Preparation and photochromic properties of oligomeric poly(dimethylsiloxane) with the spiropyran or spirooxazine moiety in the side chain

Spirobenzopyran 1 , with the 3-(diethoxymethylsilyl)-propyl group at the N atom, was synthesized. The condensation reaction of the spiropyran 1 and diethoxydimethylsilane gave oligomeric poly(dimethylsiloxane) with the spiropyran moiety in the side chain. The oligomer was photochromic; its colour changed from colorless to purple-red on uv irradiation and the color faded on visible irradiation or on standing in the dark. The half-decay time of the thermal decoloration was about twice that of monomeric spiropyran dissolved in the dimethylsiloxane oligomer. Photochromic poly(dimethylsiloxane) with the spirooxazine moiety in the side chain was also prepared.     

Linear NiII-MnIII2-NiII tetramers: an oligomeric component of the MnIII2NiII single-chain magnets

Heterometallic linear tetramers [Mn(5-R-saltmen)Ni(pao)(bpy)(2)](2)(ClO(4))(4) (5-R-saltmen(2-) = N,N'-1,1,2,2-tetramethylethylene bis(5-R-salicylideneiminate); pao(-) = pyridine-2-aldoximate; bpy = 2,2'-bipyridine, R = H, 1; Cl, 2; Br, 3; MeO, 4) have been synthesized and structurally characterized. These compounds exhibit a [Ni(II)-NO-Mn(III)-(O)(2)-Mn(III)-ON-Ni(II)] skeleton where -ON- is an oximate bridge between Mn(III) and Ni(II) ions and -(O)(2)- is a bi-phenolate bridge between Mn(III) ions. These tetramers can be seen as oligomeric units of the heterometallic Mn(III)(2)-Ni(II) chain observed in a family of single-chain magnets (Clérac, R.; Miyasaka, H.; Yamashita, M.; Coulon, C. J. Am. Chem. Soc. 2002, 124, 12837. Miyasaka, H.; Clérac, R.; Mizushima, K.; Sugiura, K.; Yamashita, M.; Wernsdorfer, W.; Coulon, C. Inorg. Chem. 2003, 42, 8203.). Magnetic measurements on these tetramers confirm the nature of the magnetic interactions reported for the Mn(III)(2)-Ni(II) chains: a strong antiferromagnetic Mn(III)/Ni(II) coupling via the oximate bridge (J(Ni-Mn) ranges from -23.7 to -26.1 K) and a weak ferromagnetic Mn(III)/Mn(III) coupling through the bi-phenolate bridge (J(Mn-Mn) ranges from +0.4 to +0.9 K). These magnetic interactions lead to tetramers with an S = 2 ground state.     

Preparation,structures, and redox and emission characteristics of the isothiocyanate complexes of hexarhenium(III) clusters [Re6(mu3-E)8(NCS)6]4- (E = S,Se)

Hexarhenium(III) complexes with terminal isothiocyanate ligands, [(n-C(4)H(9))(4)N](4)[Re(6)(mu(3)-S)(8)(NCS)(6)] (1) and (L)(4)[Re(6)(mu(3)-Se)(8)(NCS)(6)] (L(+) = PPN(+) (2a), (n-C(4)H(9))(4)N(+) (2b)), have been prepared by three different methods. Complex 1 was prepared by the reaction of [(n-C(4)H(9))(4)N](4)[Re(6)(mu(3)-S)(8)Cl(6)] with molten KSCN at 200 degrees C, while 2b was obtained by refluxing the chlorobenzene-DMF (2:1 v/v) solution of [Re(6)(mu(3)-Se)(8)(CH(3)CN)(6)](SbF(6))(2) and [(n-C(4)H(9))(4)N]SCN. The [Re(6)(mu(3)-Se)(8)(NCS)(6)](4)(-) anion was also obtained from a mixture of Cs(2)[Re(6)(mu(3)-Se)(8)Br(4)] and KSCN in C(2)H(5)OH by a mechanochemical activation at room temperature for 20 h and isolated as 2a. The X-ray structures of 1 and 2a.4DMF have been determined (1, C(70)H(144)N(10)S(14)Re(6), monoclinic, space group P2(1)/n (No. 14), a = 14.464(7) A, b = 22.059(6) A, c = 16.642(8) A, beta = 113.62(3) degrees, V = 4864(3) A(3), Z = 2; 2a.4DMF, C(162)H(144)N(14)O(4)P(8)S(6)Se(8)Re(6), triclinic, space group P1 (No. 2), a = 15.263(2) A, b = 16.429(2) A, c = 17.111(3) A, alpha = 84.07(1) degrees, beta = 84.95(1) degrees, gamma = 74.21(1) degrees, V = 4098.3(8) A(3), Z = 1). All the NCS(-) ligands in both complexes are coordinated to the metal center via nitrogen site with the Re-N distances in the range of 2.07-2.13 A. The redox potentials of the reversible Re(III)(6)/Re(III)(5)Re(IV) process in acetonitrile are +0.84 and +0.70 V vs. Ag/AgCl for [Re(6)(mu(3)-S)(8)(NCS)(6)](4)(-) and [Re(6)(mu(3)-Se)(8)(NCS)(6)](4)(-), respectively, which are the most positive among the known hexarhenium complexes with six terminal anionic ligands. The complexes show strong red luminescence with the emission maxima (lambda(max)/nm), lifetimes (tau(em)/micros), and quantum yields (phi(em)) being 745 and 715, 10.4 and 11.8, and 0.091 and 0.15 for 1 and 2b, respectively, in acetonitrile. The data reasonably well fit in the energy-gap plots of other hexarhenium(III) complexes. The temperature dependence of the emission spectra and tau(em) of 1 and [(n-C(4)H(9))(4)N](4)[Re(6)(mu(3)-S)(8)Cl(6)] are also reported.     

Destructive and non-destructive determination of titanium in yttrium,niobium and tantalum oxides by photon activation

Destructive and non-destructive procedures have been developed for the determination of titanium by photon activation analysis. The non-destructive analyses with an internal standard method are performed on niobium and tantalum oxides while destructive determinations, including non-isotope addition and radiochemical separation, are applied to yttrium oxide samples.     

MnIII2 (5-Rsaltmen)2NiII(pao)2(L)]2+: an S(T)=3 building block for a single-chain magnet that behaves as a single-molecule magnet

Mn(III)-Ni(II)-Mn(III) linear-type trinuclear complexes bridged by oximate groups were selectively synthesized by the assembly reaction of [Mn2(5-Rsaltmen)2(H2O)2](ClO4)2 (5-Rsaltmen2-=N,N'-(1,1,2,2-tetramethylethylene) bis(5-R-salicylideneiminate); R=Cl, Br) with [Ni(pao)2(phen)] (pao-=pyridine-2-aldoximate; phen=1,10-phenanthroline) in methanol/water: [Mn2(5-Rsaltmen)2Ni(pao)2(phen)](ClO4)2 (R=Cl, 1; R=Br, 2). Structural analysis revealed that the [Mn(III)-ON-Ni(II)-NO-Mn(III)] skeleton of these trimers is in every respect similar to the repeating unit found in the previously reported series of 1D materials [Mn2(saltmen)2Ni(pao)2(L1)2](A)(2) (L(1)=pyridine, 4-picoline, 4-tert-butylpyridine, N-methylimidazole; A=ClO4-, BF4-, PF6-, ReO4-). Recently, these 1D compounds have attracted a great deal of attention for their magnetic properties, since they exhibit slow relaxation of the magnetization (also called single-chain magnet (SCM) behavior). This unique magnetic behavior was explained in the framework of Glauber's theory, generalized for chains of ferromagnetically coupled anisotropic spins. Thus, in these 1D compounds, the [Mn(III)-ON-Ni(II)-NO-Mn(III)] unit was considered as an S(T)=3 anisotropic spin. Direct-current magnetic measurements on 1 and 2 confirm their S(T)=3 ground state and strong uniaxial anisotropy (D/k(B) approximately -2.4 K), in excellent agreement with the magnetic characteristic deduced in the study on the SCM series. The ac magnetic susceptibility of these trimers is strongly frequency-dependent and characteristic of single-molecule magnet (SMM) behavior. The relaxation time tau shows a thermally activated (Arrhenius) behavior with tau0 approximately 1x10(-7) s and Delta(eff)/k(B) approximately 18 K. The effective energy barrier for reversal of the magnetization Delta(eff) is consistent with the theoretical value (21 K) estimated from |D| S2T. The present results reinforce consistently the interpretation of the SCM behavior observed in the [Mn2(saltmen)2Ni(pao)2(L1)2](A)2 series and opens new perspectives to design single-chain magnets.     

Trapping effect of eugenol on hydroxyl radicals induced by L-DOPA in vitro

Many researchers have stated that eugenol might inhibit lipid peroxidation at the stage of initiation, propagation, or both, and many attempts have been made to elucidate the mechanism of its antioxidant activity. Nevertheless, details of its mechanism are still obscure. This study was carried out to investigate the trapping effect of eugenol on hydroxyl radical generated from L-3,4-dihydroxyphenylalanine (DOPA) in MiliQ water and the generation mechanism of the hydroxyl radical by this system which uses no metallic factor. This was studied by adding L-DOPA and 5,5-dimethyl-1-pyrroline N-oxide (DMPO) to phosphate buffered saline (PBS) or MiliQ water, and the generation of hydroxyl radical was detected on an ESR spectrum. By this method, the effect of antioxidants was detected as a modification of ESR spectra. We found that the eugenol trapped hydroxyl radicals directly, because it had no iron chelating action, did not trap L-DOPA semiquinone radical and inhibited hydroxyl radicals with or without iron ion.     

Practical synthesis of a neuropeptide Y antagonist via stereoselective addition to a ketene

[Reaction: see text]. The synthesis of neuropeptide Y antagonist 1, currently under clinical investigation for the treatment of obesity, is described. The convergent synthesis from trans-spirolactone carboxylic acid intermediate 2a and aminopyrazole 3 is predicated on a stereoselective route to the former. The coupling reaction of ethyl 4-oxocyclohexanecarboxylate (10a) with lithiated isonicotinamide 11 was investigated in detail, but even optimized conditions only provided a 45:55 ratio of trans:cis isomers (12a:12b). While selective crystallization schemes were developed to isolate the thermodynamically less stable trans isomer 2a, improved stereocontrol was subsequentially achieved by the application of ketene chemistry. The ketene formation and quench was investigated under a variety of conditions aimed at maximizing the trans:cis ratio. Reacting a mixture of carboxylic acids 2a and 2b with POCl3 in THF, followed by concomitant addition of tert-butyl alcohol in the presence of TMEDA at 35 degrees C provided a 4:1 ratio of trans:cis tert-butyl esters (18a:18b) via in situ ketene formation. Ester hydrolysis, followed by selective crystallization of undesired 2b as the HCl salt, led to isolation of 2a in 47% overall yield. Aminopyrazole intermediate 3 was synthesized via the condensation reaction of 2-fluorophenylhydrazine hydrochloride (4a) with acrylonitrile derivative 5 in 65-70% yield. Coupling of advanced intermediates 2a and 3b via activation with thionyl chloride gave a 92% yield of 1.     

Aqueous phase behavior of a 1-O-phytanyl-beta-D-xyloside/water system. Glycolipid-based bicontinuous cubic phases of crystallographic space groups Pn3m and Ia3d

Temperature- and concentration-dependent aqueous phase diagram of a novel alkylglycoside, 1-O-phytanyl-beta-D-xyloside (beta-Xyl(Phyt)), was studied using small-angle X-ray scattering, polarizing optical microscopy, and differential scanning calorimetry. The phases found in this system include an Lc phase, an Lalpha phase, an HII phase, two inverted cubic phases of crystallographic space groups Pn3m and Ia3d, and a fluid isotropic phase, FI. The phase diagram of the beta-Xyl(Phyt)/water system is similar to that for the 1-monooleylglycerol (MO)/water system, suggesting that the phase behavior is largely determined by the overall molecular shape rather than the details of surfactant molecular structure. Moreover, the structural parameters of the beta-Xyl(Phyt) liquid crystals are also similar to those of the MO/water, due primarily to the similar molecular dimensions of two molecules. As compared to the MO/water system, however, the beta-Xyl(Phyt)/water system displays a lower value of TK ( approximately 8.(5) degrees C) and a wider temperature window for the mesophases (8.(5)-120 degrees C). Moreover, beta-Xyl(Phyt) is chemically more robust than MO, as the ether linkage is more stable against hydrolysis than the ester linkage and the phytanyl chain is fully saturated.