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At least 433 records · Page 24Linked to original sources
PubMed2000

Synthesis, crystal structure, EXAFS, and magnetic properties of catena [mu-tris(1,2-bis(tetrazol-1-yl)propane-N1,N1')iron(II)] bis(perchlorate). First crystal structure of an iron(II) spin-crossover chain compound.

[Fe(btzp)3](ClO4)2 (btzp = 1,2-bis(tetrazol-1-yl)propane) represents the first structurally characterized Fe(II) linear chain compound exhibiting thermal spin crossover. It shows a very gradual spin transition (T1/2 = 130 K) which has been followed by magnetic susceptibility measurements and 57Fe Mössbauer spectroscopy. The structure has been solved at 200 and 100 K by single-crystal X-ray analysis. It crystallizes in the trigonal space group P3c1 with Z = 2 Fe(II) units at both temperatures. The molecular structure consists of chains running along the c axis in which the Fe(II) ions are linked by three N4,N4' coordinating bis(tetrazole) ligands. The main difference between the two forms appears to be in the Fe-N bond lengths, which are 2.164(4) A at 200 K and 2.038(4) A at 100 K. The Fe-Fe separations are 7.422(1) A at 200 K and 7.273(1) A at 100 K. The EXAFS results are consistent with the crystal structure. In both spin states, the FeN6 octahedron is almost regular within the EXAFS resolution. The Fe-N distance is found as 2.16(2) A at 300 K and 2.00(2) A at 40 K. The absence of the "7 A peak" in the EXAFS spectra of [Fe(btzp)3](ClO4)2, in contrast with what has been observed for the [Fe(4-R-1,2,4-triazole)3]-(anion)2 chain compounds, confirms that this peak can be used as the signature of a metal alignment only when it involves a strongly enhanced multiple scattering M-M-M path, with M-M spacing less than 4 A. Irradiation with green light at 5 K has led to the population of the metastable high-spin state for the iron(II) ion. The nature of the spin-crossover behavior has been discussed on the basis of the structural features.

Journal Article↗
PubMed2002

A metal-organic bilayer open framework with a dynamic component: single-crystal-to-single-crystal transformations.

A metal-organic bilayered open framework, [Ni2(C26H52N10)]3[BTC]4.6C5H5N.36H2O (BOF-1, 1), has been prepared by the self-assembly of a new bismacrocyclic nickel(II) complex [Ni2(C26H52N10)(Cl)4].H2O (A) and sodium 1,3,5-benzenetricarboxylate (Na3BTC) in the mixture of water/DMSO/pyridine. The X-ray crystal structure of 1 shows that 2D layers with the cavities of brick-wall motifs (22.6 x 14.3 A2) are formed by the coordination of the nickel(II) complex with BTC3- ions and that the two 2D layers are linked with the p-xylyl bridging groups of the bismacrocycles as pillars to generate 3D channels in the bilayered framework. The voids of the channels occupy 61% of the total volume, which are filled with pyridine and water guest molecules. When 1 was dried at 75 degrees C for 1.5 h, [Ni2(C26H52N10)]3[BTC]4.4H2O (2) resulted by maintaining the single-crystallinity, which exhibited a dramatic decrease in the interlayer spacing as well as changes in the cell parameters. Solid 2 differentiates various alcohols such as MeOH, EtOH, isopropyl alcohol, and benzyl alcohol in toluene. When 1 was immersed in insoluble solvents such as pyridine and benzene, some guest molecules were exchanged with the aromatic molecules to give [Ni2(C26H52N10)]3[BTC]4.20pyridine.6H2O (3) and [Ni2(C26H52N10)]3[BTC]4.14benzene.19H2O (4), respectively. The guest-exchange processes also involve single-crystal-to-single-crystal transformation.

Journal Article↗
PubMed2004

X-ray diffraction analysis of nonequilibrium states in crystals: observation of an unstable conformer in flash-cooled crystals.

Some molecules with a molecular skeleton similar to that of stilbenes and azobenzenes show orientational disorder in the crystals. If the disorder is dynamic, a conformational interconversion takes place through a pedal motion. In this study X-ray diffraction analyses of (E)-stilbene (1) and azobenzene (2) were carried out at various temperatures. We succeeded in observing thermodynamic nonequilibrium states that were generated by fast freezing of the conformational interconversion at low temperatures. The populations of the two conformers in crystals of 1 at 90 K varied with the cooling rate. Flash cooling of a crystal of 2 from room temperature to 90 K made it possible to observe the minor unstable conformer that does not exist in the equilibrium state at the same temperature.

Journal Article↗
PubMed2004

Crystal-to-crystal guest exchange of large organic molecules within a 3D coordination network.

Single-crystal-to-single-crystal guest exchanges of large guest molecules [triphenylene (3a), anthracene (3b), perylene (3c), and triphenylphosphine oxide (3d)] were successfully performed in a large channel of a 3D coordination network (2) having a planar ligand, (1). Crystallographic analysis revealed efficient stackings between the planar guests (3a-c) and the ligand. The crystals of the inclusion complexes of 3a-c showed drastic color change because of strong donor-acceptor interactions between the electron-deficient ligand (1) and electron-rich guests (3a-c).

Journal Article↗
PubMed2005

Guest-induced asymmetry in a metal-organic porous solid with reversible single-crystal-to-single-crystal structural transformation.

A metal-organic honeycomb-like 2D pillared-bilayer open framework has been constructed which shows dynamic sponge-like single-crystal-to-single-crystal transformation upon dehydration and rehydration. The dehydrated acentric nonporous phase transformed to the porous centric phase with the selective adsorbate concomitant with the structural transformation correlated with the single-crystal structure determination.

Journal Article↗
PubMed2006

Role of crystal-amorphous interaction in phase equilibria of crystal-amorphous polymer blends.

A self-consistent theory has been developed for determination of phase diagrams of a crystalline polymer solution. Although the original Flory diluent theory captures the liquidus line, the theory is incapable of accounting for the solidus line due to the inherent assumption of complete immiscibility of solvent in the solid crystal. The present theory considers all possible interactions involving amorphous-amorphous and crystal-amorphous interactions. The self-consistent solutions predict various phase diagrams involving liquid-liquid, pure solid, and liquid-solid coexistence regions bound by liquidus and solidus lines. In the limit of complete insolubility of solvent in neat solid crystal, the original Flory diluent theory is recovered.

Journal Article↗
PubMed2006

Measurements of interfacial viscoelasticity with a quartz crystal microbalance: influence of acoustic scattering from a small crystal-sample contact.

We discuss the influence of a limited contact size on measurements of high-frequency interfacial viscoelasticity performed with a combination of a quartz crystal microbalance (QCM) and the Johnson-Kendall-Roberts (JKR) apparatus. In this instrument, a sphere-plate contact is established between an elastomeric lens and a quartz resonator. The analysis is carried out in the frame of the sheet-contact model, which states that both the shift of resonance frequency and the bandwidth are proportional to the contact area as long as the contact area is much smaller than the crystal itself. In particular, the ratio of the shift in bandwidth and the shift in frequency (termed the D-f ratio) is predicted to be constant and independent of geometry. However, the experiment does show a slight increase in the D-f ratio with the contact radius when the contact radius is comparable to the wavelength of sound inside the crystal. This effect can be explained by acoustic scattering.

Journal Article↗
PubMed2005

Concomitant dimorphs of tri-O-[p-halobenzoyl]-myo-inositol 1,3,5-orthoformates with different halogen bonding contacts: first order crystal-to-crystal thermal phase transition of kinetic form to the thermodynamic form.

Crystallization of tri-O-[p-halobenzoyl]-myo-inositol 1,3,5-orthoformates from ethyl acetate-petroleum ether solution produced concomitant dimorphs that have different halogen bonding contacts; the kinetic form with C-Br...O-C contacts upon heating to 185 degrees C, converts completely to the thermodynamic form with C-Br...O=C contacts via crystal-to-crystal first order phase transition.

Journal Article↗
PubMed2005

Generation of frustrated liquid crystal phases by mixing an achiral nematic-smectic-C mesogen with an antiferroelectric chiral smectic liquid crystal.

By mixing the achiral liquid crystal HOAB, exhibiting a nematic (N)-smectic-C (SmC) mesophase sequence, with the chiral antiferroelectric liquid crystal (AFLC) (S,S)-M7BBM7, forming the antiferroelectric SmC(a)(*) phase, at least seven different mesophases have been induced which neither component forms on its own: a twist-grain-boundary (TGB(*)) phase, two or three blue phases, the untilted SmA(*) phase, as well as all three chiral smectic-C-type "subphases," SmC(alpha)(*), SmC(beta)(*), and SmC(gamma)(*). The nature of the induced phases and the transitions between them were determined by means of optical and electro-optical investigations, dielectric spectroscopy, and differential scanning calorimetry. The induced phases can to a large extent be understood as a result of frustration, TGB(*) at the border between nematic and smectic, the subphases between syn and anticlinic tilted smectic organization. X ray scattering experiments reveal that the smectic layer spacing as well as the degree of smectic order is relatively constant in the whole mixture composition range in which AFLC behavior prevails, whereas both these parameters rapidly decrease as the amount of HOAB is increased to such an extent that no other smectic-C-type phase than SmC/SmC(*) exists. By tailoring the composition we are able to produce liquid crystal mixtures exhibiting unusual phase sequences, e.g., with a direct isotropic-SmC(a)(*) transition or a temperature range of the SmC(beta)(*) subphase of about 50 K.

Journal Article↗
PubMed2003

Elucidation of crystal form diversity of the HIV protease inhibitor ritonavir by high-throughput crystallization.

Pharmaceutical compounds are molecular solids that frequently exhibit polymorphism of crystal form. One high profile case of polymorphism was ritonavir, a peptidomimetic drug used to treat HIV-1 infection and introduced in 1996. In 1998, a lower energy, more stable polymorph (form II) appeared, causing slowed dissolution of the marketed dosage form and compromising the oral bioavailability of the drug. This event forced the removal of the oral capsule formulation from the market. We have carried out high-throughput crystallization experiments to comprehensively explore ritonavir form diversity. A total of five forms were found: both known forms and three previously unknown forms. The novel forms include a metastable polymorph, a hydrate phase, and a formamide solvate. The solvate was converted to form I via the hydrate phase by using a simple washing procedure, providing an unusual route to prepare the form I "disappearing polymorph" [Dunitz, J. D. & Bernstein, J. (1995) Acc. Chem. Res. 28, 193-200]. Crystals of form I prepared by using this method retained the small needle morphology of the solvate and thus offer a potential strategy for particle size and morphology control.

Crystallography, X-Ray↗
PubMed1975

Crystallization and crystal data of monellin.

Crystals of monellin, a sweet protein from Dioscoreophyllum cumminsii, were grown by vapor diffusion of 20% ethanol into buffered protein solution. The crystals are orthorhombic, belonging to space group P2(1)2(1)2, with a = 54.4 A, b = 113.0 A, c = 40.8 A, and V = 250,300 A(3). The asymmetric unit contains two complete molecules of monellin. The diffraction pattern of this crystal form extends to at least 2.5 A, indicating that x-ray structural analysis is possible to near-atomic resolution.

Journal Article↗
PubMed2001

Protein intermediate trapped by the simultaneous crystallization process. Crystal structure of an iron-saturated intermediate in the Fe3+ binding pathway of camel lactoferrin at 2.7 a resolution.

This is the first protein intermediate obtained in the crystalline state by the simultaneous process of Fe(3+) binding and crystal nucleation and is also the first structure of an intermediate of lactoferrin in the Fe(3+) binding pathway. Lactoferrin is an iron-binding 80-kDa glycoprotein. It binds Fe(3+) very tightly in a closed interdomain cleft in both lobes. The iron-free structure of lactoferrin, on the other hand, adopts an open conformation with domains moving widely apart. These studies imply that initial Fe(3+) binding must be in the open form. The protein intermediate was crystallized by the microdialysis method. The protein solution, with a concentration of 100 mg/ml in 10 mm Tris-HCl, pH 8.0, was loaded in a capillary and dialyzed against the same buffer containing 26% (v/v) ethanol placed in a reservoir. FeCl(3) and CO(3)(2-) in excess molar ratios to that of protein in its solution were added to the reservoir buffer. The crystals appeared after some hours and grew to the optimum size within 36 h. The structure was determined by molecular replacement method and refined to final R- and R-free factors of 0.187 and 0.255, respectively. The present structure showed that the protein molecule adopts an open conformation similar to that of camel apolactoferrin. The electron density map clearly indicated the presence of two iron atoms, one in each lobe with 4-fold coordinations: two by the protein ligands of Tyr-92(433) OH and Tyr-192(526) OH and two other coordination sites occupied by oxygen atoms of bidentate CO(3)(2-) ions leading to a tetrahedral intermediate. The CO(3)(2-) anion is stabilized through hydrogen bonds with the synergistic anion-binding site Arg-121(463) and with Ser-122 Ogamma in the N-lobe and Thr-464 Ogamma in C-lobe. The third oxygen atom of CO(3)(2-) interacts with a water molecule in both lobes.

Animals↗
PubMed1993

Calcium pyrophosphate dihydrate crystal deposition and other crystal deposition diseases.

Recent advances in understanding the pathogenesis and mechanisms of tissue damage related to calcium-containing crystals are highlighted in this review. The clinical spectrum of diseases related to crystal deposition has broadened and includes distinct neurologic syndromes associated with hypertrophy and calcification of the ligamentum flavum or posterior longitudinal ligament in the cervical spine. Diagnostic methods of crystal identification are also reviewed.

Aged↗
PubMed2004

Bistable nematic and smectic anchoring in the liquid crystal octylcyanobiphenyl (8CB) adsorbed on a MoS2 single crystal.

We have studied the anchoring directions imposed on 4-n-octyl-4(')-cyanobiphenyl (8CB) smectic-A and nematic phases by a single crystal of molybdenum disulfide (MoS2). Combining optical microscopy and x-ray diffraction under grazing incidence we have demonstrated the occurrence of a bistable planar anchoring. A previous study of the two-dimensional (2D) network of adsorbed 8CB molecules under the liquid crystal film allows a direct connection to be made between the interface structure and the anchoring directions, demonstrating that bistability is induced by the presence of two dipolar groups in the skeleton of the 2D network. It is demonstrated that the Landau-de Gennes theory cannot account for the observed anchoring in the nematic phase. The Landau-de Gennes free energy has to be associated with a coupling with both the surface order and the MoS2 substrate to explain the experimental observations. The hypothesis of a nematic layer under the liquid crystal bulk is postulated in the smectic phase.

Journal Article↗
PubMed2004

Homogeneous crystallization of poly(ethylene oxide) confined to droplets: the dependence of the crystal nucleation rate on length scale and temperature.

We present a study of homogeneous nucleation in polymer crystallization. Crystal nucleation is observed within discrete droplets of poly(ethylene oxide) that are formed by the dewetting of a thin film. The samples provide an ensemble of impurity-free droplets, with length scales that can easily be measured. Droplet crystallization is found in two distinct temperature regimes corresponding to homogeneous and heterogeneous nucleation. Here we focus on homogeneous nucleation and show that the nucleation rate scales with the volume of the crystallizable domain, indicating that we are observing homogeneous nucleation in the bulk of the droplets. In addition, the dependence of the nucleation rate on temperature is consistent with classical nucleation theory.

Journal Article↗
PubMed2004

Conical second harmonic generation in a two-dimensional chi(2) photonic crystal: a hexagonally poled LiTaO3 crystal.

A new type of conical second-harmonic generation was discovered in a 2D chi((2)) photonic crystal-a hexagonally poled LiTaO3 crystal. It reveals the presence of another type of nonlinear interaction-a scattering involved optical parametric generation in a nonlinear medium. Such a nonlinear interaction can be significantly enlarged in a modulated chi((2)) structure by a quasi-phase-matching process. The conical beam records the spatial distribution of the scattering signal and discloses the structure information and symmetry of the 2D chi((2)) photonic crystal.

Journal Article↗
PubMed2000

Crystallization and preliminary characterization of crystals of human protein kinase CK2.

The heterotetrameric recombinant holoenzyme of human protein kinase CK2 was purified to homogeneity. It degraded spontaneously to a stable and fully active state in which the catalytic subunit was about 5 kDa smaller than the wild type. The degraded enzyme was crystallized using polyethylene glycol 3350 as precipitant. The crystals belong to the hexagonal space group P6(3). They have unit-cell parameters a = b = 176.0, c = 93.6 A and diffract X-rays to at least 3.5 A resolution. The calculated crystal packing parameter is V(M) = 3.22 A(3) Da(-1), suggesting that one CK2 tetramer is contained in the asymmetric unit and that the solvent content of the unit cell is 62%.

Casein Kinase II↗