TRA in the neurointerventionalist community. This study aims to obtain neurointerventionalist perspectives on their adoption of TRA. MATERIALS AND METHODS: Online survey distributed to neurointerventionalists. RESULTS: A total of 55 neurointerventionalists, 52 of whom utilized TRA, responded to our survey. Overall, participants were not concerned about TRA's technical feasibility for diagnostic or therapeutic neurointerventions or about procedural complications. Most of our cohort adopted TRA due to its increased patient comfort and to reduce access site complications. In-institution interventionalists were strongly perceived to be the most effective method of teaching TRA when compared to other methods. Catheters and equipment issues were reported by about 30% of our cohort as a barrier to TRA adoption. CONCLUSIONS: The neurointerventionalist community largely perceives TRA to be technically feasible and was not concerned about its procedural complications. In-person institutionalists are strongly perceived to be the most effective method of teaching the approach. A significant barrier to adoption seems to be related to catheters and equipment issues.

Binding interaction study on human serum albumin with bactericidal gold nanoparticles synthesized from a leaf extract of Musa balbisiana: a multispectroscopic approach.

This study describes the eco-friendly, low-cost and room-temperature synthesis of gold nanoparticles from Musa balbisiana leaf extract, which acts as both reducing and stabilizing agent, and characterized by ultraviolet-visible (UV-vis) light spectroscopy, fourier transform infrared (FTIR) spectroscopy, field emission scanning electron microscopy (FE-SEM), analytical transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDAX) and dynamic light scattering (DLS) instruments. These nanoparticles showed an average diameter of 33.83 ± 3.39 nm, which was confirmed from the size distribution histogram. The bactericidal activity of these nanoparticles was confirmed using bacteria Escherichia coli and Staphylococcus aureus at 1 and 2 nM minimum inhibitory concentrations, respectively. The interaction between nanoparticles and human serum albumin (HSA) was investigated, as this plays significant roles in biological systems. The nature of interaction, binding parameters and structural variation of HSA in the presence of these nanoparticles have been evaluated using several useful spectroscopic approaches such as UV-vis, FTIR, time-resolved and steady-state fluorescence, and circular dichroism in addition to the measurement of zeta potential. This interaction study revealed that static quenching occurs in this process with minimal alteration in the secondary structure, but the native structure of HSA remained unaltered. The binding constant and thermodynamic parameters of this interaction process were also evaluated.

Molecular binding of toxic phenothiazinium derivatives, azures to bovine serum albumin: A comparative spectroscopic, calorimetric, and in silico study.

In this paper, the comparative binding behavior of antimalarial drug azure A, azure B and azure C with bovine serum albumin (BSA) has been studied. The interaction has been confirmed by multispectroscopic (UV, fluorescence, Fourier transform infrared (FT-IR), and circular dichroism) and molecular docking techniques. The experimental results show that azure B has the highest BSA binding affinity followed by azure A and azure C. The experimental evidence of binding showed a static quenching mechanism in the interaction azures with BSA. The isothermal titration calorimetry result reveals that the binding was exothermic with positive entropy contribution in each case. The thermodynamic parameters ΔH, ΔG, and ΔS at 25°C were calculated, which indicates that the weak van der Waals forces and hydrogen bonding rather than the hydrophobic effect played an important role in the interaction. According to the theory of Förster nonradiative energy transfer, the distance (r) between the donor (BSA) and acceptor azures found to be <7 nm in all the case. The circular dichroism and FT-IR studies show that the content of α-helix structure has increased for the azures-BSA system. Overall, experimental studies characterize the interaction dynamics and energetics of the binding of three toxic analogs towards the physiologically relevant serum albumins. We hope, the outcome of this work will be most helpful for synthesizing a new type of phenothiazinium derivatives of the better therapeutic application.

Green synthesis of silver nanoparticles using Pongamia pinnata seed: Characterization, antibacterial property, and spectroscopic investigation of interaction with human serum albumin.

In recent years, green synthesized nanoparticles from plant extract have drawn a great interest due to their prospective nanomedicinal application. This study investigates a proficient, safer, and sustainable way for the preparation of AgNPs using medicinal plant Pongamia pinnata (family: Leguminoseae, species: Pinnata) seeds extract without using any external reducing and stabilizing agent. Both ultraviolet-visible spectrum at λmax  = 439 nm and energy dispersive X-ray spectra proof the formation of AgNPs. An average diameter of the AgNPs was 16.4 nm as revealed from transmission electron microscope. Hydrodynamic size (d = ~19.6 nm) was determined by dynamic light scattering (DLS). Zeta potential of AgNPs was found to be -23.7 mV, which supports its dispersion and stability. Fourier transform infrared study revealed that the O â”€ H, C â• O, and C-O-C groups were responsible for the formation of AgNPs. The antibacterial activity of the synthesized AgNPs was checked against Escherichia coli ATCC 25922. AgNPs at its LD50 dose exhibited synergistic effect with ampicillin. Because protein-AgNPs association greatly affects its adsorption, distribution, and functionality and can also influence the functions of biomolecules. So in order to understand the adsorption and bioavailability, we investigated by fluorescence, ultraviolet-visible, and circular dichroism spectroscopic methods the interaction of synthesized AgNPs toward human serum albumin. The binding affinity and binding sites of human serum albumin toward AgNPs were measured by using the fluorescence quenching data. The circular dichroism spectroscopic results revealed that there was a negligible change of α-helical content in their native structure. Overall, these AgNPs show versatile biological activities and may be applied in the field of nanomedicine.

Teaching Old Compounds New Tricks: DDQ-Photocatalyzed C-H Amination of Arenes with Carbamates, Urea, and N-Heterocycles.

The C-H amination of benzene derivatives was achieved using DDQ as photocatalyst and BocNH2 as the amine source under aerobic conditions and visible light irradiation. Electron-deficient and electron-rich benzenes react as substrates with moderate to good product yields. The amine scope of the reaction comprises Boc-amine, carbamates, pyrazoles, sulfonimides and urea. Preliminary mechanistic investigations indicate arene oxidation by the triplet of DDQ to radical cations with different electrophilicity and a charge transfer complex between the amine and DDQ as intermediate of the reaction.

Insights into the Thermodynamics of Polymer Nanodot-Human Serum Albumin Association: A Spectroscopic and Calorimetric Approach.

With the advent of newer luminescent nanoparticles for bioimaging applications, their complex interactions with individual biomolecules need to be understood in great detail, before their direct application into cellular environments. Here, we have presented a systematic and detailed study on the interaction between luminescent polymer nanodots (PNDs) and human serum albumin (HSA) in its free and ligand-bound state with the help of spectrophotometric and calorimetric techniques. At physiological pH (pH = 7.4), PNDs quench the intrinsic fluorescence of HSA as a consequence of ground-state complex formation. The binding stoichiometry and various thermodynamic parameters have been evaluated by using isothermal titration calorimetry and the van't Hoff equation. It has been found that the association of PNDs with HSA is spontaneous (ΔG0 = -32.48 ± 1.24 kJ mol-1) and is driven by a favorable negative standard enthalpy change (ΔH0 = -52.86 ± 2.12 kJ mol-1) and an unfavorable negative standard entropy change (ΔS0 = -68.38 ± 2.96 J mol-1 K-1). These results have been explained by considering hydrogen bonding interactions between amino and hydroxyl groups (-NH2 and -OH) of PNDs and carboxylate groups (-COO-) of glutamate (Glu) and aspartate (Asp) residues of HSA. The binding constant of PNDs with HSA is estimated to be 4.90 ± 0.19 × 105 M-1. Moreover, it has been observed that warfarin-bound HSA (war-HSA) shows a significantly lower binding affinity (Kb = 1.15 ± 0.19 × 105 M-1) toward PNDs, whereas ibuprofen-bound HSA (ibu-HSA) shows a slightly lower affinity (Kb = 3.47 ± 0.13 × 105 M-1) compared with the free HSA. In addition, our results revealed that PNDs displace warfarin from site I (subdomain IIA) of HSA because of the partial unfolding of war-HSA. We hope that the present study will be helpful to understand the fundamental interactions of these biocompatible PNDs with various biological macromolecules.

Correction: Pyrido[1,2-a]pyrimidinium ions - a novel bridgehead nitrogen heterocycles: synthesis, characterisation, and elucidation of DNA binding and cell imaging properties.

Correction for 'Pyrido[1,2-a]pyrimidinium ions - a novel bridgehead nitrogen heterocycles: synthesis, characterisation, and elucidation of DNA binding and cell imaging properties' by Susanta Kumar Manna et al., Org. Biomol. Chem., 2015, 13, 8037-8047.

Photon Harvesting in Sunscreen-Based Functional Nanoparticles.

The ultraviolet light component in the solar spectrum is known to cause several harmful effects, such as allergy, skin ageing, and skin cancer. Thus, current research attention has been paid to the design and fundamental understanding of sunscreen-based materials. One of the most abundantly used sunscreen molecules is Avobenzone (AB), which exhibits two tautomers. Here, we highlight the preparation of spherically shaped nanoparticles from the sunscreen molecule AB as well as from sunscreen-molecule-encapsulated polymer nanoparticles in aqueous media and study their fundamental photophysical properties by steady-state and time-resolved spectroscopy. Steady-state studies confirm that the AB molecule is in the keto and enol forms in tetrahydrofuran, whereas the enol form is stable in the case of both AB nanoparticles and AB-encapsulated poly(methyl methacrylate) (PMMA) nanoparticles. Thus, the keto-enol transformation of AB molecules is restricted to a nanoenvironment. An enhancement of photostability in both the nanoparticle and PMMA-encapsulated forms under UV light irradiation is observed. The efficient excited energy transfer (60 %) from AB to porphyrin molecules opens up further prospects in potential applications as light-harvesting systems.

Pyrido[1,2-a]pyrimidinium ions--a novel bridgehead nitrogen heterocycles: synthesis, characterisation, and elucidation of DNA binding and cell imaging properties.

A novel class of bridgehead nitrogen heterocycles, pyrido[1,2-a]pyrimidinium ions, has been readily synthesized by a two-step one-pot reaction in high yields (up to 93%). These ionic compounds are bench stable and moisture tolerant and have highly fluorescent properties (quantum yield up to 0.65). A characteristic bright bluish fluorescence was observed in polar solvents such as acetonitrile and fluorescent intensity gradually diminishes with decreasing the polarity of the medium, which becomes almost negligible in toluene. These compounds also show interesting bioactivity. DNA interaction, imaging, and viability experiments with human leukemic Jurkat and KG-1A cells revealed that they are potential candidates for cancer diagnosis.

Organocatalytic glycosylation by using electron-deficient pyridinium salts.

A new organocatalytic glycosylation method based on electron-deficient pyridinium salts is reported. At ambient temperature and catalyst loadings as low as 1 mol %, 2-deoxyglycosides were formed from benzyl- and silyl-protected glycals and primary or secondary glycosyl acceptors, with excellent yields and anomeric selectivity. Mechanistic investigations point to alcohol-pyridinium conjugates (1,2-addition products) as key intermediates in the catalytic cycle.

Anion-binding catalysis by electron-deficient pyridinium cations.

A new activation principle in organocatalysis is presented: halide binding through Coulombic interactions. This mode of catalysis was realized by using 3,5-di(carbomethoxy)pyridinium ions that carry an additional electron-withdrawing substituent on the nitrogen atom, for example, pentafluorobenzyl or cyanomethyl. For the N-pentafluorobenzyl derivative, Coulombic interaction with the pyridinium moiety is complemented in the solid state by anion-π interactions with the perfluorophenyl ring. Bromide and chloride are bound by these cations in a 1:1 stoichiometry. Catalysis of the C-C coupling between 1-chloroisochroman (and related electrophiles) with silyl ketene acetals occurs at -78 °C and at low catalyst loading (2 mol%).

Complex management of pulmonary embolism in APLA syndrome: a case study of ECMO and bivalirudin utilization.

We report a case of a 22-year-old female with antiphospholipid antibody (APLA) syndrome who presented with severe dyspnea. Diagnostic imaging confirmed pulmonary embolism (PE), and treatment comprised unfractionated heparin and apixaban. APLA syndrome was diagnosed based on clinical, serological, and radiological findings. During evaluation, the patient developed cardiogenic shock necessitating catheter-directed thrombolysis, followed by veno-arterial extracorporeal membrane oxygenation (VA-ECMO) due to deteriorating condition and suspected heparin-induced thrombocytopenia (HIT). Surgical embolectomy with bivalirudin use followed, and a hybrid veno-arterial-venous (VAV) ECMO setup was implemented. Postoperatively, the patient improved, transitioning to veno-venous (VV) ECMO and eventually ECMO withdrawal. ECMO is a valuable tool for managing complex cardiorespiratory cases like PE. In the context of HIT and APLA syndrome, prompt anticoagulant transition is vital, and bivalirudin is an effective heparin alternative. Our study highlights the challenges involved in managing patients needing ECMO support with immunothrombotic conditions like HIT and APLA syndrome.

Hydrogen bonding interpolymer complex formation and study of its host-guest interaction with cyclodextrin and its application as an active delivery vehicle.

Interpolymer complex formation through hydrogen bonding has been investigated between two polymers: poly(acrylamide) (PAAm) and poly(vinyl alcohol) (PVA). The differential properties of the interpolymer complex with varying molecular weights of PVA have been studied by taking three different molecular weights of PVA. Furthermore, the host-guest interaction between the interpolymer complexes prepared and ß-cyclodextrin (ß-CD) has also been studied in detail. PAAm can form interpolymer complexes with PVA because of a cooperative hydrogen bonding interaction. The addition of ß-CD to a dilute aqueous solution of PAAm-PVA results in a competition between interpolymer hydrogen bonding and host-guest interactions. In this article, we have tried to decipher the complex chemistry that occurs in the microheterogeneous solution. The PAAm-PVA binary system and the PAAm-PVA-ß-CD ternary systems have been well characterized by using a fluorescent probe, coumarin-102. Dynamic light scattering (DLS), Fourier transform infrared (FTIR), fluorescence microscopy, and time-resolved fluorescence studies have been performed to substantiate steady-state fluorescence experiments. The results indicate the occurrence of a competitive interaction between the hydrogen bonding of the interpolymer complexes and the host-guest interaction with ß-CD, whereby the later predominates. It is probable that the hydrophobic cavity of ß-CD is threaded with linear polymers, thus forming a macromolecular supraassembly. It has also been concluded that PAAm preferentially interacts with ß-CD by compromising its interaction with PVA. The enhanced deposition and retention of actives with this system was studied with a single species regrowth assay, antibacterial efficacy and the cell viability were studied using the live-dead staining protocol. This therefore opens new avenues in the targeted delivery of actives.

New autopsy technique in COVID-19 positive dead bodies: opening the thoracic cavity with an outlook to reduce aerosol spread.

AIMS: After the advent of the COVID-19 pandemic, most countries have modified some of their health-related regulations. However, this has not been in the case of the postmortem of deceased because it has a legal aspect. Thus, the healthcare providers knowingly or unknowingly faced the threat of COVID-19 exposure from those dead bodies. To introduce an autopsy technique that reduces the droplet spreads, especially in those mortuaries where the biosafety mechanism is not highly equipped. METHODS: The validity of the new incision was achieved through the calculation of the Scale Content Validity Index (SCVI) taking inputs from 17 forensic specialists. The subjects for the new technique were selected from the patients who were RTPCR positive for COVID-19 or clinically or radiologically showing features of COVID-19. RESULTS: The dissection procedure was finalised by achieving the SCVI at 0.92. The chest cavity was approached through the abdominal cavity by opening the diaphragm and dissecting out the contents of the chest using a long blade knife. CONCLUSIONS: The advantage of this approach is that the autopsy surgeon and pathologists do not have to open the chest cavity by dissecting the Sternum, and hence the chance of droplet infection becomes almost nil. This technique is complete, simple, less time-consuming and conducive for sample collection, and even reduces the possibility of body fluid seepage following a postmortem examination.

Spine Deformity Associated with Chiari I Malformation and Syringomyelia.

The management of scoliosis in patients with Chiari I malformation and syringomyelia is a complex decision-making process, which is changing due to evolving evidence. Headache and scoliosis are common presenting symptoms of an underlying Chiari. History, physical examination, and screening with MRI are cornerstones of diagnosis. Posterior fossa decompression provides curve stabilization or regression in about half of patients. In those who require spinal fusion, careful attention must be paid to intraoperative neurological monitoring data to minimize risk of neurologic injury.