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11.
The results of magnetic resonance studies on ferrimagnetic (GdxY1?x)Co2 compounds, both below and above the Curie points, are presented. The ferrimagnetic resonance measurements show that the effective g values can be described by using the Wangsness relation. The spectroscopic splitting factors of cobalt atoms are not composition dependent. In the paramagnetic range the thermal variation of the linewidth is not linear and the g values are a function of temperature. This behavior is analyzed in correlation with the magnetic data. 相似文献
12.
Cornelia Bohne Adelaide Faljoni-Alario Giuseppe Cilento 《Photochemistry and photobiology》1988,48(3):341-347
Abstract— The interaction of serum albumin-bound acceptors with enzyme-generated and protected triplet species was studied in two types of systems. Chlorophyll-a bound to bovine and human serum albumins is efficiently excited by enzymatically generated triplet acetone and acetaldehyde. When the Chl-a concentration is much lower than that of the albumin the interaction occurs with chlorophyll in an aggregate in which one Chl-a is surrounded by several protein molecules. When the Chl-a concentration is higher than that of the protein, the aggregate contains the proteins and fluorescent chlorophylls in a 1:1 ratio. The excess chlorophylls, although able to interact with the donors, are not fluorescent.
In another study, probes bound to various specific sites of serum albumins were used as quenchers of the enzymatically generated triplet acetone. The efficiency of quenching by all the bound probes is equal and in one case even stronger than for the free probes.
A model for the interaction of the excited species contained in the enzyme with the acceptor(s) located in the protein is proposed.
The present results provide further evidence that enzyme-generated and protected triplet carbonyl species can interact through a collisional process with acceptors bound to or constituents of macromolecules. 相似文献
In another study, probes bound to various specific sites of serum albumins were used as quenchers of the enzymatically generated triplet acetone. The efficiency of quenching by all the bound probes is equal and in one case even stronger than for the free probes.
A model for the interaction of the excited species contained in the enzyme with the acceptor(s) located in the protein is proposed.
The present results provide further evidence that enzyme-generated and protected triplet carbonyl species can interact through a collisional process with acceptors bound to or constituents of macromolecules. 相似文献
13.
Zusammenfassung Es wurden eine Reihe von Substitutionsreaktionen mit entwässertem K3[Cr(NCS)6] und aromatischen Aminen, ohne Verwendung von Lösungsmitteln, durchgeführt. Es wurde beobachtet, da die sehr schwachen Basen mit pK-Werten 14–16, wie die isomeren Mono- und Dinitro-aniline, die Anthranil- und Sulfanilsäuren, für diese Substitutionsreaktionen ungeeignet sind. Die Alkyl-anilinderivate, wie daso-, m- undp-Toluidin (pK=10–11) bilden dagegen leicht reineckesalzähnliche Verbindungen: Amin· H[Cr(Toluidin)2(NCS)4]. Die Zusammensetzung der neuen Komplexanionen wurde bei einer Reihe von doppelten Umsetzungsreaktionen mit den Chlorhydraten einiger heterocyclischen Aminen festgestellt.Für die Klärung einiger Strukturfragen wurden spektrophotometrische Untersuchungen im UV und IR durchgeführt und die thermische Stabilität bzw. der Mechanismus des Pyrolysenvorganges auf thermogravimetrischem Wege verfolgt.
Mit 8 Abbildungen 相似文献
Substitution reactions of anhydrous K3[Cr(NCS)6] with aromatic amines without applying of solvents were studied.It was observed, that the very weak bases (pK-values 14–16, e.g. isomeric mono- and dinitro-anilines, the anthranilic and sulfanilic acids) are unsuitable for substitution reactions. The alkylaniline derivates e.g.o-, m- andp-toluidine (pK=10–11) form easily reineckesalt analogous compounds: Amin· ·H[Cr(toluidine)2(NCS)4]·The formula of the 3 new complex anions: [Cr(toluidine)2 (NCS)4]- was established by preparative methods, with a series of double decomposition reactions, using chlorohydrates of some heterocyclic amines for this purpose. From spectroscopical investigations (UV and IR) some structural problems are resolved and discussed.The thermal stability and the mechanism of pyrolysis of these salts was studied by thermogravimetric analysis.
Mit 8 Abbildungen 相似文献
14.
M. Ştefănescu M. Stoia O. Ştefănescu A. Popa M. Simon C. Ionescu 《Journal of Thermal Analysis and Calorimetry》2007,88(1):19-26
Hybrid organic-inorganic materials,
silica – polyols (ethylene-glycol – EG; 1,2 propane diol –
1,2PG; 1,3 propane diol – 1,3PG and glycerol – GL), were prepared
by a sol-gel process starting from tetraethylorthosilicate (TEOS) and polyols,
in acid catalysis. The resulting materials were studied by thermal analysis
(in air and nitrogen), FTIR and solid state 29Si-NMR
spectroscopy. These techniques evidenced the presence of polyols in the silica
matrix both hydrogen bounded and chemically bounded in the silica network.
The thermal analysis proves to be the most appropriate technique to evidence
the organic chains linked in the matrix network and to follow the thermal
evolution of the gels to the SiO2 matrix. 相似文献
15.
Wolfgang A. Herrmann Cornelia Weber Manfred L. Ziegler Orhan Serhadli 《Journal of organometallic chemistry》1985,297(2):245-254
The diazoolefines of composition N2CCR2 (R/R = CH3/CH3 and(-CH2-)5) are suitable precursors of the corresponding vinylidene ligands CCR2. Thus, treatment of the RhRh complex [(η5-C5Me5)Rh(μ-CO)]2 (1) with the N-nitrosourethanes 2a and 2b, resp., in the presence of lithium t-butoxide yields the otherwise inaccessible μ-vinylidene complexes (μ-CCR2)[(η5-C5Me5)Rh(CO)]2 (R = CH3 (3a), R,R = (-CH2-)5 (3b)). The analogous cobalt compound (μ-CCMe2)[(η5-C5Me5)Co(CO)]2 (5a) is obtained similarly. This procedure extends the well-documented diazoalkane method for the synthesis of μ-alkylidene complexes to the less stable diazoalkenes. A single-crystal X-ray diffraction study of the dimethylvinylidene derivative 3a shows the CMe2 ligand to adopt an almost symmetrically metal-bridging position (d(RhC) 197.8(1) and 204.3(1) pm), with a rhodium-rhodium single bond completing a three-membered Rh2C-metallacycle (d(RhRh) 268.4(0) pm) analogous with cyclopropane. 相似文献
16.
The parallel between orbital first and second electric moments and statistical first and second central moments is noted. Three measures of orbital spatial distribution in terms of their moments are proposed, and applied to the LMO's in a series of ten-electron hydrides. Consistent differences between bond and lone pair distributions are found. Using the statistical interpretation, for each LMO an effective solid angle around the central atom is postulated. 相似文献
17.
Torsten Meyer Thomas Hellweg Stefan Spange Stephanie Hesse Christian Jger Cornelia Bellmann 《Journal of polymer science. Part A, Polymer chemistry》2002,40(18):3144-3152
Polyvinylamine hydrogels with silica particles encapsulated (PVAm/silica) were produced by a two‐step synthesis. In the first step, polyvinylformamide/silica (PVFA/silica) hybrids were synthesized from vinylformamide (VFA) and 1,3‐divinylimidazolidin‐2‐one (1,3‐bisvinylethyleneurea, BVU), as the crosslinker, by radical copolymerization in silica/water suspensions using different compositions of VFA/BVU. The target product PVAm/silica was obtained by acidic hydrolysis of the PVFA/silica hydrogels in a second step. The chemical structures of both hydrogels, PVFA/silica and PVAm/silica, respectively, were revealed by solid‐state 13C(1H) cross‐polarity/magic‐angle spinning NMR spectroscopy. Both hydrogels swelled significantly in water. The swelling capacity of the two systems was characterized by the correlation length ξ (or hydrodynamic blob size) of the network meshes with small‐angle neutron scattering experiments. ξ is significantly larger for PVAm/silica than for PVFA/silica, which corresponds to the observed higher swelling capacity of this polyelectrolyte material. Furthermore, the swelling behavior of the hybrid hydrogels was quantitatively described in terms of free swell capacity, centrifuge‐retention capacity, adsorption against pressure, and free swell rate as compared with values of the corresponding copolymer hydrogels. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3144–3152, 2002 相似文献
18.
The transferability of the first and second order electric moments of localized orbitals have been shown. Some moment characteristics have also been investigated. The standard deviation of first order localized moments is less than 2.0%. The standard deviation of second order electric moment components are larger: although they do not exceed 4.0% for bond orbitals, for lone pair ones they vary about 1.5–10.1%. 相似文献
19.
A series of dimethyldihydropyrene derivatives was studied to elucidate the photochemical mechanism associated with the switching between the dimethyldihydropyrene (DHP, closed) and metacyclophanediene (CPD, open) forms of the molecule. Quantum yields of ring opening and closure, fluorescence quantum yields and lifetimes, as well as laser flash photolysis studies were performed to establish the effect of substituents on the switching efficiency. Ring opening of the DHPs occurs from the first singlet excited state. The low quantum yields for the ring opening reaction observed (< or =0.042) are a consequence of the low rate constant (< or =1.7 x 10(7) s(-1)) for this process. The quantum yields for ring closure of the CPD were determined for select compounds and were of the order of 0.1-0.4. These results show that the efficiency for ring opening of this class of compounds is intrinsically low, but can be modulated to some extent by the introduction of substituents. These properties should be taken into account when considering what type of photoswitching devices DHPs might be useful for. 相似文献
20.
Zaharescu M. Jitianu A. Brăileanu A. Madarász J. Novák CS. Pokol G. 《Journal of Thermal Analysis and Calorimetry》2003,71(2):421-428
Hybrid materials with different amounts of organics permanently bound on the inorganic network obtained in the TEOS-MTEOS
(tetraethoxysilan-methyltriethoxysilan) system are used for obtaining coatings with different optical and mechanical properties.
To study the thermal stability of the mentioned materials, compositions with different molar ratios of the precursors were
prepared. The influence of the solvent and water amounts on the gelation process was also investigated. The gels obtained
were characterised by IR spectrometry and their decomposition temperatures were determined by DTA/TG. Thermal stability of
the gels is rather influenced by their composition than the conditions of the gelation process.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献