Photophysical studies on binding of curcumin to bovine serum albumins

The excited-state photophysical properties of curcumin in the presence of bovine serum albumin (BSA) have been studied. The absorption and fluorescence changes in curcumin on binding to BSA have been followed at varying concentrations of either curcumin or BSA to determine the binding constant, which has been found to be approximately 10(4) to 10(5) M(-1). Stopped-flow kinetics studies suggested at least two distinct kinetic steps for the binding of curcumin to BSA. The photophysical properties of the singlet-excited state of the curcumin-BSA complex have also been studied. Whereas the absorption spectrum of curcumin is redshifted, the fluorescence spectrum of curcumin was blueshifted in the presence of BSA. The fluorescence quantum yield of curcumin on complexing with BSA was approximately 0.05. Steady-state fluorescence anisotropy studies showed a significant increase in the anisotropy value of 0.37 in BSA-bound curcumin. The fluorescence decay of the curcumin-BSA complex followed a biexponential decay with fluorescence lifetimes of 413 ps (33%) and 120 ps (67%). On the basis of these complementary results, it has been concluded that curcumin shows very high binding to BSA, probably at the hydrophobic cavities inside the protein.     

Oxomolybdenum(VI) and (IV) complexes of pyrazole derived ONO donor ligands – synthesis,crystal structure studies and spectroelectrochemical correlation

Four cis-dioxomolybdenum complexes of general formula [MoO₂(Lⁿ)EtOH] (n = 1–4) and one oxomolybdenum(IV) complex [MoO(L⁴)EtOH], with potentially tridentate Schiff bases derived from 5-methyl pyrazole-3-carbohydrazide and salicylaldehyde/substituted salicylaldehyde/o-hydroxy acetophenone have been prepared. The Mo(IV) complex is derived from the Mo(VI) dioxo complex by oxotransfer reaction with PPh₃. The complexes are characterized by elemental analysis, electronic spectra, IR, ¹H NMR, and by cyclic voltammetry. All the Mo(VI) species are crystallographically characterized. The complexes have a distorted octahedral structure in which the ligand behaves as a binegative donor one, leaving the pyrazole –N uncoordinated towards the metal center. It is also revealed from the crystal structure that the Mo(VI) center enjoys an NO₅ donor environment.     

Polyhydrido Copper Nanoclusters with a Hollow Icosahedral Core: [Cu30H18{E2P(OR)2}12] (E=S or Se; R=nPr,iPr or iBu)

Although atomically precise polyhydrido copper nanoclusters are of prime interest for a variety of applications, they have so far remained scarce. Herein, this work describes the synthesis of a dithiophosphate-protected copper(I) hydride-rich nanocluster (NC), [Cu₃₀H₁₈{S₂P(OnPr)₂}₁₂] ( 1_H ), fully characterized by various spectroscopic methods and single-crystal X-ray diffraction. The X-ray structure of 1_H reveals an unprecedented central Cu₁₂ hollow icosahedron. Six faces of this icosahedron are capped by Cu₃ triangles, the whole Cu₃₀ core being wrapped by twelve dithiophosphate ligands and the whole cluster has ideal S₆ symmetry. The locations of the 18 hydrides in 1_H were ascertained by a single-crystal neutron diffraction study. They are composed of three types: capping μ₃-H, interstitial μ₄-H (seesaw) and μ₅-H ligands (square pyramidal), in good agreement with the DFT simulations. The numbers of hydrides and ligand resonances in the ¹H NMR spectrum of 1_H are in line with their coordination environment in the solid state, retaining the S₆ symmetry in solution. Furthermore, two new Se-protected polyhydrido copper nanoclusters, [Cu₃₀H₁₈{Se₂P(OR)₂}₁₂] ( 2_H : R=iPr 3_H : R=iBu) were synthesized from their sulfur relative 1_H via ligand displacement reaction and their X-ray structures feature the exceptional case where both the NC shape and size are fully conserved during the course of ligand exchange. DFT and TD-DFT calculations allow understanding the bonding and optical properties of clusters 1_H – 3_H . In addition, the reaction of 1_H with [Pd(PPh₃)₂Cl₂] in the presence of terminal alkynes led to the formation of new bimetallic Cu−Pd alloy clusters [PdCu₁₄H₂{S₂P(OnPr)₂}₆(C≡CR)₆] ( 4 : R=Ph; 5 : R = C₆H₄F).     

Convenient,Mild Catalytic Deprotection of Oximes to Carbonyl Compounds with Hydrogen Peroxide and Iodine Catalyst in Aqueous Acetonitrile

A clean, mild, and efficient catalytic deoximation procedure compatible with several common functional groups has been developed using 30% hydrogen peroxide activated by iodine catalyst in aqueous acetonitrile under essentially neutral conditions. The mechanistic features of an iodonium ion–driven nucleophilic cleavage of oximic C[dbnd]N have been revealed.     

Mass extrapolation of quarks and leptons to higher generations

An empirical mass formula is tested for the basic fermion sequences of charged quarks and leptons. This relation is a generalization of Barut’s mass formula for the lepton sequence (e, μ, τ......). It is found that successful mass extrapolation to the third and possibly to other higher generations (N>2) can be obtained with the first and second generation masses as inputs, which predicts the top quark massm _t to be around 20 GeV. This also leads to the mass ratios between members of two different sequences (i) and (i′) corresponding to the same higher generations (N>2).     

Diethyl 1-(p-fluoro­phenyl)-5-oxo-3-(2-thienyl)­pyrrolidine-2,2-di­carboxyl­ate

In the title compound, C₂₀H₂₀FNO₅S, the pyrrolidine ring adopts an envelope conformation. The fluoro­phenyl and thio­phene rings are individually planar. The molecular and crystal structures are stabilized by intra- and intermolecular C—H⋯O interactions.     

Preparation and Conformation of Organo‐Bridged Bis[tris(arylchalcogenolato)tin] Compounds – An Experimental and Quantum Chemical Study

Seven organo‐bridged bis[tris(arylchalcogenolato)tin] compounds with the general formulae (R′E)₃Sn–R–Sn(ER′)₃ (R = –(CH₂)₄–, 1,4‐bis(methyl)benzene, 4,4′‐bis(methyl)biphenyl; R′ = Ph, 1‐Np, 2‐Np; E = S, Se) were synthesized and characterized by means of X‐ray diffractometry as well as NMR spectroscopy. Three different conformations of the arylchalcogenolato groups ER′ with respect to the bridging group R were rationalized and explained by means of quantum chemical investigations.     

Syntheses,characterization, X-ray crystal structures and emission properties of copper(II), zinc(II) and cadmium(II) complexes of pyridyl–pyrazole derived Schiff base ligand – Metal selective ligand binding modes

The varying coordination modes of the title ligand, L [5-methyl-1-(pyridin-2-yl)-N′-[pyridin-2-ylmethylidene]pyrazole-3-carbohydrazide] towards the different metal centers is reported by preparation and characterization of Cu(II), Zn(II) and Cd(II) complexes, [Cu(L)NO₃.H₂O](NO₃) (1) [Zn(L)₂](ClO₄)₂·2DMF (2) and [Cd(L)(I)₂] (3) respectively. In 1, the neutral ligand serves as tetradentate 4 N donor where both pyridine and pyrazole nitrogen atoms of pyridyl–pyrazole part are coordinatively active, leaving the carbonyl oxygen of the carbohydrazide part inactive. The same pyridine and pyrazole N atoms remain abstained from the coordination process towards the Zn(II) and Cd(II) metal centers. For 2 and 3 the ligand behaves as a tridentate NNO donor where the two nitrogen atoms come from azomethine, pyridine of pyridine-2-carbaldehyde parts and O from carbonyl oxygen atoms (carbohydrazide part). The complex 1 and 2 are distorted octahedral while complex 3 adopts distorted square pyramidal geometry. All the complexes are X-ray crystallographically characterized.     

Control of molecular architecture by steric factors: mononuclear vs polynuclear manganese(III) compounds with tetradentate N2O2 donor Schiff bases

Three manganese(III) compounds, [Mn(III)(vanoph)(DMF)(H(2)O)]ClO(4) (1), [Mn(III)(vanoph)(N(3))(H(2)O)]·2H(2)O (2) and [Mn(III)(saloph)(μ(1,3)-N(3))](n) (3), where H(2)vanoph = N,N'-(1,2-phenylene)-bis(3-methoxysalicylideneimine), H(2)saloph = N,N'-(1,2-phenylene)-bis(salicylideneamine) are tetradentate N(2)O(2) ligands and DMF = N,N-dimethylformamide, have been prepared and characterised by elemental analysis, IR and UV-Vis spectroscopy and single-crystal X-ray diffraction studies. Compounds 1 and 2 are monomeric but compound 3 consists of a chain system with the repeating unit [Mn(III)(saloph)(N(3))] bridged by μ-1,3 azide. Compound 1 crystallises in monoclinic space group P2(1)/n with cell dimensions of a = 11.1430(2), b = 16.3594(3), c = 15.4001(3) ?, β = 108.417(1), Z = 4 whereas compounds 2 and 3 crystallise in orthorhombic space groups Pbca and Pna2(1), respectively, with cell dimensions of a = 16.069(3), b = 15.616(3), c = 18.099(4) ?, Z = 8 (for 2) and a = 18.760(9), b = 13.356(5), c = 6.616(3) ?, Z = 4 (for 3). In all the compounds, Mn(III) has a six-coordinated pseudo-octahedral geometry in which O(2), O(3), N(1) and N(2) atoms of the deprotonated di-Schiff base constitute the equatorial plane. In both compounds 1 and 2, water molecules are present in the fifth coordination sites in the apical positions. The sixth coordination sites are occupied by one O atom of a solvent DMF in compound 1 and an N atom of azide in compound 2. The coordinated water initiates hydrogen-bonded networks in both compounds 1 and 2 to form well-isolated supramolecular dimers. At room temperature the χ(M)T values for the compounds 1 and 2 remain almost constant until 30 K. Below this temperature, the χ(M)T values drastically drop to 0.72 cm(3) mol(-1) K for 1 and 0.52 cm(3) mol(-1) K for 2. The best fits were obtained with J = -0.92 cm(-1), |D| = 2.05 cm(-1), g = 2.0 and R = 8.1 × 10(-4) for 1 and J = -1.16 cm(-1), |D| = 2.05 cm(-1), g = 2.0 and R = 1.2 × 10(-3) for 2. However, in compound 3, two axial positions are occupied by the azide ions. The Mn···Mn repeating distance is 6.616 ? along the chain. Magnetic characterisation shows that the μ(1,3)-bridging azide ion mainly transmits an antiferromagnetic interaction (J = -6.36 cm(-1)) between Mn(III) ions. The presence of two methoxy groups increases the steric crowding in the H(2)vanoph moiety and thereby inhibits the formation of a polynuclear compound with this ligand.     

On Hadamard diagonalizable graphs

Of interest here is a characterization of the undirected graphs G such that the Laplacian matrix associated with G can be diagonalized by some Hadamard matrix. Many interesting and fundamental properties are presented for such graphs along with a partial characterization of the cographs that have this property.