Preparation of some nickel(II) and copper(II) complexes of the SCHIFF-Base derived from Acetophenone and Ethylenediamine

Preparation and properties of the following Ni^II and Cu^II complexes of the Schiff base derived from acetophenone and ethylenediamine (BAPE) and also of the mixed Ni^II and Cu^II chelates with BAPE and acetylacetone (acac-H) are described: In each case the Schiff base, BAPE, acts as a neutral bidentate ligand. The complexes are characterised by electronic spectra, magnetic susceptibilities, conductivities and elemental analyses. Pseudotetrahedral structure is proposed for M(BAPE)C1₂, while tetragonal structure for [M(BAPE)(acac)(H₂O)₂]C_lO₄ (M = Ni and Cu). The complex [Ni(BAPE) (acac)]ClO₄ has been found to be square planar.     

Titration curves of p-aminobenzoic acid–formaldehyde polymer in relation to its structure

p-Aminobenzoic acid and formaldehyde were condensed in the presence of acid catalyst. The linear condensation polymer thus obtained was then separated into four fractions by a fractional precipitation method. Conductometric titrations were carried out on these four polymer fractions and the conglomerate in nonaqueous solvents with acid as well as base. The titration curves indicated a large number of additional breaks before the complete neutralization of COOH or NH₂ groups. These observations have been interpreted in terms of degree of polymerization and the structure of the polymer.     

Anwendung der Massenspektrometrie zur Strukturaufklärung von Alkaloiden. 4. Mitt.: Zur Struktur des Rhazidins

Rhazidin kann durch LiAlH₄-Reduktion in Quebrachamin übergeführt werden. Für den basischen Bestandteil des Alkaloides ergibt sich daher Formel V. Umgekehrt ist die Verbindung V durch Oxydation von Quebrachamin mit Peressigsäure in guter Ausbeute zugänglich.

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Maximum-likelihood estimator for dual phase extraction in holographic moire

A maximum-likelihood (ML) method based on spectral estimation theory for the extraction of dual phase distributions in holographic moire in the presence of nonsinusoidal waveforms, noise, and the miscalibration of piezoelectric (PZT) devices is proposed. The extraction of these phases requires incorporating two PZTs into the moire setup. ML estimators are asymptotically efficient for sufficient data samples. The approach presented uses a direct stochastic algorithm called probabilistic global search Lausanne for minimizing the ML function.     

Shape analysis based critical Eotvos numbers for buoyancy induced partial detachment of oil drops from hydrophilic surfaces

Removal of oil drops from solid surfaces immersed in an aqueous medium is of interest in many applications. It has been shown that drop shape analysis can be used to predict conditions at which the stability limit of a lighter than water oil drop on a solid surface immersed in an aqueous bath is reached (Adv. Colloid Interface Sci. 98 (2002) 265). However the above analysis is restricted to cases where the contact angle made by the drop is below 90degrees and when the surface conditions result in a 'pinned' contact line. In this paper, it is shown that drop shape analysis can be used to predict the critical conditions at which drop stability limit is reached for drop contact angles of 90degrees and above, which is encountered with 'hydrophilic' surfaces. This critical condition can predict the occurrence of partial oil drop detachment, before complete removal due to 'roll-up', which occurs when the hydrophilic surface is adequately smooth which prevents 'pinning' of the contact line. The critical conditions at which partial drop detachment occurs can also be approximately predicted from simple force balances. It has been shown (Adv. Colloid Interface Sci. 98 (2002) 265) that for contact angles less than 90degrees, the critical limit based on shape analysis appears to resolve the differences that arise due to alternate expressions for capillary retention force. This paper shows that even for contact angles above 90degrees, the critical conditions predicted from the shape analysis resolves the differences in the predictions from the alternate force balances. Drop shape analysis used in this paper is based on the 'Arc-length' form of Young-Laplace or 'drop shape' equation, which is different from the 'Y vs X' form of the above equation that is used in Adv. Colloid Interface Sci. 98 (2002) 265. The above drop shape equation is solved by a fourth order Runge-Kutta technique and it is shown that for angles less than 90degrees, the two forms of the drop shape equation, predict almost identical values of the critical Eotvos number. This paper highlights the competing effects of interfacial tension lowering induced drop instability and 'roll-up', a term that is used to describe the retraction of the contact line of an oil drop on a surface, in being the primary c ause for drop detachment.     

Ionic Assembly,Anion–π, Magnetic,and Electronic Attributes of Ambient Stable Naphthalenediimide Radical Ions

Organic spin-based molecular materials are considered to be attractive for the generation of functional materials with emergent optoelectronic, magnetic, or magneto-conductive properties. However, the major limitations to the utilization of organic spin-based systems are their high reactivity, instability, and propensity for dimerization. Herein, we report the synthesis, characterization, and magnetic and electronic studies of three ambient stable radical ions ( 1 a^.+ , 1 b^.+ , and 1 c^.+ ). The radical ions 1 b^.+ and 1 c^.+ with BPh₄⁻ and BF₄⁻ counter anions, respectively, were synthesized in excellent yields by means of anion metathesis of 1 a^.+ with Br⁻ as its counter anion. Notably, synthesis of 1 a^.+ was achieved in an ecofriendly, solvent-free protocol. The radical ions were characterized by means of single-crystal X-ray diffraction studies, which revealed the discrete nature of the radical ions and extensive hydrogen-bonding interactions within the radical ions and with the counter anions. Thus, radical ions can be organized to form infinite supramolecular arrays using weak noncovalent interactions. In addition, the Br⁻, BF₄⁻, and BPh₄⁻ anions formed diverse types of anion–π interactions with the naphthalene and imide rings of the radical ions. The radical ions were characterized by means of X-band electron paramagnetic resonance (EPR) spectroscopy in solution and in the solid state. Magnetic studies revealed their paramagnetic nature in the range of 10 to 300 K. The radical ions exhibited high resistivity approaching the gigaohm (GΩ) scale. In addition, the radical ions exhibited panchromism.     

H2-release from alcohols,diols, and compounds with amino functionality promoted by titanium(II) sandwich complex, [Cp2Ti]: a theoretical approach

Structural Chemistry - The role of Ti(II) sandwich complex, [Cp2Ti], generated by the combination of [Cp2TiCl2] and two equivalents of nBuLi, in situ, in toluene has been investigated theoretically...     

Investigation of folding patterns in homo-oligomers of (R)-β2,2-amino acids with carbohydrate side chain

The study describes the synthesis of new β^2,2-peptides made from geminally disubstituted β^2,2-amino acid and their folding propensities. The (R)-C-linked carbo-β^2,2-amino acid [(R)-β^2,2-Caa] was prepared from d-glucose and converted into the homo-oligomeric di-, tetra-, and hexapeptides. The conformational studies were carried out using NMR (in CDCl₃), CD, IR, and MD calculations. These β^2,2-peptides were interestingly stabilized by five-membered (mr) inter-residue H-bonds NH(i)?O(i-1) (furanoside) and a 6-mr intra-residue H-bond between amide proton (NH(i)) and the oxygen of –OMe(i) at the C3 carbon of the carbohydrate side chain. These results amply demonstrate that the ‘epimerization’ at the spiro carbon center has an effect on the conformational behavior of these peptides. Finding of these, H-bonding patterns, which are not so common to stabilize the folds in this class of β^2,2-Caa derived peptides would further facilitate augmentation in the domain of foldamer.