Effect of Heartfulness Meditation on Oxidative Stress and Mindfulness in Healthy Participants.

BACKGROUND: Mental health issues are a major cause of poor life outcomes. Heartfulness (HFN) meditation is recommended for stress management and daily awareness. Although studies have shown that HFN can improve burnout and well-being, the biological mechanism underlying oxidative stress markers in a healthy human is unclear. OBJECTIVE: The purpose of this study was to determine whether HFN meditation benefits mindfulness responses and also to examine the impact of HFN meditation on oxidative stress in healthy individuals. METHODS: This prospective study involved 60 healthy individuals aged 18-24, divided into experimental and control groups, and implemented an HFN meditation intervention over 12 weeks. Both groups' serum malondialdehyde and serum nitrate levels were examined before and after the intervention. Additionally, psychometric evaluations concerning mindfulness and experiential avoidance were conducted utilizing scales such as the Mindful Attention Awareness Scale (MAAS), Five-Facet Mindfulness Questionnaire (FFMQ), Self-Compassion Scale (SCS), and Experiential Avoidance (EA). RESULTS: Following a three-month intervention period, serum malondialdehyde (MDA) levels in the experimental group did not show a significant increase, whereas in the control group, there was a significant increase (p < 0.000). Conversely, serum nitrate levels in the experimental group exhibited a significant increase (p < 0.05). Additionally, psychological stress decreased, as indicated by various questionnaire tools such as MAAS, FFMQ, SCS, and EA, with mindfulness showing an increase. However, a decrease in EA was seen. CONCLUSION: Heartfulness meditation has a positive impact on both mindfulness and oxidative stress. This suggests that consistent, long-term participation in HFN meditation could enhance mental health and foster overall well-being.

Exploring the neuropharmacological properties of scopoletin-rich Evolvulus alsinoides extract using in-silico and in-vitro methods.

OBJECTIVES: This study investigates the neuropharmacologic properties of Scopoletin, a bioactive compound in Evolvulus alsinoides (EA) extract, for managing cognitive impairment using in-vitro, in-silico, and zebrafish embryo toxicity assays. METHODS: The study estimates Scopoletin concentration in EA extract using HPTLC, assesses antioxidant properties using 2,2-Diphenyl-1-picrylhydrazyl (DPPH) and ferric reducing ability of plasma (FRAP) assays, and uses bioinformatic tools for scopoletin targets. Zebrafish embryo toxicity (ZET) is used to assess its toxicological profile. RESULTS: 0.0076% w/w Scopoletin in the samples was quantified using HPTLC, further studies on the DPPH (0.5 mM) and FRAP gave EC50 at 440.0 µg/ml and 84.29 µg/ml respectively. Twelve common targets associated with cognitive impairment (CI) were identified, along with possible pathways and molecular interactions. Our results indicate significant binding affinities of Scopoletin with ERAP1, SCN3A, and COMT. Molecular dynamics simulations further confirm the stability of these interactions. ZET assessment demonstrated mortality after 450 µg/ml concentration of EA extract. CONCLUSION: The study verifies the presence of Scopoletin in EA, along with their targets playing a crucial role in neurogenesis and neuroplasticity. The ZET demonstrated concentration-dependent effects, emphasizing the importance of dosage considerations in developing new formulations or therapeutics. This comprehensive study contributes valuable insight into the therapeutic potential of Scopoletin from EA for cognitive impairment, paving the way for further research.

Resolving the topology of encircling multiple exceptional points.

Non-Hermiticity has emerged as a new paradigm for controlling coupled-mode systems in ways that cannot be achieved with conventional techniques. One aspect of this control that has received considerable attention recently is the encircling of exceptional points (EPs). To date, most work has focused on systems consisting of two modes that are tuned by two control parameters and have isolated EPs. While these systems exhibit exotic features related to EP encircling, it has been shown that richer behavior occurs in systems with more than two modes. Such systems can be tuned by more than two control parameters, and contain EPs that form a knot-like structure. Control loops that encircle this structure cause the system's eigenvalues to trace out non-commutative braids. Here we consider a hybrid scenario: a three-mode system with just two control parameters. We describe the relationship between control loops and their topology in the full and two-dimensional parameter space. We demonstrate this relationship experimentally using a three-mode mechanical system in which the control parameters are provided by optomechanical interaction with a high-finesse optical cavity.

Pyrolysis Characteristics and Determination of Kinetic and Thermodynamic Parameters of Raw and Torrefied Chinese Fir.

Torrefaction influences the structural and physicochemical properties of biomass, thus further altering its thermal degradation behavior. In this study, the pyrolysis characteristics, reaction kinetics, and thermodynamic parameters of raw and torrefied Chinese fir (CF) were investigated. The torrefaction was conducted at 220 °C (mild) and 280 °C (severe), the pyrolysis was performed from ambient temperature to 600 °C, and four different heating rates (i.e., 5, 15, 25, and 35 °C/min) were adopted. The activation energy for pyrolysis was estimated by adopting three isoconversional methods. The master-plot method was employed to analyze the reaction mechanism. Furthermore, thermodynamic parameters, i.e., the enthalpy change (ΔH), Gibbs free energy change (ΔG), and entropy change (ΔS), were calculated. The average activation energy increased with the torrefaction temperature, whose values estimated by using different methods ranged from 88.57 to 97.70, from 121.04 to 126.35, and from 167.51 to 179.74 kJ/mol for raw, mildly, and severely torrefied CF samples, respectively. A compensation effect between the activation energy and pre-exponential factor was observed for all samples. The degradation process was characterized as endothermic, involving the formation of activated complexes and requiring extra energy for torrefied samples.

Impact of Heartfulness meditation practice on anxiety, perceived stress, well-being, and telomere length.

Objective: Exhaustion, stress, and burnout have all been found to be reduced using techniques like yoga and meditation. This study was carried out to check the effectiveness of Heartfulness practice (a form of meditation) on certain psychological and genetic variables. Methods: A total of 100 healthy individuals (aged 18-24) were recruited and randomized into two groups-Heartfulness intervention and control group. The intervention was carried out for 03 months. Participants from both groups were analysed for their cortisol levels and telomere length before and after the intervention. Psychometric measures of anxiety, perceived stress, well-being and mindfulness were carried out using Beck Anxiety Inventory (BAI), Perceived Stress Scale (PSS), WHO-Well-being Index (WHO-WBI) and Five Facet Mindfulness Questionnaire (FFMQ). Results: The cortisol levels in the meditators group significantly decreased (p < 0.001) after the intervention as compared to the non-meditators group, whereas, the telomere length increased in the mediators group. This increase was not significant (p > 0.05). Anxiety and perceived stress also decreased post intervention, and well-being as well as mindfulness increased, as assessed by the questionnaire tools, although the decrease in perceived stress was statistically insignificant (p > 0.05). A negative correlation was observed between telomere length and cortisol (stress biomarker), whereas a positive correlation was found between telomere length and well-being. Conclusion: Our data provide evidence that Heartfulness meditation practice can improve our mental health. Additionally, telomere length is shown to be affected by cortisol levels, and this meditation practice can also help to increase telomere length, and thereby slow down cellular aging. However, future studies with larger sample size are required to confirm our observations.

Hybrid hydrodynamic cavitation (HC) technique for the treatment and disinfection of lake water.

Water reclamation from lakes needs to be accomplished efficiently and affordably to ensure the availability of clean, disinfected water for society. Previous treatment techniques, such as coagulation, adsorption, photolysis, ultraviolet light, and ozonation, are not economically feasible on a large scale. This study investigated the effectiveness of standalone HC and hybrid HC + H2O2 treatment techniques for treating lake water. The effect of pH (3 to 9), inlet pressure (4 to 6 bar), and H2O2 loading (1 to 5 g/L) were examined. At pH = 3, inlet pressure of 5 bar and H2O2 loadings of 3 g/L, maximum COD and BOD removal were achieved·H2O2 was observed to significantly improve the performance of the HC when used as a chemical oxidant. In an optimal operating condition, a COD removal of 54.5 % and a BOD removal of 51.5 % using HC alone for 1 h is observed. HC combined with H2O2 removed 64 % of both COD and BOD. The hybrid HC + H2O2 treatment technique resulted in a nearly 100% removal of pathogens. The results of this study indicate that the HC-based technique is an effective method for removing contaminants and disinfection of the lake water.

Microbial Population Dynamics in Lemnaceae (Duckweed)-Based Wastewater Treatment System.

The dynamic microflora associated within, and in the surrounding aquatic environment, has been found to be responsible for the functional properties of many aquatic plants. The aim of the current work was to evaluate the effectiveness of Lemnaceae-based wastewater treatment system under tropical conditions and investigate the changes in the aquatic microflora upon plant growth. A biological wastewater treatment system was designed and investigated using mixed Lemnaceae culture comprising Lemna minor and Spirodela polyrhiza in a batch mode. A significant reduction in total solids (31.8%), biochemical oxygen demand (93.5%), and chemical oxygen demand (73.2%) was observed after seven days of duckweed growth using a low inoculum. A preliminary study on the change in the microbial population diversity and functionality, in the wastewater before and after treatment, revealed an increase in the denitrifying microflora in wastewater post-Lemnaceae treatment. Dominance of 10 bacterial phyla, contributing for 98.3% of the total bacterial communities, was recorded, and ~ 50.6% loss of diversity post-treatment of wastewater was revealed by the Shannon Index. Among 16 bacterial families showing relative abundance of ≥ 1% in untreated wastewater, Methylobacteriaceae, Pseudomonadaceae, Brucellaceae, Rhodobacteraceae, and Acetobacteraceae prevailed in the water post-treatment by duckweeds. This is a novel work done on the dynamics of aquatic microflora associated with Lemnaceae under tropical Indian conditions. It confirms the application of Lemnaceae-based wastewater treatment system as effective biofilter and calls for further studies on the active involvement of the endophytic and aquatic microflora in the functions of these plant.

Automobile service station waste assessment and promising biological treatment alternatives: a review.

Unprecedented growth in the automobile sector has led to an increased number of automobile service stations across all major cities especially in the developing countries. These service stations release huge amounts of waste that contain objectionable levels of oil and grease (O&G) and heavy metals, amongst other environmentally toxic compounds. Not much literature is available on the hazardous nature, public health concerns, and sustainable treatment options of such an industrial waste. This review throws light on the nuisances caused by the automobile industry waste, the various conventional and promising physical-chemical remediation measures adopted, and the scope of bioremediation for the same. Work on the use of microbial enzymes such as lipases and microbial surface-active agents (biosurfactants) as emerging promising candidates for the bioremediation of metals and O&G contaminated automobile service centre wastewater and soil are especially highlighted in this review article. The adoption of constructed wetlands and regular scientific monitoring of service sector are the aspects that would prove to be critical in sustainable and ecological automobile service station waste management. Stricter environment regulations, along with the growing ecological and environmental awareness, call for stringent monitoring of the service station waste and its treatment in an environmentally sustainable manner. This review can effectively aid in revealing potential hazards of this industrial sectors and in policy making for effective environmental monitoring.

Measuring the knot of non-Hermitian degeneracies and non-commuting braids.

Any system of coupled oscillators may be characterized by its spectrum of resonance frequencies (or eigenfrequencies), which can be tuned by varying the system's parameters. The relationship between control parameters and the eigenfrequency spectrum is central to a range of applications1-3. However, fundamental aspects of this relationship remain poorly understood. For example, if the controls are varied along a path that returns to its starting point (that is, around a 'loop'), the system's spectrum must return to itself. In systems that are Hermitian (that is, lossless and reciprocal), this process is trivial and each resonance frequency returns to its original value. However, in non-Hermitian systems, where the eigenfrequencies are complex, the spectrum may return to itself in a topologically non-trivial manner, a phenomenon known as spectral flow. The spectral flow is determined by how the control loop encircles degeneracies, and this relationship is well understood for [Formula: see text] (where [Formula: see text] is the number of oscillators in the system)4,5. Here we extend this description to arbitrary [Formula: see text]. We show that control loops generically produce braids of eigenfrequencies, and for [Formula: see text] these braids form a non-Abelian group that reflects the non-trivial geometry of the space of degeneracies. We demonstrate these features experimentally for [Formula: see text] using a cavity optomechanical system.

Isolation and development of a microbial consortium for the treatment of automobile service station wastewater.

AIM: This work aims to investigate the nature of waste being generated by automobile service stations (ASS) and to devise a microbial-based formulation for the treatment of ASS wastewater. METHODS AND RESULTS: Analysis of soil and water samples from the vicinity of different ASS in and around the Pune city region (India) revealed the presence of significant amounts of many heavy metals including zinc (Zn) 13.8-175.44 mg kg-1 , nickel (Ni) 0.6-5.5 mg kg-1 and copper (Cu) 8.07-179.2 mg kg-1 as well as oil and grease (O&G). A consortium, consisting of selected members from the ASS soil bacterial isolates, was formulated. The selection of consortium members was based on their ability to degrade hydrocarbons, tolerate heavy metals, and produce biosurfactant and lipase. The developed microbial consortium was capable of reducing the concentration of Ni, manganese (Mn) and chromium (Cr) by 69.25%, 14.63% and 84.93%, respectively, and O&G by 71.8% in the aqueous medium under laboratory conditions. CONCLUSIONS: Wastewater and soil analysis confirmed the presence of a high amount of O&G and metals in and around ASS. The developed microbial consortium holds potential for the treatment of wastewater rich in O&G and heavy metals. SIGNIFICANCE AND IMPACT OF THE STUDY: There is a dearth of scientific studies in India on the wastewater and polluted soils associated with ASS. This work reveals and confirms the hazardous nature of ASS and the need for the development and feasibility of microbial-based technology for the sustainable bioremediation of such sites.

Employing waste to manage waste: Utilizing waste biomaterials for the elimination of hazardous contaminant [Cr(VI)] from aqueous matrices.

Pollution caused due to discharge of toxic and hazardous chemical contaminants from industrial processes is an issue of major environmental concern. Hexavalent chromium [Cr(VI)] is one such known toxic heavy metal contaminant emanated largely from various industrial processes. Since physical-chemical treatment techniques are beset with several problems, there is an increased attention on the use of waste biomaterials/biomass as sorbents for the elimination of heavy metals from aqueous matrices. The main purpose of this study was to evaluate the effectiveness of some low-cost waste biomaterials such as fruit wastes, agricultural and industrial waste/byproducts, waste parts of photosynthetic plants, aquatic plants and fungal biomass collected from different sources for the biosorption of Cr(VI) from aqueous matrices. Amid the tested biomaterials, wood apple shell (WAS) biomass (Limonia acidissima) was found to be highly efficient biosorbent for Cr(VI) sorption. In majority of biomass, it was observed that biosorption of Cr(VI) took place at acidic pH with optimum pH ranging from 2.0 to 5.0. Loading capacity of WAS biomass (29.37 mg/g) was higher than that of conventional adsorbent activated charcoal (26.56 mg/g), which was used as control. Cr(VI) treated biomass (WAS) was characterized using instrumental techniques such as Scanned Electron Microscopy (SEM) and Energy Dispersive X-ray (EDX) confirmed the adsorption of Cr(VI). Boehm titration and FTIR studies were conducted to ascertain the presence of functional groups responsible for Cr(VI) sorption by WAS biomass. The WAS biomass removed Cr(VI) from industrial wastewater with an efficiency of >99.9% thus complying with the statutory limits. Considering the economical aspect, the selected biomass can be viewed as a potential candidate for the elimination of toxic contaminant from wastewater.

Biomanagement of hexavalent chromium: Current trends and promising perspectives.

Chromium (Cr) is most widely used heavy metal with vast applications in industrial sectors such as metallurgy, automobile, leather, electroplating, etc. Subsequently, these industries discharge large volumes of toxic Cr containing industrial wastewaters without proper treatment/management into the environment, causing severe damage to human health and ecology. This review gives some novel insights on the existing, successful and promising bio-based approaches for Cr remediation. In lieu of the multiple limitations of the physical and chemical methods for remediation, various biological means have been deciphered, wherein dead and live biomass have shown immense capabilities of removing/reducing and/or remediating Cr from polluted environmental niches. Adsorption of Cr by various agro-based waste and reduction/precipitation by different microbial groups have shown promising results in chromium removal/recovery. Various microbial based agents and aquatic plants like duckweeds are emerging as efficient adsorbents of metals and their role in chromium bioremediation is an effective green technology that needs to be harnessed effectively. The role of iron and sulphur reducing bacteria have shown potential for enhanced Cr remediation. Biosurfactants have revealed immense scope as enhancers of microbial metal bioremediation and have been reported to have potential for use in chromium recovery as well. The authors also explore the combined use of biochar and biosurfactants as a potential strategy for chromium bioremediation for the development of technology worth adopting. Cr is non-renewable and finite resource, therefore its safe removal/recovery from wastes is of major significance for achieving social, economic and environmental sustainability.

Indeterminate growth of the umbel inflorescence and bulb is associated with increased expression of the TFL1 homologue, AcTFL1, in onion.

TERMINAL FLOWER1 (TFL1) is a key gene for maintenance of vegetative and inflorescence indeterminacy and architecture. In onion, flowering and bulbing are two distinct developmental phases, each under complex environmental regulatory control. We have identified two CEN/TFL1-like genes from onion designated as AcTFL1 and AcCEN1. AcTFL1 is expressed during bulbing and inflorescence development with expression increasing with indeterminate growth of the umbel and the bulb suggesting possible conservation of function. Increase in AcTFL1 expression during umbel growth is associated with a simultaneous reduction in expression of AcLFY. Expression of AcTFL1 within the bulb is lowest in the outermost layers and highest in the innermost (youngest) layers. Bulb storage at room temperature or in cold leads to a gradual reduction in AcTFL1 levels in the meristem-containing tissues, the decrease being faster in the variety not requiring vernalization. Constitutive expression of AcTFL1, but not AcCEN1 complements the Arabidopsis tfl1-14 mutant and delays flowering in wild type suggesting conservation of the AcTFL1 function even in the distantly related Arabidopsis. Taken together, AcTFL1 appears to be the functional counterpart of TFL1 and regulates indeterminate growth of the umbel inflorescence as well as bulb development in onion.

Synthesis and biological evaluation of some new tricyclic pyrrolo[3,2-e]tetrazolo[1,5-c]pyrimidine derivatives as potential antitubercular agents.

A series of new tricyclic pyrrolo[3,2-e]tetrazolo[1,5-c]pyrimidines 8a-l were synthesized and characterized by IR, NMR (1 H and 13 C), and mass spectral analysis. The newly synthesized compounds 8a-l were inspected for their in vitro antitubercular activity against Mycobacterium tuberculosis (MTB) H37 Ra using an established XTT reduction menadione assay (XRMA). The title compounds exhibited minimum inhibitory concentrations (MIC90 ) ranging from 0.09 to >30 µg/mL. Five compounds (8c, 8i-l) were further confirmed for their dose-dependent effect against MTB. These compounds were evaluated in the THP-1 infection model, where 8i (MIC90 = 0.35 µg/mL), 8j (MIC90 = 1.17 µg/mL), 8k (MIC90 = 2.38 µg/mL), and 8l (MIC90 = 1.17 µg/mL) demonstrated significant antitubercular activity. All the ex vivo active compounds showed insignificant cytotoxicity against the human cancer cell lines, HeLa, MCF-7, and THP-1. Inactivity of all these compounds against Gram positive and Gram negative bacteria indicates their specificity. Molecular docking studies in the active site of the sterol 14alpha-demethylase (CYP51) enzyme revealed a similar binding mode to the native ligand in the crystal structure, thereby helping to understand the ligand-protein interactions and to establish a structural basis for inhibition of MTB. The results suggest novel pharmacophores as selective and specific inhibitors against MTB that can be explored further to synthesize lead compounds against tuberculosis. In summary, the results clearly indicate the identification of some novel, selective, and specific inhibitors against MTB that can be explored further for potential antitubercular drugs.

A Novel Poly(vinylidene fluoride)-Based 4-Miktoarm Star Terpolymer: Synthesis and Self-Assembly.

A well-defined amphiphilic miktoarm polymer incorporating poly(vinylidene fluoride) (PVDF), polystyrene (PS), and poly(ethylene glycol) (PEG) blocks was synthesized via a combination of atom-transfer radical polymerization (ATRP), iodine transfer radical polymerization (ITP), and copper-catalyzed azide-alkyne cycloaddition (CuAAC). Morphology and self-assembly of this star polymer were examined in organic solvents and in water. The aggregates formed in water were found to possess unusual frustrated topology due to immiscibility of PS and PVDF. The polymer was evaluated for transport of small hydrophobic molecules in water.

Well-defined multiblock poly(vinylidene fluoride) and block copolymers thereof: a missing piece of the architecture puzzle.

Unprecedented synthesis of multiblock poly(vinylidene fluoride) (PVDF, up to 16 300 g mol-1) with narrow-dispersity blocks (D = 1.26) mediated by a fluorinated cyclic xanthate via reversible addition-fragmentation chain transfer (RAFT) polymerization is reported. The as-synthesized multiblock PVDF was employed as a macroRAFT agent to prepare valuable multiblock copolymers with potential applications in emerging areas.

Bio-affinity of copper(II) complexes with nitrogen and oxygen donor ligands: Synthesis, structural studies and in vitro DNA and HSA interaction of copper(II) complexes.

Reported herein the binding affinity between Human Serum Albumin and the DNA binding and cleavage activity of three copper(II) complexes, [Cu(phen)(o-van)ClO4] (1), [Cu(phen)(gly)]ClO4 (2) and [Cu(L1)2(H2O)2] (3) wherein 1 and 2 are synthesized with 1,10-phenanthroline (phen) and co-ligands (o-van: o-vanillin; gly: glycine) and 3 with a ligand 2-hydroxy-3-methoxybenzylidene-4H-1,2,4-triazol-4-amine (H1L1). Complex 2 crystallizes in monoclinic (P21/n) space group shows square pyramidal geometry. The complex 3 crystallizes in monoclinic (P21/a) space group. All the three complexes exhibit binding affinity towards the transport protein Human Serum albumin (HSA). Quantitative evaluation of the thermodynamics of interaction and the results obtained from fluorescence spectroscopy suggest that metal coordinated glycynate, o-vanillin and perchlorate groups have a major role to play in the binding process, the latter two being stronger in the binding of complex 1. The coordinated water in complex 3 also plays an important role in the binding, which makes binding of complex 3 with HSA stronger than that of complex 2. Experimental results indicate that the binding affinity of the complexes towards CT-DNA is in the order 1>3>2 implying that complex 1 binds stronger than complex 3 and 2.The DNA cleaving activity of all the three complexes was explored in the presence of reactive oxygen compound, H2O2. All the three complexes have primarily shown the DNA cleaving activity.

Crystal structure of Zn(ZnCl4)2(Cho)2: the transformation of ions to neutral species in a deep eutectic system.

A neutral molecular complex, Zn(ZnCl4)2(Cho)2, has been isolated from the well-known choline chloride/ZnCl2 deep eutectic system (DES) and its crystal structure has been determined. The structure demonstrates the possibility of isolating unusual coordination complexes from DES which departs from the well-established observation of such systems being formed from large, ionic metal complexes or oligomers.

Versatility of Two Diimidazole Building Blocks in Coordination-Driven Self-Assembly.

A series of discrete molecular architectures was synthesized via self-assembly of two "linear" diimidazole donors [L1 = 1,4-di(1H-imidazol-1-yl)benzene and L2 = 1,1'-(2,5-dimethyl-1,4-phenylene)bis(1H-imidazole)] independently with cis-[(tmeda)Pd(NO3)2] [tmeda = N,N,N',N'-tetramethylethane-1,2-diamine], cis-[(tmeda)Pt(NO3)2], a diplatinum(II) acceptor (bisPt), and Pd(NO3)2. The donors L1 and L2 are isostructural with four hydrogens in the benzene ring of L1, whereas in L2 two of such hydrogens are substituted by methyl groups. The assemblies were characterized by NMR spectroscopy and electrospray ionization mass spectrometry analyses along with single-crystal structure determination of three of them. While the self-assembly of L1 with cis-[(tmeda)Pd(NO3)2] solely formed a [3 + 3] self-assembled molecular triangle (1), L2 with the same acceptor predominantly resulted in the formation of a [4 + 4] molecular square (3). Such a dramatic change in the final outcome in the coordination-driven self-assembly by simple alkyl substitution of isostructural donors is remarkable. Interestingly, self-assembly of L1 and L2 with analogous Pt(II) acceptor cis-[(tmeda)Pt(NO3)2] yielded mixtures of [3 + 3] triangle and [4 + 4] square, where the molecular triangles (4 and 6) were the predominant products in both the cases. The same donors in combination with a 0° acceptor bisPt independently formed the expected [2 + 2] metallo-macrocycles (8 and 9). Surprisingly, the macrocycle (9) involving L2 is found to exist in more than one conformation at room temperature. Moreover, the diimidazole donors formed unprecedented Pd6L12 molecular spheres (10 and 11) when they were separately treated with Pd(NO3)2. The imidazole moieties in the ligands are found to appear in versatile orientations in the synthesized molecules due to their rotational flexibility to produce required bite angles for the particular architecture.

Versatile Reactivity and Theoretical Evaluation of Mono- and Dinuclear Oxidovanadium(V) Compounds of Aroylazines: Electrogeneration of Mixed-Valence Divanadium(IV,V) Complexes.

The substituted hydrazones H2L(1-4) (L(1-4) = dibasic tridentate ONO(2-) donor ligands) obtained by the condensation of 2-hydroxy-1-naphthaldehyde and 2-aminobenzoylhydrazine (H2hnal-abhz) (H2L(1)) , 2-hydroxy-1-naphthaldehyde and 2-hydroxybenzoylhydrazine (H2hnal-hbhz) (H2L(2)), 2-hydroxy-1-acetonaphthone and benzoylhydrazine (H2han-bhz) (H2L(3)), or 2-hydroxy-1-acetonaphthone and 2-aminobenzoylhydrazine (H2han-abhz) (H2L(4)) are prepared and characterized. Reaction of ammonium vanadate with the appropriate H2L(1-4) results in the formation of oxidoethoxidovanadium(V) [V(V)O(OEt)(L(1-4))] (1-4) complexes. All compounds are characterized in the solid state and in solution by spectroscopic techniques (IR, UV-vis, (1)H, (13)C, and (51)V NMR, and electrospray ionization mass spectrometry). Single-crystal X-ray diffraction analysis of 1, 3, and 4 confirms the coordination of the corresponding ligands in the dianionic (ONO(2-)) enolate tautomeric form. In solution, the structurally characterized [V(V)O(OEt)(L)] compounds transform into the monooxido-bridged divanadium(V,V) [(V(V)OL)2-µ-O] complexes, with the processes being studied by IR and (1)H, (13)C, and (51)V NMR. The density functional theory (DFT) calculated Gibbs free energy of reaction 2[V(V)O(OEt)(L(4))] + H2O ⇆ [(V(V)OL(4))2-µ-O] + 2EtOH is only 2-3 kcal mol(-1), indicating that the dinuclear complexes may form in a significant amount. The electrochemical behavior of the complexes is investigated by cyclic voltammetry, with the V(V)-V(IV) E1/2(red) values being in the range 0.27-0.44 V (vs SCE). Upon controlled potential electrolysis, the corresponding (L)(O)V(IV)-O-V(V)(O)(L) mixed-valence species are obtained upon partial reduction of the [(V(V)OL)2-µ-O] complexes formed in solution, and some spectroscopic characteristics of these dinuclear mixed-valence complexes are investigated using DFT calculations and by electron paramagnetic resonance (EPR), with the formation of V(IV)-O-V(V) species being confirmed by the observation of a 15-line pattern in the EPR spectra at room temperature.