Coloqui nou, en quel so Felip yl so Jusep, llauradors de lhòrta de Valencia (molt Patriòtes y pòc tontos) discurrixen sobrel Obelisco y Estatua del nòstre amat Rey, manda colocar en la plaça dels Desamparats [Texto impreso]

Hay un ejemplar encuadernado con: Poesías colocadas en el pórtico del Convento de San Francisco de Valencia (NP849.91/3086).

Hybrid characteristics of oligonucleotides consisting of isonucleoside 2′,5′-anhydro-3′-deoxy-3′-(thymin-1-yl)-d-mannitol with different linkage modes

Oligonucleotides consisting of the isonucleoside repeating unit 2′,5′-anhydro-3′-deoxy-3′-(thymin-1-yl)-d-mannitol (4) were synthesized with the monomeric unit 4 incorporated into oligonucleotides as 1′→4′ linkage 4a (oligomer I) or 6′→4′ linkage 4b (oligomer II). The hybrid properties of the two oligonucleotides I and II with their complementary strands were investigated by thermal denaturation and CD spectra. Oligonucleotide I (4a) formed a stable duplex with d(A)14 with a slightly reduced Tm value of 36.6°C, relative to 38.2°C for the control duplex d(T)14/d(A)14, but oligomer II (4b) failed to hybridize with a DNA complementary single strand. The spectrum of the duplex oligomer I/d(A)14 showed a positive CD band at 217 nm and a negative CD band at 248 nm attributable to a B-like conformation. Molecular modeling showed that in the case of oligomer I the C6′ hydroxy group of each unit could be located in the groove area when hybridized to the DNA single strand, which might contribute additional hydrogen bonding to the stability of duplex formation.

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Observation of a 331 K (58 °C) spin transition for bis[hydrotris(1,2,4-triazol-1-yl)borate]iron(II) by variable temperature infrared spectroscopy and magnetic susceptibility measurements

Fe{HB(CHN)} is observed by variable temperature infrared and magnetic studies to have a spin transition between the low spin S = 0 and high spin S = 2 states at 331 K (58 °C) with thermal hysteresis of ~1.5 K. Changes in the triazole ligand IR absorptions demonstrate that distant non-metal-ligand vibrations are altered upon the change in electronic structure associated with the spin-crossover can be used to monitor the the spin-crossover transition.

Conformational Evaluation of Indol-3-yl-N-alkyl-glyoxalylamides and Indol-3-yl-N,N-dialkyl-glyoxalylamides

Restricted rotation in indol-3-yl-N-alkyl- and indol-3-yl-N,N-dialkyl-glyoxalylamides can in principle give the syn-periplanar and anti-periplanar rotamers. In asymmetrically disubstituted glyoxalylamides, steric effects lead to the occurrence of both rotamers, as observed by NMR spectroscopy. The predominant peak corresponds with the anti rotamer, in which the bulkier alkyl group is orientated trans to the amide carbonyl group. In monoalkylated glyoxalylamides, only one set of peaks is observed, consistent with the presence of only one rotamer. Crystal structures of 5-methoxyindole-3-yl-N-tert-butylglyoxalylamide, indole-3-yl-N-tert-butylglyoxalylamide, and indole-3-yl-N-isopropylglyoxalylamide reported here reveal a syn conformation held by an intramolecular N-HO hydrogen bond.

A new 3-D polymeric spin transition compound: [tris(1,4-bis-(tetrazol-1-yl) butane-N1,N1′)iron(II)] bis(perchlorate)

A series of novel polymeric compounds of formula [M(btzb)3][ClO4]2 (Mll = Fe, Ni or Cu) with btzb = 1,4-bis-(tetrazol-1-yl)butane have been prepared and their physical properties investigated. The btzb ligand has been prepared and its crystal structure determined, together with a tentative crystal structure of the 3-D compound [Fe(btzb)3][ClO4]2. The model of the latter shows two symmetry-related, interpenetrating Fe-btzb networks in which the iron(II) ions approach each other as close as 8.3 and 9.1 Å. This supramolecular catenane undergoes a sharp thermal spin transition around 160 K with hysteresis (20 K) along with a pronounced thermochromic effect. The spin crossover behaviour has been followed by magnetic, DSC, optical spectroscopy and 57Fe Mössbauer spectroscopy measurements. Irradiation with green light at low temperature leads to population of the metastable high-spin state for the thermally active iron(ll) ions. The nature of the spin crossover behaviour has been discussed in detail.

Structure and physical properties of [µ-Tris(1,4-bis(tetrazol-1-yl)butane-N4,N4‘')iron(II)] Bis(hexafluorophosphate), a new Fe(II) spin-crossover compound with a three-dimensional threefold interlocked crystal lattice

[μ-Tris(1,4-bis(tetrazol-1-yl)butane-N4,N4‘)iron(II)] bis(hexafluorophosphate), [Fe(btzb)3](PF6)2, crystallizes in a three-dimensional 3-fold interlocked structure featuring a sharp two-step spin-crossover behavior. The spin conversion takes place between 164 and 182 K showing a discontinuity at about T1/2 = 174 K and a hysteresis of about 4 K between T1/2 and the low-spin state. The spin transition has been independently followed by magnetic susceptibility measurements, 57Fe-Mössbauer spectroscopy, and variable temperature far and midrange FTIR spectroscopy. The title compound crystallizes in the trigonal space group P30¯(No. 147) with a unit cell content of one formula unit plus a small amount of disordered solvent. The lattice parameters were determined by X-ray diffraction at several temperatures between 100 and 300 K. Complete crystal structures were resolved for 9 of these temperatures between 100 (only low spin, LS) and 300 K (only high spin, HS), Z = 1 [Fe(btzb)3](PF  6)2:  300 K (HS), a = 11.258(6) Å, c = 8.948(6) Å, V = 982.2(10) Å3; 100 K (LS), a = 10.989(3) Å, c = 8.702(2) Å, V = 910.1(4) Å3. The molecular structure consists of octahedral coordinated iron(II) centers bridged by six N4,N4‘ coordinating bis(tetrazole) ligands to form three 3-dimensional networks. Each of these three networks is symmetry related and interpenetrates each other within a unit cell to form the interlocked structure. The Fe−N bond lengths change between 1.993(1) Å at 100 K in the LS state and 2.193(2) Å at 300 K in the HS state. The nearest Fe separation is along the c-axis and identical with the lattice parameter c.

Quinols as novel therapeutic agents. 2.1 4-(1-arylsulfonylindol- 2-yl)-4-hydroxycyclohexa-2,5-dien-1-ones and related agents as potent and selective antitumor agents

A series of substituted 4-(1-arylsulfonylindol-2-yl)-4-hydroxycyclohexa-2, 5-dien-1-ones (indolylquinols) has been synthesized on the basis of the discovery of lead compound 1a and screened for antitumor activity. Synthesis of this novel series was accomplished via the "one-pot" addition of lithiated (arylsulfonyl)indoles to 4,4-dimethoxycyclohexa-2,5-dienone followed by deprotection under acidic conditions. Similar methodology gave rise to the related naphtho-, 1H-indole-, and benzimidazole-substituted quinols. A number of compounds in this new series were found to possess in vitro human tumor cell line activity substantially more potent than the recently reported antitumor 4-substituted 4-hydroxycyclohexa-2,5-dien-1-ones1 with similar patterns of selectivity against colon, renal, and breast cell lines. The most potent compound in the series in vitro, 4-(1-benzenesulfonyl-6-fluoro-1H-indol- 2-yl)-4-hydroxycyclohexa-2,5-dienone (1h), exhibits a mean GI50 value of 16 nM and a mean LC50 value of 2.24 μM in the NCI 60-cell-line screen, with LC50 activity in the HCT 116 human colon cancer cell line below 10 nM. The crystal structure of the unsubstituted indolylquinol 1a exhibits two independent molecules, both participating in intermolecular hydrogen bonds from quinol OH to carbonyl O, but one OH group also interacts intramolecularly with a sulfonyl O atom. This interaction, which strengthens upon ab initio optimization, may influence the chemical environment of the bioactive quinol moiety. In vivo, significant antitumor activity was recorded (day 28) in mice bearing subcutaneously implanted MDA-MB-435 xenografts, following intraperitoneal treatment of mice with compound 1a at 50 mg/kg.

catena-[μ-tris(1,2-bis(tetrazol-1-yl)ethane-N4,N4')iron(II)] bis(tetrafluoroborate): Synthesis, structure, spectroscopic and magnetic characterisation of a chain-type coordination polymer spin-crossover compound.

In analogy to a common synthesis of 1-substituted 5-H tetrazoles (Tetrahedron Lett. 36 (1995)1759; Beloruss. Gos. Univ., Minsk, USSR. Khim. Geterotsikl. Soedin. 11 (1985) 1521; Beloruss. Gos. Univ., Minsk, USSR. Khim. Geterotsikl. Soedin. 1 (1991) 66; BGU, Belarus. Vestsi Akad. Navuk Belarusi, Ser. Khim. Navuk 1 (1992) 73), the new bidentate ligand 1,2-bis(tetrazol-1-yl)ethane [endi] was synthesized and characterized by X-ray diffraction, NMR, IR and UV–Vis spectroscopy. By using iron(II) tetrafluoroborate hexahydrate the complexation with this ligand yields a 1-dimensional linear coordination polymer similar to the recently published chain compound (Inorg. Chem. 39 (2000) 1891) exhibiting a thermally induced spin-crossover phenomenon. Similar to the 1,2-bis(tetrazol-1-yl)propane-bridged compound, our 1,2-bis(tetrazol-1-yl)ethane-bridged compound shows a gradual spin transition, but the spin-crossover temperature T1/2≈140 K is found to be 10 K above the other T1/2. The T1/2 was determined by temperature-dependent 57Fe-Mössbauer, far FT-IR and UV–Vis spectroscopy as well as by temperature-dependent magnetic susceptibility measurements. Single crystals of the complex were grown in situ from a solution of the ligand and iron(II) tetrafluoroborate. The X-ray structure determinations of both the high spin as well as the low spin state of the compound revealed a solid state structure, which is comparable to that of catena-[Fe(1,2-bis(tetrazole-1-yl)propane)3](ClO4)2 (Inorg. Chem. 39 (2000) 1891; 2nd TMR-TOSS Meeting, 4th Spin Crossover Family Meeting, Lufthansa Training Center, Seeheim/Germany, April 30–May 2, 1999). Both the 1,2-bis(tetrazol-1-yl)propane-bridged and our compound do not show a thermal hysteresis effect (J. Am. Chem. Soc. 115 (1993) 9810; Inorg. Chim. Acta 37 (1979) 169; Chem. Phys. Lett. 93 (1982) 567). The synthesis of the complex described in the experimental section yielded a fine powdered product being poorly soluble in most common solvents. The single crystal measurements were done with crystals obtained by various diffusion methods. Most of them yielded either thin needles or small hexagonal prism crystals depending on the specific conditions.

Crystal structure and physical properties of the new linear chain compound [Cu(1,2-bis(tetrazol-1-yl)ethane)3](ClO4)2

The synthesis and crystal structure of a novel one-dimensional Cu(II) compound [Cu(1,2-bis(tetrazol-1-yl)ethane)3](ClO4)2 are described. The single-crystal X-ray structure determination was carried out at 298 K. The molecular structure consists of a linear chain in which the Cu(II) ions are linked by three N4,N4' coordinating bis(tetrazole) ligands in syn conformation. The Cu(II) ions are in a Jahn-Teller distorted octahedral environment (Cu(1)-N(11)=2.034(2) Å, Cu(1)-N(21)=2.041(2) Å and Cu(1)-N(31)=2.391(2) Å). The Cu⋯Cu separations are 7.420(3) Å.

Synthesis and evaluation of N-(3-oxo-2,3-dihydro-1H-pyrazol-4-yl)-1H-indole-carboxamides as cholecystokinin antagonists

The structure-activity relationship optimization of the pyrazoline template 3a resulted in novel 3-oxo-1,2-diphenyl-2,3-dihydro-1H-pyrazol-4-yl)-indole carboxamides 4a-4e. These non-peptidal CCK ligands have been shown to act as potent CCK 1 ligands in a [125]I-CCK-8 receptor binding assay. The best amides (4c and 4d) of this series displayed an IC50 of 20/25 CCK 1 for the CCK 1 receptor. In a subsequent in-vivo evaluation using various behaviour pharmacological assays, an anxiolytic effect of these novel 3-oxo-1,2-diphenyl-2,3-dihydro-1H-pyrazol-4-yl)-indole carboxamides was found at high doses in the elevated plus-maze. In the despair swimming test, a model for testing antidepressants, an ED50 of 0.33/0.41 mg kg -1 was determined for amide 4c/4d and the antidepressant effect had a magnitude comparable to desimipramine. © 2006 The Authors.