Synergistic effect of chrysin and kaempferol in ameliorating Cerebral Ischemic Reperfusion injury in rat by controlling expression of proinflammatory mediators NF-κB and STAT3.

OBJECTIVES: The two flavonoids kaempferol and chrysin are known to possess anti-inflammatory and antioxidant activities. In addition, these two flavonoids were reported to display synergistic effects against inflammation. The present study aims to provide an analysis of the combined effects of kaempferol and chrysin on ischemic rat brain induced by endothelin-1. METHODS: The neurological deficit score and infarct area of the brain were determined post drug treatment. Histopathological sections displayed the morphological changes in the brain tissue. The brain tissues were processed for assessing the antioxidant and anti-inflammatory activity by measuring superoxide dismutase activity, catalase activity, level of reduced glutathione, brain malondialdehyde, and amount of calcium. The expression level of inflammatory molecules was analyzed by western blotting and immunohistochemistry. RESULTS: The infarct area, neurological score and NF-κB and STAT3 expression levels were significantly reduced. DISCUSSION: The analysis of neuroprotective synergistic activity of kaempferol and chrysin indicated the therapeutic potential of the combination in alleviating cerebral ischemia by controlling expression of proinflammatory mediators.

Role of Redox-Inactive Metal Ions in Modulating the Reduction Potential of Uranyl Schiff Base Complexes: Detailed Experimental and Theoretical Studies.

A mononuclear uranyl complex, [UO2L] (1), has been synthesized with the ligand N,N'-bis(3-methoxy-2-hydroxybenzylidene)-1,6-diamino-3-azahexane (H2L). The complex showed a reversible U(VI)/U(V) redox couple in cyclic voltammetric measurements. The reduction potential of this couple showed a positive shift upon the addition of redox-inactive alkali- and alkaline-earth Lewis acidic metal ions (Li+, Na+, K+, Ca2+, Sr2+, and Ba2+) to an acetonitrile solution of complex 1. The positive shift of the reduction potential has been explained on the basis of the Lewis acidity and internal electric-field effect of the respective metal ions. The bimetallic complexes [UO2LLi(NO3)] (2), [UO2LNa(BF4)]2 (3), [UO2LK(PF6)]2 (4), [(UO2L)2Ca]·(ClO4)2·CH3CN (5), [(UO2L)2Sr(H2O)2]·(ClO4)2·CH3CN (6), and [(UO2L)2Ba(ClO4)]·(ClO4) (7) have also been isolated in the solid state by reacting complex 1 with the corresponding metal ions and characterized by single-crystal X-ray diffraction. Density functional theory calculations of the optimized [UO2LM]n+ complexes have been used to rationalize the experimental reduction and electric-field potentials imposed by the non-redox-active cations.

Controlled tuning of radiative-nonradiative transition via solvent perturbation: Franck-Condon emission vs. aggregation caused quenching.

Organic molecules with tunable fluorescence quantum yield are attractive for opto-electronic applications. A fluorophore with tunable fluorescence quantum yield should be a better choice for a variety of applications that demand fluorophores with different quantum yields. Here organic emitters with a continuous bell-shaped fluorescence yield profile would be promising in view of sustainability and reusability; however, fluorophores with these properties are rarely reported. A bis-indole derivative, 3,3'-bisindolyl(phenyl)methane (BIPM), was synthesised and found to undergo a unique 'rise-and-fall' profile in fluorescence yield with a compositional change of the 1,4-dioxane (DiOx)-H2O solvent system. A predominant interplay of two contrasting factors, (a) polarity and proticity induced emission enhancement and (b) aggregation caused fluorescence quenching, on either side of a crossover solvent composition (∼50% fW), resulted in a continuous bell-patterned fluorescence yield profile. Interestingly, these two factors could be observed individually or simultaneously by adjusting the H2O fraction. Detailed spectroscopic, electron microscopic and computational studies have been performed to substantiate the photophysics behind the solvent regulated modulation of fluorescence quantum yield.

Estimation of the reducing power and electrochemical behavior of few flavonoids and polyhydroxybenzophenones substantiated by bond dissociation energy: a comparative analysis.

Oxidative stress that damages cellular components affects various organs including the brain. It is thus believed to play an active role in neurodegenerative diseases, wherein the intrinsic antioxidant enzymes metabolize toxic intermediates. For therapeutic purpose, instead of antioxidant enzymes, small organic compounds as antioxidants may be more effective. Here, reducing power and electrochemical behavior of some flavanols, flavanonols, flavones, flavonols and O-methylated flavonols have been estimated and confirmed by the calculated bond dissociation energy. Compared to other classes, flavonols exhibited increased reducing power that decreased with methylation of the oxygen atom in the B-ring. Gossypetin emerged as the most effective of these flavonols. Generally, compounds with two hydroxyl groups in two consecutive positions of the phenyl ring and an enolic group in the C-ring with more preference for the hydroxyl group in the ortho position with respect to each other in the catechol moiety showed major activity. 5 position of the A-ring showed the least effect on the activity. The present understanding therefore may be applied for identifying compounds to be used as scaffold for designing potent antioxidants.

Family of Isomeric CuII-LnIII (Ln = Gd, Tb, and Dy) Complexes Presenting Field-Induced Slow Relaxation of Magnetization Only for the Members Containing GdIII.

The strategic design and synthesis of two isomeric CuII complexes, [CuLA] and [CuLB], of asymmetrically dicondensed N2O3-donor Schiff-base ligands (where H2LA and H2LB are N-salicylidene-N'-3-methoxysalicylidenepropane-1,2-diamine and N-3-methoxysalicylidene-N'-salicylidenepropane-1,2-diamine, respectively) have been accomplished via a convenient CuII template method. These two complexes have been used as metalloligands for the synthesis of three pairs of Cu-Ln isomeric complexes [CuL(µ-NO3)Ln(NO3)2(H2O)]·CH3CN (for complexes 1A-3A, L = LA, and for complexes 1B-3B, L = LB and Ln = Gd, Tb, and Dy, respectively), all of which have been characterized structurally. In all six isomorphous and isostructural complexes, the decacoordinated LnIII centers and pentacoordinated CuII centers possess sphenocorona and square-pyramidal geometries, respectively. The isomeric pair of Cu-Gd compounds shows field-induced slow relaxation of magnetization, although they present the typical isotropic behavior of GdIII complexes, indicating that slow relaxation is not due to the usual energy barrier originating from the magnetic anisotropy. The isostructural derivatives with the ion-anisotropic lanthanides TbIII and DyIII do not show slow magnetic relaxation with or without a direct-current bias field, demonstrating that the magnetic response of the isotropic system CuII-GdIII occurs through different mechanisms than the rest of the Ln cations.

Exchange-Bias Quantum Tunneling of the Magnetization in a Dysprosium Dimer.

Single-molecule magnets (SMMs) have been shown to possess bewildering phenomena leading to their proposal in several futuristic applications ranging from data storage devices to the basic unit of quantum computers. The main characteristic for the proposal of SMMs in such schemes is their inherent and intriguing quantum mechanical properties, which in turn, could be exploited in novel devices with larger capacities, such as for data storage or enhanced properties, such as quantum computers. In the quest of SMMs displaying such intriguing quantum effects, herein, we explore the synthesis, structural, and magnetic characterization of a dimeric dysprosium-based SMM composed of a tetradentate Schiff-base ligand with formula [Dy2(HL)2(benz)2(NO3)2]. Magnetic studies show that the complex is an SMM, while sub-Kelvin µ-SQUID studies revealed the exchange-bias characteristics of the system attributed to the presence of exchange interaction between the Dy3+ pair.

The Effect of Guest Metal Ions on the Reduction Potentials of Uranium(VI) Complexes: Experimental and Theoretical Investigations.

Two mononuclear uranyl complexes, [UO2 L1 ] (1) and [UO2 L2 ]⋅0.5 CH3 CN⋅0.25 CH3 OH (2), have been synthesized from two multidentate N3 O4 donor ligands, N,N'-bis(5-methoxysalicylidene)diethylenetriamine (H2 L1 ) and N,N'-bis(3-methoxysalicylidene)diethylenetriamine (H2 L2 ), respectively, and have been structurally characterized. Both complexes 1 and 2 showed a reversible UVI /UV couple at -1.571 and -1.519 V, respectively, in cyclic voltammetry. The reduction potential of the UVI /UV couple shifted towards more positive potential on addition of Li+ , Na+ , K+ , and Ag+ metal ions to acetonitrile solutions of complex 2, and the resulting potential was correlated with the Lewis acidity of the metal ions and was also justified by theoretical DFT calculations. No such shift in reduction potential was observed for complex 1. All four bimetallic products, [UO2 L2 Li0.5 ](ClO4 )0.5 (3), [UO2 L2 Na(ClO4 )]2 (4), [UO2 L2 Ag(NO3 )(H2 O)] (5), and [(UO2 L2 )2 K(H2 O)2 ]PF6 (6), formed on addition of the Li+ , Na+ , Ag+ , and K+ metal ions, respectively, to acetonitrile solutions of complex 2, were isolated in the solid state and structurally characterized by single-crystal X-ray diffraction. In all the species, the inner N3 O2 donor set of the ligand encompasses the equatorial plane of the uranyl ion and the outer open compartment with O2 O'2 donor sites hosts the second metal ion.

Joining of Trinuclear Heterometallic CuII2-MII (M = Mn, Cd) Nodes by Nicotinate to Form 1D Chains: Magnetic Properties and Catalytic Activities.

In the present work, four new heterometallic coordination complexes, {[(CuL)2Mn(nic)(H2O)2](ClO4)(0.5H2O)}n (1), {[(CuL)2Cd(nic)(H2O)2](ClO4)(H2O)}n (2), [(CuL)2Mn(nic)2]·2CH3OH (3), and [(CuL)2Cd(nic)2]·2CH3OH (4) (where H2L = N,N'-bis(α-methylsalicylidene)-1,3-propanediamine and nic = nicotinate ion), have been synthesized and characterized by single-crystal X-ray crystallography. In complexes 1 and 2, the nicotinate ion acts as a bifunctional linker (N,O donor) and joins the linear trinuclear nodes to form 1D polymeric chains. However, in complexes 3 and 4, the nicotinate ion uses only the oxygen atoms of the carboxylic acid (O donor) to bind to the metal centers, forming discrete linear trinuclear units, while the pyridyl nitrogen (N donor atom) remains free. The dc magnetic susceptibility measurements show that the CuII and MnII ions are antiferromagnetically coupled in both 1 and 3, with exchange coupling constants (JMn-Cu) of -20.57 ± 0.08 and -9.38 ± 0.08 cm-1, respectively. Among the four complexes, 1 and 3 show catechol oxidase and phenoxazinone synthase like catalytic activities. The turnover numbers (kcat) of complexes 1 and 3 for catecholase activity are 1121 and 720 h-1, respectively, at an optimum pH of 8.0 and for phenoxazinone synthase activity are 429 and 398 h-1, respectively, at an optimum pH of 9.7. The higher kcat values of 1 for both reactions are attributable to a water molecule coordinated to the central MnII atom that facilitates the substrate-catalyst binding. An ESI-mass spectral analysis indicates that trinuclear heterometallic species, e.g., [(CuL)2Mn(nic)(H2O)]+ for 1 and [(CuL)2Mn(nic)]+ for 3, are the active species that bind to the substrate, and on that basis, probable mechanisms through the formation of radical intermediates have been proposed.

Reaction of Cu(II) Chelates with Uranyl Nitrate to Form a Coordination Complex or H-Bonded Adduct: Experimental Observations and Rationalization by Theoretical Calculations.

Four new heterometallic Cu(II)-U(VI) species, [{(CuL1)(CH3CN)}UO2(NO3)2] (1), [{(CuL2)(CH3CN)}UO2(NO3)2] (2), [{(CuL3)(H2O)}UO2(NO3)2] (3), and [UO2(NO3)2(H2O)2]·2[CuL4]·H2O (4), were synthesized using four different metalloligands ([CuL1], [CuL2], [CuL3], and [CuL4], respectively) derived from four unsymmetrically dicondensed N,O-donor Schiff bases. Single-crystal structural analyses revealed that complexes 1, 2, and 3 have a discrete dinuclear [Cu-UO2] core in which one metalloligand, [CuL], is connected to the uranyl moiety via a double phenoxido bridge. Two chelating nitrate ions complete the octa-coordination around uranium. Species 4 is a cocrystal, where a uranyl nitrate dihydrate is sandwiched between two metalloligands [CuL4] by the formation of strong hydrogen bonds between the H atoms of the coordinated water molecules to U(VI) and the O atoms of [CuL4]. Spectrophotometric titrations of these four metalloligands with uranyl nitrate dihydrate in acetonitrile showed a well-anchored isosbestic point between 300 and 500 nm in all cases, conforming with the coordination of [CuL1], [CuL2], [CuL3], and the H-bonding interaction of [CuL4] with UO2(NO3)2. This behavior of [CuL4] was utilized to selectively bind metal ions (e.g., Mg2+, Ca2+, Sr2+, Ba2+, and La3+) in the presence of UO2(NO3)2·2H2O in acetonitrile. The formation of these Cu(II)-U(VI) species in solution was also evaluated by steady-state fluorescence quenching experiments. The difference in the coordination behavior of these metalloligands toward [UO2(NO3)2(H2O)2] was studied by density functional theory calculations. The lower flexibility of the ethylenediamine ring and a large negative binding energy obtained from the evaluation of H bonds and supramolecular interactions between [CuL4] and [UO2(NO3)2(H2O)2] corroborate the formation of cocrystal 4. A very good linear correlation (r2 = 0.9949) was observed between the experimental U═O stretching frequencies and the strength of the equatorial bonds that connect the U atom to the metalloligand.

Inclusion of Ln(III) in the Complexes of Co(II) with a Mannich Base Ligand: Development of Atmospheric CO2 Fixation and Enhancement of Catalytic Oxidase Activities.

The reaction of the Mannich base ligand (H2L = N, N'-dimethyl- N, N'-bis(2-hydroxy-3-methoxy-5-methylbenzyl)ethylenediamine) with Co(OAc)2·4H2O and Ln(III) nitrate salts (Ln = Gd, Tb, and Dy) under basic conditions afforded three carbonato-bridged isostructural tetranuclear heterometallic Co(II)-Ln(III) complexes (Co2Gd2L2(µ4-CO3)2(NO3)2] (1), [Co2Tb2L2(µ4-CO3)2(NO3)2] (2), and [Co2Dy2L2(µ4-CO3)2(NO3)2] (3)) by atmospheric CO2 fixation. In all structures, two dinuclear [(CoIIL)LnIII(NO3)] units are linked via two µ4-carbonato groups to form the tetranuclear CoII2LnIII2 core. The geometry around two penta-coordinated Co(II) ions is distorted square pyramid, and that around two nona-coordinated Ln(III) ions is intermediate between "spherical tricapped trigonal prism" and "spherical capped square antiprism" in all complexes. The complexes (1-3) showed catecholase-like and phenoxazinone-synthase-like catalytic activities. The kcat values calculated for the catecholase-like reaction were 254.5, 272.4, and 291.3 h-1, and for the phenoxazinone-synthase-like reaction they were 2930.6, 2965.2, and 2998.5 h-1 for complexes 1-3, respectively. The probable pathways for these two oxidase reactions have been proposed by the analyses of mass spectral data. For all of the compounds, the variable temperature magnetic susceptibility and isothermal magnetization data were investigated. The complexes exhibited overall ferromagnetic behavior, which was evident from the isothermal magnetization curves. AC magnetic susceptibility measurements revealed the slow relaxation of magnetization in complexes 2 and 3 but very negligible in 1. The activation energy barriers ( Ueff) for the slow relaxation process were evaluated and found to be 1.99, 2.79, and 8.98 K for 1, 2, and 3, respectively.

Surfactant and Cyclodextrin Induced Vesicle to Micelle to Vesicle Transformation in Aqueous Medium.

The physicochemical behavior and characteristics of lipid vesicles and micelles in aqueous medium are greatly tuned by changing the ambient physical parameters, such as temperature, pH, and ionic strength. The process is also controlled by external additives and the nature of the surfactants. In this work, we have used water-soluble surfactant and cyclodextrin to transform lipid vesicles to micelles to vesicles without changing the physical ambience. In this regard, we have used a special pyrene-tagged guest compound that readily forms excimer in water and thus acts as a reporter for the process. Giant lipid vesicles (biological cell mimics) are disrupted by cationic surfactants to form mixed elongated micelles that transform to vesicles on applying a cyclodextrin host.

Exploitation of the Flexidentate Nature of a Ligand To Synthesize Zn(II) Complexes of Diverse Nuclearity and Their Use in Solid-State Naked Eye Detection and Aqueous Phase Sensing of 2,4,6-Trinitrophenol.

Three Zn(II) complexes, [Zn2(HL)2(NO3)2]·H2O (1), [(Zn4L2)(µ3-OH)2](NO3)2·0.5H2O (2), and [(Zn6L2)( o-van)2(µ3-OCH3)2(µ3-OH)2](NO3)2 (3), have been synthesized by exploiting the flexidentate nature of a multidentate Schiff base ligand, H2L ( N, N'-bis(3-methoxysalicylidene)diethylenetriamine), by changing the reaction conditions and stoichiometry of the reactants. All three complexes are highly fluorescent in solution as well as in solid and have been used as luminescence sensors toward nitrophenol explosives in both the media. In aqueous/methanol medium, these complexes show very high selectivity and sensitivity with detection limit in ppb (2.03) or nM level (8.89 nM) for picric acid. The yellow color of all three Zn(II) complexes changes to red on mixing with small amount (∼5%) of picric acid in solid state, revealing the potential of these complexes for practical use in naked eye detection of 2,4,6-trinitrophenol (TNP) or picric acid in ambient light. In order to identify the host-guest interactions between Zn(II) complex and TNP, single crystals of the adduct of TNP with Zn(II) complex, [Zn2(HL)2(H2O)2][C6H2N3O7]2 (4), were grown. Its X-ray crystal structure reveals that two picrate ions are attached to a dinuclear host with the help of H-bonding and π···π interactions, throwing light into the quenching mechanism and selectivity of detection.

Ni(II) Complex of N2O3 Donor Unsymmetrical Ligand and Its Use for the Synthesis of NiII-MnII Complexes of Diverse Nuclearity: Structures, Magnetic Properties, and Catalytic Oxidase Activities.

A new mononuclear Ni(II) complex [NiL] (1) of an unsymmetrically dicondensed N2O3 donor ligand, H2L ( N-α-methylsalicylidene- N'-3-methoxysalicylidene-1,3-propanediamine), has been synthesized. Complex 1 on reaction with Mn(ClO4)2·6H2O and NaN3 in different molar ratios yielded three novel heterometallic NiII-MnII complexes, [(NiL)2Mn(N3)](ClO4) (2), [(NiL)2Mn2(N3)2(µ1,1-N3)2(CH3OH)2] (3), and [{(NiL)2Mn}2(µ1,3-N3)(H2O)]·(CH3OH),(ClO4)3 (4). The single crystal structure analyses show a trinuclear NiII2MnII structure for complex 2 and a tetranuclear NiII2MnII2 structure where two dinuclear NiIIMnII units are connected via µ1,1-azido and phenoxido bridges for complex 3. Complex 4 possesses a hexanuclear structure where two trinuclear NiII2MnII units are connected via a µ1,3-azido bridge. The temperature-dependent dc molar magnetic susceptibility measurements reveal that complexes 3 and 4 are antiferromagnetically coupled with the exchange coupling constants ( J) of -4.97, -0.14, -0.55 cm-1 for 3 and -3.94 cm-1 for 4. All complexes 2-4 show biomimetic catalytic oxidase activities. For catecholase like activity, the turnover numbers ( Kcat) are 768, 1985, and 2309 h-1 for complexes 2-4, respectively, whereas for phenoxazinone synthase like activity, the turnover numbers are 3240, 3360, and 13 248 h-1 for complexes 2-4, respectively. This difference in catalytic efficiencies is attributed to the variations in structures of the complexes and formation of active NiII-MnII species in solution during catalysis. The mass spectral analyses suggest the probable intermediate formation and cyclic voltammetry measurement suggest the reduction of Ni(II) to Ni(I) during catalytic reaction. The very high catalytic efficiencies for aerial dioxygen activation of all these heterometallic complexes as well as the highest activity of 4 is attributed to the coordinatively unsaturated penta-coordinated geometry or hexa-coordinated geometry with a solvent water molecule around Mn(II).

Subtle Structural Changes in (CuIIL)2MnII Complexes To Induce Heterometallic Cooperative Catalytic Oxidase Activities on Phenolic Substrates (H2L = Salen Type Unsymmetrical Schiff Base).

A new Cu(II) complex of an asymmetrically dicondensed Schiff base (H2L = N-(2-hydroxyacetophenylidene)-N'-salicylidene-1,3-propanediamine) derived from 1,3-propanediamine, salicylaldehyde, and o-hydroxyacetophenone has been synthesized. Using this complex, [CuL] (1), as a metalloligand, two new trinuclear Cu-Mn complexes, [(CuL)2Mn(N3)(H2O)](ClO4)·H2O (2) and [(CuL)2Mn(NCS)2] (3), have been prepared. Single-crystal structural analyses reveal that complexes 2 and 3 both have the same bent trinuclear {(CuL)2Mn}2+ structural unit in which two terminal bidentate square-planar (CuL) units are chelated to the central octahedral Mn(II) ion. This structural similarity is also evident from the variable-temperature magnetic susceptibility measurements, which suggest that compounds 2 and 3 are both antiferromagnetically coupled with comparable exchange coupling constants (-21.8 and -22.3 cm-1, respectively). The only difference between 2 and 3 lies in the coordination around the central Mn(II) ion; in 3, two SCN- groups are coordinated to the Mn(II), leaving a neutral complex, but in 2, one N3- group and one H2O molecule are coordinated to give a positively charged species. The presence of such a labile H2O coligand makes 2 catalytically active in mimicking two well-known polynuclear copper proteins, catecholase and phenoxazinone synthase. The turnover numbers (kcat) for the aerial oxidation of 3,5-di-tert-butylcatechol and o-aminophenol are 1118 and 6581 h-1, respectively, values which reflect the facility of the heterometallic catalyst in terms of both efficiency and catalytic promiscuity for aerial dioxygen activation. The mechanisms of these biomimetic oxidase reactions are proposed for the first time involving any heterometallic catalyst on the basis of mass spectral analysis, EPR spectroscopy, and cyclic voltammetry. The evidence of the intermediates indicates possible heterometallic cooperative activity where the substrates bind to a Mn(II) center and Cu(II) plays the role of an electron carrier for transformation of the phenolic substrates to their respective products with the reduction of aerial dioxygen.

Strong ferromagnetic exchange interactions in hinge-like Dy(O2Cu)2 complexes involving double oxygen bridges.

Two trinuclear isomeric compounds, [{(Cu(II)(salpn))(Me(CO)Me)}2Dy(III)(NO3)3] (1) and [{Cu(II)(salpn)}2Dy(III)(H2O)(NO3)3]·MeOH (2), along with one polymeric compound, {[{Cu(II)(salpn)}2Dy(III)(NO3)3bpy]·MeOH·H2O}n (3), were synthesized using a metalloligand, [Cu(II)(salpn)], where H2salpn and bpy stand for N,N'-bis(salicylidene)-1,3-propanediamine and 4,4'-bipyridine, respectively. Compounds 1 and 2 were selectively prepared with two solvents: the less polar acetone led to the exclusive crystallization of 1 with a transoid trinuclear architecture, while more polar solvent methanol provided sole construction of 2 with a cisoid trinuclear architecture. Compound 3 was prepared from 1 or 2 after bpy was introduced as a bridge. The Dy and Cu ions are doubly bridged with oxygen atoms, and the core DyO2Cu skeletons are characterized by different "butterfly angles" of 140.9(1)°, 147.1(19)°, and 142.4(2)° for 1, 2, and 3, respectively. We have examined the molecular structures and magnetic properties of 1-3 using high-frequency electron paramagnetic resonance (HF-EPR), magnetization, and magnetic susceptibility techniques. These compounds showed slow magnetization reversal in the measurements of alternating current magnetic susceptibility. We analyzed EPR frequency-field diagrams using an effective spin-Hamiltonian including only one doublet of Dy sublevels and found that the exchange couplings are ferromagnetic in all compounds. The exchange coupling parameters JDy-Cu of 1, 2, and 3 were determined as 2.25 ± 0.05, 1.82 ± 0.04, and 1.79 ± 0.04 K, respectively. These values are larger than those found in previous research using EPR analysis on [Cu(II)(L(A))(C3H6O)Dy(III)(NO3)3] (H2L(A) = N,N'-bis(3-methoxysalicylidene)-1,3-diamino-2,2-dimethylpropane) and [Dy(III)L(B)2(NO3)2{Cu(II)(CH3OH)}2](NO3)(CH3OH) (H2L(B) = 2,6-bis(acetylaceto)pyridine). The present result shows an advantage of doubly oxygen-bridged motifs to built strong ferromagnetic interactions between lanthanide and transition metal ions. We found that the exchange coupling strength is sensitive to the structural parameters such as bond angles, bond lengths, and butterfly angles. Precise determination of the exchange parameters would contribute to development of exchange-coupled 4f-3d heterometallic complexes.

Ferro- to antiferromagnetic crossover angle in diphenoxido- and carboxylato-bridged trinuclear Ni(II)2-Mn(II) complexes: experimental observations and theoretical rationalization.

Three new trinuclear heterometallic Ni(II)-Mn(II) complexes have been synthesized using a [NiL] metalloligand, where H2L = N,N'-bis(salicylidene)-1,3-propanediamine. The complexes [(NiL)2Mn(OCnn)2(CH3OH)2]·CH3OH (1), [(NiL)2Mn(OPh)2(CH3OH)2][(NiL)2Mn(OPh)2]·H2O (2), and [(NiL)2Mn(OSal)2(CH3OH)2]·2[NiL] (3) (where OCnn = cinnamate, OPh = phenylacetate, OSal = salicylate) have been structurally characterized. In all three complexes, in addition to the double phenoxido bridge, the two terminal Ni(II) atoms are linked to the central Mn(II) by means of a syn-syn bridging carboxylate, giving rise to a linear structure. Complexes 1 and 2 with Ni-O-Mn angles of 97.24 and 96.43°, respectively, exhibit ferromagnetic interactions (J(Ni-Mn) = +1.38 and +0.50 cm(-1), respectively), whereas 3 is antiferromagnetic (J(Ni-Mn) = -0.24 cm(-1)), having an Ni-O-Mn angle of 98.51°. DFT calculations indicate that there is a clear magneto-structural correlation between the Ni-O-Mn angle and J(Ni-Mn) values, which is in agreement with the experimental results.

Supramolecular 2D/3D isomerism in a compound containing heterometallic Cu(II)2Co(II) nodes and dicyanamide bridges.

Three new heterometallic copper(II)-cobalt(II) complexes [(CuL(2))2Co{dca}2]·H2O(1), [(CuL(1))2Co{dca}2]n (2a), and [(CuL(1))2Co{dca}2]n (2b) [dca(-) = dicyanamide = N(CN)2(-)] have been synthesized by reacting the "metallo-ligand" [CuL(1)] or [CuL(2)] with cobalt(II) perchlorate and sodium dicyanamide in methanol-water medium (where H2L(1) = N,N'-bis(salicylidene)-1,3-propanediamine and H2L(2) = N,N'-bis(α-methylsalicylidene)-1,3-propanediamine). The three complexes have been structurally and magnetically characterized. Complex 1 is a discrete trinuclear species in which two metallo-ligands coordinate to a cobalt(II) ion through the phenoxido oxygen atoms along with two terminally coordinated dicyanamide ions. On the other hand, complexes 2a and 2b are one of the very scarce examples of supramolecular isomers since they present the same [(CuL(1))2Co{dca}2] trinuclear units (very similar to the trinuclear core in 1) and differ only in their superstructures. Thus, although each Cu2Co trimer in 2a and 2b is connected to four other Cu2Co trimers through four µ1,5-dca(-) bridges, 2a presents a square two-dimensional structure (each Cu2Co trimer is connected to four in-plane Cu2Co trimers); whereas, 2b shows a triangular three-dimensional lattice (each Cu2Co trimer is connected to three in-plane and one out-of-plane trimers). Variable-temperature magnetic susceptibility measurements show the presence of moderate antiferromagnetic exchange interactions (ferrimagnetic) in all the cases mediated through the double phenoxido bridges that have been fitted with an anisotropic model including spin-orbit coupling in the central Co(II) ion.

Isolation of two different Ni2Zn complexes with an unprecedented cocrystal formed by one of them and a "coordination positional isomer" of the other.

A new homometallic trinuclear Ni(II) complex [(NiL)2Ni(NCS)2] (1) and three heterometallic trinuclear Ni(II)-Zn(II)-Ni(II) complexes [(NiL)2Zn(NCS)2] (2), [(NiL)2Zn(NCS)2(CH3OH)2]·2CH3OH (3) and {[(NiL)2Zn(NCS)2(CH3OH)2]} {[(NiL)2Zn(NCS)2]} (4) have been synthesized by using the "complex as ligand" approach with the "metalloligand" [NiL] (H2L = N,N'-bis(salicylidene)-1,3-propanediamine) and thiocyanate in different ratios. All the complexes have been structurally and magnetically characterized. In the isomorphous complexes 1 and 2, the two terminal square planar Ni atoms and the central octahedral nickel atom (in 1) or zinc atom (in 2) are arranged in a bent structure where two cis κN-SCN(-) thiocyanate ions are coordinated to the central atom. The chemical composition of 3 is very similar to that of 2 but, in 3, the central Zn atom is tetrahedral and the κN-SCN(-) thiocyanate ions occupy an axial position of each terminal nickel atom (which now are octahedral with the sixth position occupied by a methanol molecule). Complex 4 consists of two closely related trinuclear units 4A and 4B. In 4A, the coordination environments of the metals are identical to those of 3 whereas 4B is a "coordination position isomer" of complex 2 with the central square pyramidal Zn and one of the terminal square pyramidal Ni atoms coordinated by two κN-SCN(-) thiocyanate ions. Complex 4 is a unique example of a cocrystal formed by two similar trinuclear units (4A and 4B) where 4A is identical to an existing complex (3) and 4B is a "coordination position isomer" of another existing complex (2).

Solid lipid nanoparticle: A potent vehicle of the kaempferol for brain delivery through the blood-brain barrier in the focal cerebral ischemic rat.

Kaempferol is major flavonoid present in Convolvulus pluricaulis. This phytochemical protects the brain against oxidative stress, neuro-inflammation, neurotoxicity, neurodegeneration and cerebral ischemia induced neuronal destruction. Kaempferol is poorly water soluble. Our study proved that solid lipid nanoparticles (SLNs) were efficient carrier of kaempferol through blood-brain barrier (BBB). Kaempferol was incorporated into SLNs prepared from stearic acid with polysorbate 80 by the process of ultrasonication. Mean particle size and zeta potential of kaempferol loaded solid lipid nanoparticles (K-SLNs) were 451.2 nm and -15.0 mV. Atomic force microscopy showed that K-SLNs were spherical in shape. Fourier transformed infrared microscopy (FTIR) showed that both stearic acid and kaempferol were present in K-SLNs. X-ray diffraction (XRD) and differential scanning calorimetry (DSC) revealed that the matrices of K-SLNs were in untidy crystalline state. Entraptment efficiency of K-SLNs was 84.92%. In-vitro drug release percentage was 93.24%. Kaempferol loaded solid lipid nanoparticles (K-SLNs) showed controlled release profile. In-vitro uptake study showed significant efficiency of K-SLNs to cross blood-brain barrier (BBB). After oral administration into the focal cerebral ischemic rat, accumulation of fluorescent labeled K-SLNs was observed in the brain cortex which confirmed its penetrability into the brain. It significantly decreased the neurological deficit, infarct volume and level of reactive oxygen species (ROS) and decreased the level of pro-inflammatory mediators like NF-κB and p-STAT3. Damaged neurons and brain texture were improved. This study indicated increased bioavailability of kaempferol into the brain tissue through SLNs formulation.

Shift of the reduction potential of nickel(II) Schiff base complexes in the presence of redox innocent metal ions.

With the objective of gaining insight into the modulation of the reduction potential of the Ni(II/I) couple, we have synthesized two mononuclear nickel(II) complexes, NiLen (H2Len = N,N'-bis(3-methoxysalicylidene)-1,2-diamino-2-methylpropane) and NiLpn (H2Lpn = N,N'-bis(3-methoxysalicylidene)-1,3-diamino-2,2-dimethylpropane) of two N2O4 donor ligands and recorded their cyclic voltammograms. Both the nickel complexes show reversible reduction processes for the Ni(II/I) couple in acetonitrile solution but the reduction potential of NiLpn (E1/2 = -1.883 V) is 188 mV more positive than that of NiLen (E1/2 = -2.071 V). In the presence of redox inactive metal ions (Li+, Na+, K+, Mg2+, Ca2+ and Ba2+), the reduction potentials are shifted by 49-331 mV and 99-435 mV towards positive values compared to NiLen and NiLpn, respectively. The shift increases with the decrease of the pKa of the respective aqua-complexes of the metal ion but is poorly co-linear; however, better linearity is found when the shift of the mono- and bi-positive metal ion aqua complexes is plotted separately. Spectrophotometric titrations of these two nickel complexes with the guest metal ions in acetonitrile showed a well-anchored isosbestic point in all cases, confirming the adduct formation of NiLen and NiLpn with the metal ions. Structural analysis of single crystals, [(NiLen)Li(H2O)2]·ClO4 (1), [(NiLpn)Li(H2O)]·ClO4 (2), [(NiLpn)2Na]·BF4 (3) and [(NiLpn)2Ba(H2O)(ClO4)]·ClO4 (4), also corroborates the heterometallic adduct formation. The orbital energies of the optimised heterometallic adducts from which electron transfers originated were calculated in order to explain the observed reduction process. A strong linear connection between the calculated orbital energies and the experimental E1/2 values was observed. According to MEP and 2D vector field plots, the largest shift for divalent metal ions is most likely caused by the local electric field that they impose in addition to Lewis acidity.