Annealing effects on the magnetization of Co–Ni–B amorphous nanoparticles

Chemically prepared (Co_xNi_1−x)_1−yB_y (x=0.5, 0.75, 1; y≈0.4) amorphous fine particles were characterized by X-ray diffraction, DTA and TGA, and in situ magnetic measurement as a function of annealing temperature in an inert atmosphere. Magnetic measurement performed in as-prepared and 150°C annealed samples shows an increase of the saturation magnetization and magnetic moment after thermal treatment. Room temperature magnetization increases by factors of 3.5, 1.8, and 1.5, for x=0.5, 0.75, and 1, respectively. These measurements may indicate a local re-ordering of the amorphous phase at temperatures much lower than the full crystallization temperature.     

Infrared and Raman spectroscopic investigation of Eu3+-doped mono and Di-urethanesil hybrid siliceous materials

The general features of two series of sol-gel derived materials, designatedurethanesils (Ut), have been investigated by infrared and Raman spectroscopies with the goal of elucidating the chemical environment of the Eu³⁺ cations. The host frameworks of the two families of ormolytes studied have been represented by m-Ut(350) and d-Ut(300), where m stands for mono, d stands for di, 350 and 300 are the average molecular weights of the organic precursors (poly(ethylene glycol) methyl ether, PEGME, and poly(ethylene glycol), PEG, respectively). The hybrid matrix of the mono-xerogels is composed by a siliceous backbone bonded by means of urethane linkages (-NHC (=O)O-) to pendant methyl end capped oligopolymer chains with approximately 7 oxyethylene units, whereas that of the di-xerogels is based on a siliceous network grafted through urethane groups to both ends of poly(oxyethylene) segments containing about 6 (OCH₂CH₂) repeat units. Both classes of materials have been doped with europium triflate (Eu(CF₃SO₃)₃). The doped samples have been identified by m-Ut(350)_nEu(CF₃SO₃)₃ and d-Ut(300)_nEu(CF₃SO₃), where n is the molar ratio of (OCH₂CH₂) repeat units per Eu³⁺ ion. Materials with n ranging from ∞ to 5 have been analyzed. The spectral data obtained provide evidence that the cations begin to coordinate to the ether oxygen atoms of the oligopolymer chains at n=40 in the mono-urethanesils and at n=10 in the di-urethanesils. In mono-urethanesils samples with n>40 and in di-urethanesils materials with n>10, the Eu³⁺ coordinate exclusively to the carbonyl oxygen atoms of the urethane linkages. Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16–22, 2001.     

Paraxial designing of planar waveguide variable-index focusing elements: Part 2—lenses of elliptical symmetry

A paraxial ray-optics formalism proposed for designing radially symmetric variable-index lenses is extended to the case of lenses of elliptical symmetry of the index profile.     

Effect of the environment on the stability of surfactant–polypeptide self‐assembled complexes: Molecular dynamics simulations of stoichiometric complexes formed by N‐dodecyltrimethylammonium and poly(α,L‐glutamate) in chloroform,methanol, and water

A series of molecular dynamics simulations have been performed to study the supramolecular structure of self‐assembled complexes formed by N‐dodecyltrimethylammonium cations and the synthetic polypeptide poly(α,L ‐glutamate). The influence of the type of solvent has been investigated, considering explicit environments of chloroform, water, and methanol on a stoichiometric complex containing 15 residues. In chloroform, the complex stabilizes in a regular structure: the polypeptide adopts an α‐helix conformation that is regularly surrounded by surfactant molecules to form electrostatic interactions through a multiple interaction pattern. However, this structure destabilizes in methanol and water: (a) the α‐helix unfolds in the two solvents and (b) the electrostatic links between the surfactant molecules and the polyanion are disrupted in aqueous solution, although these interactions are still preserved in methanol. The role of the solvent environment in stabilizing or destabilizing the polypeptide secondary structure, the organization of the surfactant molecules, and predominantly the surfactant–polypeptide supramolecular organization is discussed in detail. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1122–1133, 2006     

Proper holomorphic maps between Reinhardt domains and strictly pseudoconvex domains

LetR be a Reinhardt domain andD a bounded simply connected strictly pseudoconvex domain withC ^∞ boundary. We prove that any proper holomorphic mapF:R →D is, up to biholomorphism ofD, of the form \((z_1^{d_1 } , z_2^{d_2 } , \ldots , z_n^{d_n } )\) withd ₁,d ₂,…,d _n ∈ IN.     

Development and critical comparison of greener flow procedures for nitrite determination in natural waters

Two greener procedures for flow-injection spectrophotometric determination of nitrite in natural waters were developed and critically compared. Replacement of toxic reagents, waste minimization and treatment were exploited to attend the standards of clean chemistry. The flow system was designed with solenoid micro-pumps in order to minimize reagent consumption and waste generation. The first procedure is based on the Griess diazo-coupling reaction with sulfanilamide and N-(1-naphthyl)ethylenediamine (NED) yielding an azo dye, followed by photodegradation of the low amount of waste generated based on the photo-Fenton reaction. The second procedure is based on the formation of iodine from nitrite and iodide in acid medium in order to avoid the use of toxic reagents. For Griess method, linear response was achieved up to 1.0 mg L^− 1, described by the equation A = − 0.007 + 0.460C (mg L^− 1), r = 0.999. The detection limit was estimated as 8 μg L^− 1 at the 99.7% confidence level and the coefficient of variation was 0.8% (n = 20). The sampling rate was estimated as 108 determinations per hour. The consumption of the most toxic reagent (NED) is reduced 55-fold and 20-fold in comparison to batch method and flow injection with continuous reagent addition, respectively. A colorless residue was obtained by in-line photodegradation with reduction of 87% of the total organic carbon content. The results obtained for natural water samples were in agreement with those achieved by the reference method at the 95% confidence level. For the nitrite–iodide method, linear response was observed up to 2.0 mg L^− 1, described by the equation A = − 0.024 + 0.148C (mg L^− 1), r = 0.999. The detection limit was estimated as 25 μg L^− 1 at the 99.7% confidence level and the coefficient of variation was 0.6% (n = 20). The sampling rate was estimated as 44 determinations per hour. Despite avoiding the use of toxic reagents, the nitrite–iodide method presented worst performance in terms of selectivity and sensitivity.     

DSC study of charge-transfer complexes of polynuclear aromatic hydrocarbons with nitroaromatic acceptors

Charge-transfer, crystalline complexes of 1,3,5-trinitrobenzene (TNB), 2,4,7- trinitro-9-fluorenone (TNF). and 2,4,5,7-tetranitro-9-fluorenone (TENF) with eleven polynuclear aromatic hydrocarbons were compared for thermal stability, ΔH and ΔS of melting. Factors possibly influencing the above parameters are discussed.Melting does not induce separation of the components; these complexes can be repeatedly crystallized and melted without variation of the ΔH of melting, thereby indicating high thermal stability.With a few exceptions, melting temperatures of the complexes increase in the order TNB<TNF<TENF: so do ΔH and ΔS of melting. A number of crystal transitions were observed.     

Tuning the Properties of Copper(II) Complexes with Tetra‐ and Pentadentate Bispidine (=3,7‐Diazabicyclo[3.3.1]nonane) Ligands

The synthesis of a series of tetra‐ and pentadentate bispidine‐type ligands (bispidine=3,7‐diazabicyclo[3.3.1]nonane) – tetradentate ligands are donor‐substituted at C(2) and C(4), pentadentate ligands have an additional donor at N(3) or N(7), with pyridine, 2‐methylpyridine, or quinoline donor moieties – and of their Cu^II complexes are reported, together with single‐crystal structural analyses and solution studies (electrochemistry, electronic and EPR spectroscopy). Depending on the ligand geometry and on the co‐ligands (solvent or counter anion), there are various structural forms (pseudo‐Jahn–Teller elongation along all three molecular axes), and the structural data are correlated with the spectroscopic and electrochemical parameters.     

Vanadyl salen complexes covalently anchored to an imidazolium ion as catalysts for the cyanosilylation of aldehydes in ionic liquids

Two vanadyl salen complexes having peripheral styryl substituents have been reacted with 1-methyl-3-(3-mercaptopropyl)-imidazolium chloride using azoisobutyronitrile as radical initiator. The resulting compounds contain at the same time a vanadyl salen complex and one imidazolium cation. In agreement with the expectations in view of their structure, these compounds were insoluble in conventional organic solvents, but completely miscible in imidazolium ionic liquids. These vanadyl salen complexes bonded to an imidazolium cation are highly active and reusable catalysts for the cyanosilylation of aldehydes. Moderate enantiomeric excesses were obtained using the chiral version of this complex.     

A comparative study of several HPLC methods for determining free amino acid profiles in honey

A study of the viability of three derivatizing reagents for obtaining amino acid profiles in honey through high performance liquid chromatography (HPLC) is presented. A method using diode array detection based on a reaction with diethyl ethoxymethylene malonate (DEMM) and two other methods using fluorescence detection based on derivatization with fluorenylmethyl chloroformate (FMOC-Cl) and 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate (AQC) have been developed. The three methods yield detection limits close to the ppb level, but vary in relation to other analytical characteristics. The use of methyl chloroformate derivatives allows the profile to be obtained with the greatest sensitivity within a short time frame. On applying such methods to honey samples of diverse botanical origin, we observe that the proline values obtained are always lower than those found using the official spectrophotometric method, thereby underlining the advisability of using HPLC methods to reduce uncertainty in these results.