Anion-directed template synthesis and hydrolysis of mono-condensed Schiff base of 1,3-pentanediamine and o-hydroxyacetophenone in Ni-II and Cu-II complexes

Bis(o-hydroxyacetophenone)nickel(II) dihydrate, on reaction with 1,3-pentanediamine, yields a bis-chelate complex [NiL2]center dot 2H(2)O (1) of mono-condensed tridentate Schiff base ligand HL {2-[1-(3-aminopentylimino)ethyl]phenol}. The Schiff base has been freed from the complex by precipitating the Nil, as a dimethylglyoximato complex. HL reacts smoothly with Ni(SCN)(2)center dot 4H(2)O furnishing the complex [NiL(NCS)] (2) and with CuCl2 center dot 2H(2)O in the presence of NaN3 or NH4SCN producing [CuL(N-3)](2) (3) or [CuL(NCS)] (4). On the other hand, upon reaction with Cu(ClO4)(2)center dot 6H(2)O and Cu(NO3)(2)center dot 3H(2)O, the Schiff base undergoes hydrolysis to yield ternary complexes [Cu(hap)(pn)(H2O)]ClO4 (5) and [Cu(hap)(pn)(H2O)]NO3 (6), respectively (Hhap = o-hydroxyacetophenone and pn = 1,3-pentanediamine). The ligand HL undergoes hydrolysis also on reaction with Ni(ClO4)(2)center dot 6H(2)O or Ni(NO3)(2)center dot 6H(2)O to yield [Ni(hap)(2)] (7). The structures of the complexes 2, 3, 5, 6, and 7 have been confirmed by single-crystal X-ray analysis. In complex 2, Ni-II possesses square-planar geometry, being coordinated by the tridentate mono-negative Schiff base, L and the isothiocyanate group. The coordination environment around Cu-II in complex 3 is very similar to that in complex 2 but here two units are joined together by end-on, axial-equatorial azide bridges to result in a dimer in which the geometry around Cu-II is square pyramidal. In both 5 and 6, the Cu-II atoms display the square-pyramidal environment; the equatorial sites being coordinated by the two amine groups of 1,3-pentanediamine and two oxygen atoms of o-hydroxyacetophenone. The axial site is coordinated by a water molecule. Complex 7 is a square-planar complex with the Ni atom bonded to four oxygen atoms from two hap moieties. The mononuclear units of 2 and dinuclear units of 3 are linked by strong hydrogen bonds to form a one-dimensional network. The mononuclear units of 5 and 6 are joined together to form a dimer by very strong hydrogen bonds through the coordinated water molecule. These dimers are further involved in hydrogen bonding with the respective counteranions to form 2-D net-like open frameworks. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).

Schiff base oxovanadium(IV) complexes of phenanthroline bases showing DNA photocleavage activity at near-IR light and photocytotoxicity

Oxovanadium(IV) complexes VO(L)(B)](ClO4) (1-3) of N-2-pyridylmethylidine-2-hydroxyphenylamine (HL) Schiff base and phenanthroline bases (B), viz. 1,10-phenanthroline (phen in 1), dipyrido3,2-d: 2',3'-f] quinoxaline (dpq in 2) or dipyrido3,2-a: 2',3'-c] phenazine (dppz in 3), were prepared, characterized and their DNA binding property, photo-induced DNA cleavage activity and photocytotoxicity in HeLa cells studied. The crystal structure of 1 shows the presence of a VO2+ moiety in VO2N4 coordination geometry. The complexes show a d-d band at similar to 830 nm in DMF. The complexes display an oxidative V(V)-V(IV) response near 0.5 V versus SCE and a reductive V(IV)/V(III) response near -0.65 V in DMF -0.1 M TBAP. The complexes that are avid binders to CT DNA giving K-b values within 7.1 x 10(4) to 3.2 x 10(5) M-1, do not show any significant chemical nuclease activity in presence of 3-mercaptopropionic acid or glutathione. The dpq and dppz complexes are photocleavers of pUC19 DNA in UV-A light of 365 nm forming both O-1(2) and (OH)-O-center dot radicals and in near-IR light of 785 nm forming (OH)-O-center dot radicals. The dppz complex exhibits photocytotoxicity in visible light in HeLa cells (IC50 = 6.8 mu M). Flow-cytometric study on this complex shows a high sub-G1 phase in light compared to dark indicating PDT effect. (C) 2011 Elsevier B. V. All rights reserved.

Polyimides derived from 3,3 '-bis(N-aminophthalimide)

A novel diamine, 3,3'-bis(N-aminophthalimide) (BAPI), was prepared from 3,3'-bis(N-phenylphthalimide). Its structure was determined via IR, H-1 NMR, N-15 NMR, elemental analysis, and single-crystal X-ray diffraction analysis. A series of homo- and copolyimides were synthesized by a conventional one-step method in p-chlorophenol. The characteristic IR absorption bands of hydrazine-based imide groups were near 1780, 1750, 1350, 1100, and 730 cm(-1). The polymers showed good solubility in polar aprotic solvents and phenols at room temperature. The temperatures of 5% weight loss (T-5%) of the polyimides ranged from 495 to 530 degrees C in air. DMTA analyses indicated that the glass-transition temperatures (Tgs) of the polyimides were in the range 371-432 degrees C. These polymers had cutoff wavelengths between 350 and 400 nm. The polyimide films of 6FDA/BAPI and 4,4'-HQPDA/BAPI were colorless; other films were pale yellow or yellow.

Thermal lens technique to evaluate the fluorescence quantum yield of a schiff base

The fluorescence spectrum of the schiff base obtained from salicylaldehyde and 2-aminophenol is studied using an argon-ion laser as the excitation source and its fluorescence quantum yield (Qf) is determined using a thermal lens method. This is a nondestructive technique that gives the absolute value of Qf without the need for a fluorescence standard. The quantum-yield values are calculated for various concentrations of the solution in chloroform and also for various excitation wavelengths. The value of Qf is relatively high, and is concentration dependent. The maximum value of Qf obtained is nearly 0.78. The high value of the fluorescence quantum yield will render the schiff base useful as a fluorescent marker for biological applications. Photostability and gain studies will assess its suitability as a laser dye.

Reproducibility and accuracy of linear measurements on dental models derived from cone-beam computed tomography compared with digital dental casts.

INTRODUCTION The aim of this study was to determine the reproducibility and accuracy of linear measurements on 2 types of dental models derived from cone-beam computed tomography (CBCT) scans: CBCT images, and Anatomodels (InVivoDental, San Jose, Calif); these were compared with digital models generated from dental impressions (Digimodels; Orthoproof, Nieuwegein, The Netherlands). The Digimodels were used as the reference standard. METHODS The 3 types of digital models were made from 10 subjects. Four examiners repeated 37 linear tooth and arch measurements 10 times. Paired t tests and the intraclass correlation coefficient were performed to determine the reproducibility and accuracy of the measurements. RESULTS The CBCT images showed significantly smaller intraclass correlation coefficient values and larger duplicate measurement errors compared with the corresponding values for Digimodels and Anatomodels. The average difference between measurements on CBCT images and Digimodels ranged from -0.4 to 1.65 mm, with limits of agreement values up to 1.3 mm for crown-width measurements. The average difference between Anatomodels and Digimodels ranged from -0.42 to 0.84 mm with limits of agreement values up to 1.65 mm. CONCLUSIONS Statistically significant differences between measurements on Digimodels and Anatomodels, and between Digimodels and CBCT images, were found. Although the mean differences might be clinically acceptable, the random errors were relatively large compared with corresponding measurements reported in the literature for both Anatomodels and CBCT images, and might be clinically important. Therefore, with the CBCT settings used in this study, measurements made directly on CBCT images and Anatomodels are not as accurate as measurements on Digimodels.

Synthesis, Spectral Characterization, Crystal Structure and Thermal Behavior of Tert-butyl 2,2-bis(2,4-dinitrophenyl)ethanoate

Tert-butyl 2,2-bis(2,4-dinitrophenyl)ethanoate was prepared from the ethanolic solution of 1-chloro-2,4-dinitrobenzene, tert-butyl 3-oxobutanoate and triethylamine. Acetyl group in tert-butyl 3-oxobutanoate has cleaved off during the formation of the title molecule. UV-VIS, IR, 1H NMR, 13C NMR, Proton-Proton COSY data and single crystal XRD results support the proposed structure. Flammability test, impact sensitivity test and TG/DTA studies at different heating rates on the synthesized molecule imply that it is an insensitive high energy density material.

SYNTHESES AND MOLECULAR-STRUCTURE OF (C8H8)LN(2,4-C7H11)THF (LN=ND, ER)

LnCl3 (Ln = Nd, Er) reacts with K2C8H8 to yield the complex (C8H8)LnCl.2THF, which reacts with K(2,4-C7H11) (2,4-C7H11 = 2,4-dimethylpentadienyl) to form (C8H8)Ln(2,4-C7H11).THF. The compound (C8H8)Nd(2,4-C7H11).THF(1) crystallizes from the mixed solvent

Synthesis and Characterization Of Some Transition Metal Complexes Of Multidentate Ligands

Coordination chemistry of schiff bases is of considerable interest due to their various magnetic, catalytic and biological applications. Here it describes the spectral characterization of schiff bases and its Mn (II), Cu (II) and Ni (II) complexes. Then synthesis and spectral characterization of Zn (II), Cd (II) and Co (II) complexes of schiff base derived from 3-Formylsalicilic Acid and 1,3-diaminopropane. Then it discusses the synthesis and spectral studies of Copper (II) complexes of 2-Hydroxyacetophenone N-phenyl semicarbazone. Finally it discusses the synthesis and spectral characterization of Co (III) complexes of salicylaldehyde N-phenyl semicarbazone. The preparation and characterization of Cobalt (III) complexes of salicylaldehyde, N-phenylthiosemicarbazone containing hetrocyclic bases phenalthroline and bipyridine. Thiocyanate, azide and perchlorate ions act as coligands. Elemental analysis suggests +3 state for Cobalt. HNMR, IR and UV-visible spectra characterize the complexes.

Role of the cytoplasmic domain in Anabaena sensory rhodopsin photocycling: vectoriality of Schiff base deprotonation.

Light-induced electric signals in intact E. coli cells generated by heterologously expressed full-length and C-terminally truncated versions of Anabaena sensory rhodopsin (ASR) demonstrate that the charge movements within the membrane-embedded part of the molecule are stringently controlled by the cytoplasmic domain. In particular, truncation inverts the direction of proton movement during Schiff base deprotonation from outward to cytoplasmic. Truncation also alters faster charge movements that occur before Schiff base deprotonation. Asp(217) as previously shown by FTIR serves as a proton acceptor in the truncated ASR but not in the full-length version, and its mutation to Asn restores the natural outward direction of proton movement. Introduction of a potential negative charge (Ser(86) to Asp) on the cytoplasmic side favors a cytoplasmic direction of proton release from the Schiff base. In contrast, mutation of the counterion Asp(75) to Glu reverses the photocurrent to the outward direction in the truncated pigment, and in both truncated and full-length versions accelerates Schiff base deprotonation more than 10-fold. The communication between the cytoplasmic domain and the membrane-embedded photoactive site of ASR demonstrated here is likely to derive from the receptor's use of a cytoplasmic protein for signal transduction, as has been suggested previously from binding studies.

Hydrocarbon analyses of submarine mud volcanoes (MV) in the Kumano forearc basin

Twelve submarine mud volcanoes (MV) in the Kumano forearc basin within the Nankai Trough subduction zone were investigated for hydrocarbon origins and fluid dynamics. Gas hydrates diagnostic for methane concentrations exceeding solubilities were recovered from MVs 2, 4, 5, and 10. Molecular ratios (C1/C2<250) and stable carbon isotopic compositions (d13C-CH4 >-40 per mil V-PDB) indicate that hydrate-bound hydrocarbons (HCs) at MVs 2, 4, and 10 are derived from thermal cracking of organic matter. Considering thermal gradients at the nearby IODP Sites C0009 and C0002, the likely formation depth of such HCs ranges between 2300 and 4300 m below seafloor (mbsf). With respect to basin sediment thickness and the minimum distance to the top of the plate boundary thrust we propose that the majority of HCs fueling the MVs is derived from sediments of the Cretaceous to Tertiary Shimanto belt below Pliocene/Pleistocene to recent basin sediments. Considering their sizes and appearances hydrates are suggested to be relicts of higher MV activity in the past, although the sporadic presence of vesicomyid clams at MV 2 showed that fluid migration is sufficient to nourish chemosynthesis-based organisms in places. Distributions of dissolved methane at MVs 3, 4, 5, and 8 pointed at fluid supply through one or few MV conduits and effective methane oxidation in the immediate subsurface. The aged nature of the hydrates suggests that the major portion of methane immediately below the top of the methane-containing sediment interval is fueled by current hydrate dissolution rather than active migration from greater depth.

Synthetic studies on optically active Schiff-base ligands derived from condensation of 2-hydroxyacetophenone and chiral diamines

Three optically active Schiff-base ligands have been prepared by condensation of 2-hydroxyacetophenone with (IR,2R)-(-)-1,2-diaminocyclohexane, (1S,2S)-(-)1,2-diphenylethylenediamine or R-(+)-2,2'-diamino-1,1'-binaphthalene, respectively. The products have been characterized by their IR, H-1- and C-13-NMR spectra.

Synthesis, crystal structures and magnetic properties of two bis(μ-phenoxido)dicopper(II) complexes derived from reduced Schiff base ligands

Two phenoxido bridged dinuclear Cu(II) complexes, [Cu-2(L-1)(2)(NCNCN)(2)] (1) and [Cu-2(L-2)(2)(NCNCN)(2)]center dot 2H(2)O (2) have been synthesized using the tridentate reduced Schiff-base ligands 2-[1-(2-dimethylamino-ethylamino)-ethyl]-phenol (HL1) and 2-[1-(3-methylamino-propylamino)-ethyl]-phenol (HL2), respectively. The complexes have been characterized by X-ray structural analyses and variable-temperature magnetic susceptibility measurements. Both the complexes present a diphenoxido bridging Cu2O2 core. The geometries around metal atoms are intermediate between trigonal bipyramid and square pyramid with the Addison parameters (tau) = 0.57 and 0.49 for 1 and 2, respectively. Within the core the Cu-O-Cu angles are 99.15 degrees and 103.51 degrees and average Cu-O bond distances are 2.036 and 1.978 angstrom for compounds 1 and 2, respectively. These differences have marked effect on the magnetic properties of two compounds. Although both are antiferromagnetically coupled, the coupling constants (J = -184.3 and -478.4 cm (1) for 1 and 2, respectively) differ appreciably.

Two novel bis-azomethines derived from quinoxaline-2-carbaldehyde

The Schiff base compounds N,N0-bis[(E)-quinoxalin-2-ylmethylidene] propane-1,3-diamine, C21H18N6, (I), and N,N0-bis[(E)- quinoxalin-2-ylmethylidene]butane-1,4-diamine, C22H20N6, (II), crystallize in the monoclinic crystal system. These molecules have crystallographically imposed symmetry. Compound (I) is located on a crystallographic twofold axis and (II) is located on an inversion centre. The molecular conformations of these crystal structures are stabilized by aromatic pye stacking interactions.

Synthesis, crystal structures, magnetic properties and catecholase activity of double phenoxido-bridged penta-coordinated dinuclear nickel(II) complexes derived from reduced Schiff-base ligands: mechanistic inference of catecholase activity

Three double phenoxido-bridged dinuclear nickel(II) complexes, namely [Ni-2(L-1)(2)(NCS)(2)] (1), [Ni-2(L-2)(2)(NCS)(2)] (2), and [Ni-2(L-3)(2)(NCS)(2)] (3) have been synthesized using the reduced tridentate Schiff-base ligands 2-[1-(3-methylamino-propylamino)-ethyl]-phenol (HL1), 2-[1-(2-dimethylamino-ethylamino)-ethyl]-phenol (HL2), and 2-[1-(3-dimethylarnino-propylamino)-ethyl]-phenol (HL3), respectively. The coordination compounds have been characterized by X-ray structural analyses, magnetic-susceptibility measurements, and various spectroscopic methods. In all complexes, the nickel(II) ions are penta-coordinated in a square-pyramidal environment, which is severely distorted in the case of 1 (Addison parameter tau = 0.47) and 3 (tau = 0.29), while it is almost perfect for 2 (tau = 0.03). This arrangement leads to relatively strong antiferromagnetic interactions between the Ni(II) (S = 1) metal centers as mediated by double phenoxido bridges (with J values of -23.32 (1), -35.45 (2), and -34.02 (3) cm(3) K mol(-1), in the convention H = -2JS(1)S(2)). The catalytic activity of these Ni compounds has been investigated for the aerial oxidation of 3,5-di-tert-butylcatechol. Kinetic data analysis following Michaelis-Menten treatment reveals that the catecholase activity of the complexes is influenced by the flexibility of the ligand and also by the geometry around the metal ion. Electrospray ionization mass spectroscopy (ESI-MS) studies (in the positive mode) have been performed for all the coordination compounds in the presence of 3,5-DTBC to characterize potential complex-substrate intermediates. The mass-spectrometry data, corroborated by electron paramagnetic resonance (EPR) measurements, suggest that the metal centers are involved in the catecholase activity exhibited by the complexes.