Synthesis, crystal structures and protease activity of amino acid Schiff base iron(III) complexes

Iron(III) complexes, (NHEt3)[Fe(III)(sal-met)(2)] and (NHEt3)[Fe(III)(sal-phe)(2)], of amino acid Schiffbase ligands, viz., N-salicylidene-L-methionine and N-salicylidene L-phenylalanine, have been prepared and their binding to bovine serum albumin (BSA) and photo-induced BSA cleavage activity have been investigated. The complexes are structurally characterized by single crystal X-ray crystallography. The crystal Structures of the discrete mononuclear rnonoanionic complexes show FeN2O4 octahedral coordination geometry in which the tridentate dianionic amino acid Schiff base ligand binds through phenolate and carboxylate oxygen and imine nitrogen atoms. The imine nitrogen atoms are trans to each other. The Fe-O and Fe-N bond distances range between 1.9 and 2.1 angstrom. The sal-met complex has two pendant thiomethyl groups. The high-spin iron(III) complexes (mu(eff) similar to 5.9 mu(B)) exhibit quasi-reversible Fe(III)/Fe(II) redox process near -0.6 V vs. SCE in water. These complexes display a visible electronic hand near 480 nm in tris-HCl buffer assignable to the phenolate-to-iron(III) charge transfer transition. The water soluble complexes bind to BSA giving binding constant values of similar to 10(5) M-1. The Complexes show non-specific oxidative cleavage of BSA protein on photo-irradiation with UV-A light of 365 nm.

Formative time lags in nitrogen, oxygen and dry air In crossed electric and magnetic fields

Formative time lags in nitrogen, oxygen, and dry air are measured with and without a magnetic field over a range of gas pressures (0.05 ' p ' 20.2 torr 5 kPa to 2 MPa, electric field strengths (1.8xO14 EEs 60xlO V m l) and magnetic field strengths (85xl0-4 < B ' 16x10-2 Tesla). For experiments below the Paschen minimum, the electrodes are designed to ensure that breakdown occurs over longer gaps and for experiments above the Paschen minimum, a coaxial cylindrical system is employed. The experimental technique consists of applying pulse voltages to the gap at various constant values of E/p and B/p and measuring the time lags from which the formative time lags are separated. In the gases studed, formative time lags decrease on application of a magnetic field at a given pressure for conditions below the Paschen minimum. The voltages at which the formative time lags remain the same without and with magnetic fields are determined, and electron molecule collision frequencies (v/p) are determined using the Effective Reduced Electric Field [EREF] concept. With increasing ratio of E/p in crossed fields, v/p decreases in all the three gases. Measurements above the Paschen minimum yield formative time lags which increase on application of a magnetic field. Formative time lags in nitrogen in ExB fields are calculated assuming an average collision frequency of 8.5x109 sec-1 torr 1. It is concluded that the EREF concept can be applied to explain formative time lags in ExB fields.

The O-H Raman Frequency in Inorganic Acids

The band characteristic of the OH group has been recorded in the Raman spectra of many hydroxides and alcohols. It has not so far been observed, however, in the case of the stronger acids. Using the improved technique of complementary filters recently developed by Ananthakrishnan1, and giving long exposures varying from six to twelve days, I have succeeded in obtaining spectra with sulphuric acid and crystals of iodic, selenious and telluric acids, in which the band is clearly seen in the 4046 A. excitation. Table 1 gives the frequency shifts. The value for boric acid is taken from Ananthakrishnan's paper2.

Synthesis and structure of mixed ligand isonitroso-β-ketoiminenickel(II) complexes. Crystal structure of (1-ethoxycarbonyl-2-npropylimino-1-propanoneoximato) (1-methoxycarbonyl-2-imino-1-propanoneoximato)nickel(II)

Mixed ligand complexes of the type Ni(R-AB)(AC') and Ni(R-AC)(AB') where AB/AC denote N-bonded isonitroso- [3-ketoimino ligands, AB'/AC' denote the corresponding Obonded ligands and R = Me, Et, n-Pr are synthesised and characterised. The complexes are neutral with square planar geometry around nickel(II). The bonding isomerism of the isonitroso group is discussed on the basis of i.r. and 1H n.m.r. studies. The crystal structure of the title complex, Ni(n-Pr-IEAI)(IMAI') has been determined from diffractometer data by Patterson and Fourier methods and refined by least squares to R = 0.088 for 2209 observed reflections. Unit cell constants are: a = 11.945(2), b = 22.436(7), c = 13.248(5) ~, [3 = 95.13(2) ~ The space group is P2Jc with Z = 8. Niekel(II) has a square planar coordination of two imine nitrogens, an isonitroso-nitrogen (from n-Pr-IEAI) and another isonitrosooxygen (from IMAI').

Reactivity of Cationic Terminal Borylene Complexes: Novel Mechanisms for Insertion and Metathesis Chemistry Involving Strongly Lewis Acidic Ligand Systems

The reactions of terminal borylene complexes of the type [CpFe(CO)(2)(BNR2)](+) (R = `Pr, Cy) with heteroallenes have been investigated by quantum-chemical methods, in an attempt to explain the experimentally observed product distributions. Reaction with dicyclohexylcarbodiimide (CyNCNCy) gives a bis-insertion product, in which 1 equiv of carbodiimide is assimilated into each of the Fe=B and B=N double bonds to form a spirocyclic boronium system. In contrast, isocyanates (R'NCO, R' = Ph, 2,6-wXy1, CY; XYl = C6H3Me2) react to give isonitrile complexes of the type [CpFe(CO)(2)(CNR')]+, via a net oxygen abstraction (or formal metathesis) process. Both carbodiimide and socyanate substrates are shown to prefer initial attack at the Fe=B bond rather than the B=N bond of the borylene complex. Further mechanistic studies reveal that the carbodiimide reaction ultimately leads to the bis-insertion compounds [CpFe(CO)(2)C(NCy)(2)B(NCY)(2)CNR2](+), rather than to the isonitrile system [CpFe(CO)(2)(CNCy)](+), on the basis of both thermodynamic (product stability) and kinetic considerations (barrier heights). The mechanism of the initial carbodiimide insertion process is unusual in that it involves coordination of the substrate at the (borylene) ligand followed by migration of the metal fragment, rather than a more conventional process: i.e., coordination of the unsaturated substrate at the metal followed by ligand migration. In the case of isocyanate substrates, metathesis products are competitive with those from the insertion pathway. Direct, single-step metathesis reactivity to give products containing a coordinated isonitrile ligand (i.e. [CpFe(CO)(2)(CNR')](+)) is facile if initial coordination of the isocyanate at boron occurs via the oxygen donor (which is kinetically favored); insertion chemistry is feasible when the isocyanate attacks initially via the nitrogen atom. However, even in the latter case, further reaction of the monoinsertion product so formed with excess isocyanate offers a number of facile (low energetic barrier) routes which also generate ['CpFe(CO)(2)(CNR')](+), rather than the bis-insertion product [CpFe(CO)(2)C(NR')(O)B(NR')(O)CNR2](+) (i.e., the direct analogue of the observed products in the carbodiimide reaction).

Adducts of Silicon Tetrafluoride with Aminocyclophosphazenes : Synthesis and Characterization

Stable solid adducts of SiF4 with the following aminocyclophosphazenes have been synthesized : N3P3(NHCH2CH2NH)(NMe2)4(,1 ) ; N3P3(NHCH2CH2NH)C14(,2 ) ; N3P3(NMe2)4C12(,3 ) ; N3P3(NHMe),,(4) ; N3P3(NMe2),, (5) ; N,P,(NHMe),, (6) ; N4P4(NMe2),, (7) ; and N,P,(NHBu'),, (8). They have been characterized by elemental analysis, i.r., and n.m.r. ( H, 31 P, and 19F) spectroscopy. The composition of the adducts varies depending on the ring size and also on the nature of the substituents on the phosphorus. The number of SiF4 molecules accommodated by the ligands is larger when the ring size is large, while it is less when the ligands contain chlorine. Except in the cases of ligands (1) and (2), bonding is through the ring nitrogens. With (I), both exocyclic nitrogen and ring nitrogen atoms, and with (2) only exocyclic nitrogen atoms, participate in co-ordination. In these two cases the silicon is six-co-ordinated, while in the other cases it is five-co-ordinated.

Studies of phosphazenes. Part 14. The tautomerism of oxocyclotriphosphazadienes

The tautomeric behaviour of monohydroxycyclotriphosphazatrienes has been investigated by 31P n.m.r. spectroscopy. These derivatives exist as oxocyclotriphosphazadiene tautomers in which the hydrogen atom is attached to a ring nitrogen atom to the phosphoryl group. Three types of prototropic behaviour are observed : (a) no exchange is detected and only one tautomer is present [e.g. N3HP3(NHBut)2R3O (R = OMe or OEt)]; (b) exchange takes place between two equivalent sites and only one tautomer is observed [e.g. N3HP3R5O (R = OMe or OPh); N3HP3Ph4RO (R = OMe or OEt)]; and (c) exchange occurs between two non-equivalent sites and two tautomers are present [e.g. N3HP3Ph2R3O (R = OMe, OEt, or OPrn)]. It is shown that basicity calculations using substituent constants have predictive value since they are in good agreement with the spectroscopic observations.

ESR studies of non-silicate inorganic glasses through their glass transformation ranges

ESR spectra of three inorganic glasses doped with Mn2+ and Fe3+ have been studied through their glass transition temperatures (Tg). Spectral features in each case have been discussed with reference to site symmetries. The intensity of the ESR signal has been bound to decrease in the region of Tg. An attempt has been made to explain this interesting feature on the basis of a two-state model.

A combined XPS-UPS-EELS study of nitrogen adsorbed on clean and barium-promoted iron surfaces: The nature of the precursor to dissociation

For N2 on a clean Fe surface, the adsorbed precursor in a parallel orientation becomes predominant around 110 K, while at lower temperatures it coexists with a weakly adsorbed species. On a Ba-promoted Fe surface, however, N2 is present exclusively in the precursor state in the temperature range 80–150 K following moderate exposure. Besides exhibiting a low N-N stretching frequency of 1530 cm−1, the precursor shows a clear separation between the 5σ and 1π levels in the UPS; the precursor dissociates to give a nitridic species around 160 K.

Complexes of lanthanide nitrates with 2-N-(6-picoIyl)-benzamide

New complexes of lanthanide nitrates with 2-N-(6-picolyl)-benzamide of the formulae Ln2[6-pic-BA], [NO3l6 (Ln = Y and La-Yb) have been prepared and characterised by chemical analysis, infrared, molar conductance and electronic spectral data. Molar conductance data along with IR data point to the presence of co-ordinated nitrate groups. IR spectra prove the bidentate co-ordination of the ligand to the metal ion, through the oxygen of the secondary amide and the nitrogen of the heterocyclic ring. Electronic spectral studies in the visible region suggest an eight co-ordinate geometry around the metal ions.

Nanostructured Peptide Fibrils Formed at the Organic-Aqueous Interface and Their Use as Templates To Prepare Inorganic Nanostructures

Formation of fibril-type nanostructures of the Alzheimer's beta-amyloid diphenylalanine (L-Phe-L-Phe, FF) at the organic-aqueous interface and the factors affecting their structures have been investigated. Such nanostructures are also formed by bovine serum albumin and bovine pancreas insulin. The concentration of the precursor taken in the aqueous layer plays an important role in determining the morphology of the nanostructures, The addition of curcumin to the organic layer changes the structure of the self-assembled one-dimensional aggregates of diphenylalanine. By coating the diphenylalanine dipeptide fibrils with appropriate precursors followed by calcination in air, it has been possible to obtain one-dimensional nanostructures of inorganic materials.

Complexes of lanthanide perchlorates with 2-N-(pyridyl)benzamide

New complexes of lanthanide perchlorates with 2-N-(pyridyl) benzamide (PyBA) of the type Ln(PyBA)3(ClO4)3 where Ln = Y and La---Yb have been synthesised and characterised by analyses, conductance, IR, 13C NMR (for diamagnetic complexes only) and electronic spectra. The molar conductance and IR data point to the ionic nature of the perchlorate groups in the complexes. IR data along with the 13C NMR data unequivocally proves that the coordination of the ligand to the metal ions taken place in a bidentate fashion through the oxygen of the benzamide group and the nitrogen of the heterocyclic ring. From a comparison of the visible electronic spectral shapes of the Nd3+, Ho3+ and Er3+ complexes with those reported in the literature, a 6-coordinate geometry around the metal ion has been assigned in all the complexes.

Coordinative interaction of morpholine with divalent metallo tetraphenyl porphyrins

The formation of axially coordinated morpholine (morph) complexes of MTPP, (M = Co, Ni, Cu and Zn) has been studied. Morpholine coordinates through imino nitrogen to the metal ions with the retainment of equatorial conformation. The presence of spin-free, NiTPP (morph), (S = 1) and an equilibrium mixture of CoTPP and an oxygen adduct of CoTPP (morph) in solution have been observed.

Complexes of Lanthanide Perchlorates with N-(2-Pyrimidyl)benzamide

New complexes of lanthanide perchlorates with N-(2-pyrimidyl)benzamide (BApymH) of the general formulae [Ln(BApymH)4](ClO4)3 (where Ln = La-Yb and Y) have been synthesised and characterised by chemical analysis, molar conductivity and physical methods such as infrared and electronic spectra in the visible region. Molar conductance and infrared data point to the ionic nature of the per-chlorate groups in the complexes. IR data unequivocally proves that the coordination of the ligand to the metal ion takes place in a bidentate fashion through the oxygen of the secondary amide and nitrogen of the pyrimidine ring. From a comparison of the visible electronic spectral shapes of the Nd3+ and Ho3+ complexes with those reported in the literature, an eight coordinate geometry around the metal ion has tentatively been assigned in all the complexes.