Zn-doping effect on the energy barrier to magnetization reversal in superparamagnetic nickel ferrite nanoparticles

Measurements of ac-susceptibility and dc-magnetization were carried out on samples of Ni_1-xZn_xFe₂O₄ nanoparticles (x=0, 0.25, 0.5, 0.75) with average diameters 〈D〉≈7 nm. Values of the superparamagnetic blocking temperature T̄_B were obtained from the characteristic temperature behavior of the imaginary susceptibility χ_imag. An Arrhenius-type law, which accurately describes the relationship between the observation time τ_obs and the blocking temperature, was used to determine the effective energy barrier to magnetization reversal U_eff. A Zn-content dependence of the energy barrier is observed, where U_eff changes little for 0≤x≤0.25, it peaks at x=0.5, and decreases back upon further Zn-doping. The large increase of U_eff at x=0.5 is attributed to an enhanced magnetic anisotropy induced by the crossover between two spatial arrangements of spins in the A and B sub-lattices of the ferrimagnetic inverse spinel. PACS 75.50.Bb; 75.50.Gg; 75.30.Et     

Physicochemical and structural properties of bacteriostatic sulfonamides: Theoretical study

A theoretical study at the Hartree–Fock and density functional theory levels is performed on sulfonamide‐type bacteriostatic compounds with the aim to provide an insight into their structure–activity relationship. The basicity of the p‐amino group is analyzed by means of the proton affinities and the protonation energies, showing that molecules presenting bacteriostatic activity are less basic, i.e., they are characterized by larger protonation energies and smaller proton affinities. The acidity of the amide group is analyzed through the deprotonation energy. The results reveal that the more acidic molecules present a larger bacteriostatic activity. This result is also confirmed from a study of bond orders. A bond order analysis of the amide group suggests that the electron attracting group in these molecules is responsible for the increase in acidity. The charge of the SO₂ group is also shown to be affected by the presence of the electron attracting group and consequently related to the acidity of the molecules. A geometric analysis shows that structures in which the amino group is more coplanar with respect to the benzenic ring possess larger bacteriostatic activity. A conformational analysis of these molecules illustrates that active molecules have relatively larger torsion energy barriers. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem 94: 165–172, 2003     

A mew method of synthesis of 1,2,3,4-telrahydro-5H-5-oxo-1,4-benzodiazepines

A new one-step facile method for the synthesis of 1,12,3,4-tetrahydro5H-5-oxo-1,4-benzo-diuzepines is described. The method involves the addition of methyl anlhranilates to elhyl-enimine followed by intramolecular cyclizalion of the resulting intermediate compounds. Another attempted method starting from β-anilinoethylisocyanales is also described.     

Analogs of propranolol. Synthesis of 3-alkylamino-1-(3-benzo[b]thienyloxy)-2-propanols

The synthesis by two alternative routes of 1-(3-benzo[b]thienyloxy)-3-isopropylamino-2-propanol hydrochloride ( 1a HCl), a thiophenic isoster of Propranolol, and related compounds, is reported. The protecting and enolizing properties of the 2-methoxycarbonyl group on benzo[b]thiophene-3-one, along with its facile removal, are utilized in the first route. In the second one, conversion of 3-bromobenzo[b]thiophene in 1-(3-benzo[b]thienyloxy)-2,3-o-isopropylidenepropane is the key step. On the other hand, hydrolysis of 1-(3-benzo[b]furanyloxy)-2,3-o-isopropylidenepropane to the corresponding diol, in order to obtain a furanic isoster of Propranolol (17a ), was unsuccessful.     

Binuclear Cu2+ complex mediated discrimination between L-glutamate and L-aspartate in water

L-glutamate and L-aspartate selectivity is achieved by the action of two Cu2+ metal ions rightly disposed in a cyclophane-type macrocyclic framework; electrochemical sensing of glutamate has been achieved by adsorption of the copper complexes on graphite electrodes.     

Synthesis of 10-(4-methyl-1-piperazinyl)thieno[3,2-b][1,5]benzoxazepines

A series of the title compounds has been synthesized starting from methyl 3-hydroxythiophene-2-carboxylate. Its condensation with 2,4-dinitrochlorobenzene provides through compound 4e a way to introduce 7-substituents by means of diazonium salts reactions.     

E- and Z-isomerism of 2-acetylthiophene oximes

A study on the oximation of a number of 2-acetylthiophenes in order to ascertain the validity of contradictory results previously described is reported. The fact that the steric hindrance is smaller in 2-acetylthiophenes unsubstituted at position-3 than in acetylbenzenes allows in these cases the formation of Z oximes, which even can predominate on the E oximes in the case of a + M substitution at position-5. In the paper is also shown that the E/Z ratio of 2-acetylthiophene oximes can be deduced from the ¹H-nmr spectrum of the crude oxime mixture.     

The importance of nonconventional structures in the binding of Ni<Superscript>+</Superscript> to ethynylsilanes and ethynylgermanes

The influence of the nature of the heteroatom on the Ni⁺ gas-phase binding energies of HCC–XH₃ (X is C, Si, or Ge) compounds has been investigated through the use of high-level density functional theory methods. The structures of the corresponding Ni⁺ complexes were optimized at the B3LYP/6-311G(d,p) level of theory. Final energies were obtained in single-point B3LYP/6-311+G(2df,2p) calculations. Nonconventional complexes, in which the metal cation interacts simultaneously with the CC system and with one of the X–H bonds of the substituent XH₃ group, play a significant role in the binding of Ni⁺ to HCC–XH₃ (X is Si or Ge) derivatives. Conversely, such nonconventional complexes are not local minima of the propyne–Ni⁺ potential-energy surface. This establishes a clear distinction between unsaturated carbon derivatives and the Si- and Ge-containing analogues as far as bonding to transition-metal monocations is concerned. Actually, the attachment of Ni⁺ to HCC–XH₃ (X is Si or Ge) compounds in the gas phase yields a mixture of conventional and nonconventional complexes. These agostic-type interactions can be viewed as a dative bond from the X–H bonding orbital toward the empty s orbital of the metal, and a back-donation from the valence electron pairs of the metal into the X–H antibonding orbital of the neutral species.Proceedings of the 11th International Congress of Quantum Chemistry satellite meeting in honor of Jean-Louis Rivail     

Mass spectra of heterocyclic compounds. II-Hexahydro-1,3,5,-triazines

The twelve tri-N-sulphonylhexahydro-1,3,5-triazines (R = alkyl or aryl) exhibit a common fragmentation pattern; most of the fragments are directly or indirectly generated from the [M ? RSO₂]⁺ ion. Tri-N-Benzylsulphonylhexahydro-1,3,5-triazine (R = PhCH₂) departs from the others mainly because the key ion [M ? RSO₂]⁺ suffers a skeletal rearrangement with loss of SO₂. The rationalizations presented are supported by metastable evidence, accurate mass measurements and deuterium labelling.     

Synthesis of 2-carboxy-4-methylazetidine. A novel isomeric analog of dl-proline

L-Azetidine-2-carboxylic acid is a naturally occurring azetidine currently used in the synthesis of abnormally high molecular weight polypeptides. The synthesis of 2-carboxy-4-methylazetidine is now reported which is a novel isomeric analog of dl -proline. Reaction of α,β-dibromo carbonyl ester with three molar equivalents of benzylamine yields 1-benzyl-2-carbomethoxy-4-methyl-azetidine. Hydrolysis of the latter compound with barium hydroxide yields 1-benzyl-2-carboxyl-4-methylazetidine which, if subjected to catalytic hydrogenation., yields the title compound in practical yield. The cis configuration is tentatively assigned to the title compound on the basis of previously published arguments.