Gold-catalyzed synthesis of alkylidene 2-oxazolidinones and 1,3-oxazin-2-ones

N-Boc-protected alkynylamines are converted into the corresponding alkylidene 2-oxazolidinones or 2-oxazinones under very mild reaction conditions in the presence of 1-5 mol % of a cationic Au(I) complex. The scope of the reaction is very general, providing the cyclic carbamates in high yield regardless of the substitution at nitrogen and alkyne terminus.     

Influence of temperature on the colloidal stability of the F-DPPC and DPPC liposomes induced by lanthanum ions

The influence of La(3+) on the colloidal stability of liposomes made up by two zwitterionic phospholipids, 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and 1-palmitoyl-2-[16-fluoropalmitoyl-phosphatidylcholine (F-DPPC), in aqueous media has been investigated by dynamic light scattering and electrophoretic mobility. The critical aggregation concentration (c.a.c.) of La(3+) for F-DPPC and DPPC liposomes were experimentally obtained, and the results were compared with theoretical predictions using the Derjaguin-Landau-Verwey-Overbeek theory. In order to evaluate the influence of the state of the bilayer on the stability of liposomes, all experiments were performed at temperatures below and above the chain-melting phase-transition temperature of lipids (transition temperature of lipids). Changes in the size of both types of liposomes and high values of polydispersity in the presence of La(3+) showed that these ions induce aggregation of liposomes at 25 °C and at 60 °C. At 25 °C, when the bilayer of F-DPPC liposomes is interdigited, DPPC liposomes are more resistant to aggregation than the liposomes formed with F-DPPC. However, this difference disappears at 60 °C, when both bilayers have the same conformation. The experimental results also indicate that the c.a.c. is higher at 60 °C than at 25 °C for both types of liposomes. In fact, it has been observed by dynamic light scattering measurements that aggregation of liposomes at 25 °C can be prevented by increasing the solution temperature for La(3+) concentrations near to the c.a.c. Moreover, the behavior of these liposomes in the presence of the ion was studied at temperatures above and below the transition temperature of the phospholipids.     

Multidisciplinary physicochemical analysis of oligothiophenes end-capped by nitriles: electrochemistry, UV-vis-near-IR, IR, and Raman spectroscopies and quantum chemistry

In this article, we investigate a series of alpha,omega-dicyano end-capped oligothiophenes NC(C(4)H(2)S)(n)()CN ranging in length from the dimer to the hexamer (n = 2-6), in the neutral state as pure solids, by means of Fourier transform IR and Fourier transform Raman (FT-Raman) spectroscopies. The cyclic voltammetry analysis of the compounds in dichloromethane reveals that most of them show two oxidation and two reduction waves (i.e., a dual or amphoteric electrochemical behavior), associated with the injection of either positive or negative charges into the pi-conjugated system. The doped species are characterized by in situ vis-near-IR and FT-Raman spectrochemistries. Density functional theory calculations have been also performed, at the B3LYP/6-31G level, to assess information about the molecular geometries and vibrational features of the neutral and doped species and about the topologies of the molecular orbitals involved in the main electronic transitions that appear for the neutral forms in the visible spectral region and for the doped species in the near-IR region.     

Synthesis and structure of 5-methoxy-4-methylbenzopsoralen

5-Methoxy-4-methyl-2H-benzofuro[3,2-g]benzo-1-pyran-2-one was synthesized and its crystal structure was determined and compared with the optimal conformation arrived at by MM and AM1 theoretical calculations. The latter indicated that the tetracyclic skeleton is planar with total length (C2–C8) 9.23 å, and that the line joining the conters of the terminal-benzene and furan rings makes an angle of 30.5 with that joining the centers of the three rings of psoralen. The electronic properties of the reactive double bond in the pyran ring of1 are similar to those of simpler psoralens.     

Mixed vesicle formation on a ternary surfactant system: didodecyldimethylammonium bromide/dodecylethyldimethylammonium bromide/water

The formation of mixed aggregates has been investigated on a ternary system consisting of two cationic surfactants with similar polar heads and two and/or one 12 carbon atom hydrophobic tail, respectively, didodecyldimethylammonium bromide and dodecylethyldimethylammonium bromide and water. The study has been carried out by means of conductivity, zeta potential, and cryogenic transmission electronic microscopy (cryo-TEM) experiments on the very diluted region. A variety of mixed aggregates, microaggregates, vesicles, and micelles has been found, depending on system composition and total surfactant concentration. Mixed critical microaggregate concentration and mixed critical vesicle concentration have been determined from conductivity data. Furthermore, zeta potential and cryo-TEM experiments allow for the characterization of the aggregates/solution interface and of the shape and size of the aggregates. This experimental evidence has also been analyzed in terms of the theoretical packing parameter, P.     

New Materials Derived from Ybco: CrSr2RECu2O8 (RE = La, Pr, Nd, Eu, Gd, Tb, Dy, Y, Ho, Er, Lu)

Eleven new oxides, derived from yttrium barium copper oxide by replacing the square-planar copper [Cu-O4] of the basal plane of the triple perovskite-based structure with octahedral Cr(IV), have been prepared at high pressure and temperature. Their crystal structures have been determined, and their complex microstructure has been established by means of high-resolution electron microscopy and electron diffraction. The materials have a general formula of CrSr2RECu2O8 (RE = La, Pr, Nd, Eu, Gd, Tb, Dy, Y, Ho, Er, and Lu); they are tetragonal, show the symmetry of space group P4/mmm, and do not appear to be superconducting.     

Post-Synthetic Modification of ZIF-8 Crystals and Films through UV Light Photoirradiation: Impact on the Physicochemical Behavior of the MOF

The physicochemical modification of Metal-Organic Frameworks (MOFs) is a current challenge in the search to improve their performance in different technological applications. In this work we analyze the post-synthetic modification of ZIF-8 crystals and films through a simple and clean treatment that involves the exposure to a UV lamp under environmental conditions. It is demonstrated that a short treatment alters the MOF structure and chemistry, providing a modified ZIF-8 due to partial disconnections of its structure which increase the amount of terminal surface species such as Zn−OH and −C=N-H, but without compromising the overall MOF structure, specific surface area or thermal stability. Additionally, it leads to changes in several properties of the ZIF-8, such as its capacity to accumulate charge through pseudocapacitive processes, its interaction with nitric oxide and its light absorption behavior. This strategy of modifying ZIF-8 without the use of chemicals through a gentle disconnection of its own structure could open new perspectives of post-functionalization of crystals and films of ZIF-8 to be used in a wide range of applications.     

Exploration of ground and excited electronic states of aromatic and quinoid S,S-dioxide terthiophenes. Complementary systems for enhanced electronic organic materials

We analyze the electronic and molecular structures for the ground and excited electronic states of aromatic terthiophene (3T), the quinodimethane 3',4'-dibutyl-5,5' '-bis(dicyanomethylene)-5,5' '-dihydro-2,2':5',2' '-terthiophene (3Q), and isologues with the middle ring S-oxidized (3TO2, 3QO2). These represent extremes of electron rich and deficient ground states, often exhibiting complementary properties. Oxidizing the central sulfur atom affects the molecular structure, electron affinity, and photophysical properties of both pi systems. The consequences for 3T include de-aromatization of the central thiophene, red-shifting of the electronic absorption spectrum, and lowering of the reduction potential. The electron deficient quinoid 3QO2 shows an enhancement of electron affinity from reducing the electron-donor ability of sulfur, and a blue-shifting of its electronic absorption spectrum was seen. Fluorescence emission is quenched in the sulfonated terthiophene, and the contrary effect again would be expected upon sulfonation of a quinoid emitter. Raman vibrational spectroscopy, electrochemistry, and UV-vis and fluorescence spectroscopies are analyzed in conjunction with theoretical calculations.     

Crystal structure and electronic and magnetic properties of hexacyanoosmate(III)

The [Os(III)(CN)6]3- anion is prepared by chemical oxidation in aqueous solution and isolated as yellow prisms of [Ph4P]3[Os(III)(CN)6].6H2O (1). This species crystallizes in the triclinic space group P with cell parameters a = 13.7609(11) A, b = 16.2275(13) A, c = 17.0895(14) A, alpha = 91.4040(10) degrees , beta = 109.3600(10) degrees , gamma = 102.3970(10) degrees , V = 3497.4(5) A(3), and Z = 2. The slightly distorted octahedral moiety displays Os-C and C-N bond lengths that average 2.058 and 1.146 A, respectively. Spin-orbit-coupling splitting of the ground-state term dominates the NIR region of the electronic spectrum and the magnetic behavior of 1. The experimental information points to higher spin delocalization over the coordinated cyanides than in [Fe(III)(CN)6]3-.