Influence of bromine substitution pattern on the singlet oxygen generation efficiency of two-photon absorbing chromophores

A molecular engineering strategy based on rational variations of the bromine substitution pattern in two-photon absorbing singlet oxygen sensitizers allows studying the relations that exist between the positioning of an inter-system crossing promoter on the charge-transfer chromophore and its ability to generate singlet oxygen.     

Syntheses of pseudoceramines A-D and a new synthesis of spermatinamine, bromotyrosine natural products from marine sponges

Herein we report the total syntheses of pseudoceramine A-D (2-5) and spermatinamine (1) isolated from the marine sponge Pseudoceratina sp. Direct acyl substitution of α-hydroxyiminoesters with amine nucleophiles was developed as a key transformation. The synthetic compounds confirm the reported structures and importantly gives access to non-symmetrical spermine based natural products carrying two different bromotyrosine building blocks. Our new synthesis of spermatinamine is two steps shorter and more efficient than the previously reported sequence.     

Kinetic evaluation of sorption and desorption

Sorption is often quantified by a distribution coefficient, K _d , which is the equilibrium ratio between species sorbed to the rock and species in solution. Traditionally K _d -values are determined in batch experiments from equilibrium concentrations.     

Topography and surface energy dependent calcium phosphate formation on Sol-Gel derived TiO2 coatings

Heterogeneous nucleation and growth of calcium phosphate (CaP) on sol-gel derived TiO(2) coatings was investigated in terms of surface topography and surface energy. The topography of the coatings was derived from AFM measurements, while the surface energy was determined with contact angle measurements. The degree of precipitation was examined with scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The precipitation of CaP was found to be dependent on both topography and surface energy. A high roughness value when combining the RMS roughness parameter S(q) with the number of local maxima per unit area parameter S(ds) enhances CaP formation. The hydrophilicity of the coating was also found to be of importance for CaP formation. We suggest that the water contact angle, which is a direct measure of the hydrophilicity of the surface, may be used to evaluate the surface energy dependent precipitation kinetics rather than using the often applied Lewis base parameter.     

Differentiation of estriol glucuronide isomers by chemical derivatization and electrospray tandem mass spectrometry

This paper describes a way of differentiating between the three isomers of estriol glucuronide by the use of chemical derivatization and liquid chromatography/electrospray tandem mass spectrometry (MS/MS). In their native form, these isomers gave rise to almost identical product ion spectra, involving the neutral loss of 176 Da (i.e. monodehydrated glucuronic acid), which made it impossible to determine the position of conjugation by MS/MS alone. In order to change the fragmentation pathways, positive charges were introduced into the analytes by chemical derivatization. The following reagents were tested: 2-chloro-1-methylpyridinium iodide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide and 2-picolylamine. Interestingly, derivatization using a combination of all three reagents gave a selective fragmentation pattern that could differentiate between the isomers estriol-16-glucuronide and estriol-17-glucuronide. Estriol-3-glucuronide, which lacks a free phenolic group, could be differentiated through a different type of reaction product when exposed to 2-chloro-1-methylpyridinium iodide. Furthermore, in order to assist structural assignment of the fragments, their accurate masses were determined using a hybrid quadrupole time-of-flight mass spectrometer and fragmentation pathways were elucidated by the use of MS3 on an ion trap mass spectrometer.     

ZnGeP2 parametric oscillator pumped by a linewidth-narrowed parametric 2 microm source

A tandem optical parametric oscillator (OPO) is used to convert radiation from 1.064 microm to the mid-infrared. Spectral bandwidth narrowing close to 80 times compared with a conventional cavity was achieved by using a bulk Bragg grating as an outcoupler in a near-degenerate periodically poled KTiOPO(4) OPO. The narrowed 2,008 nm radiation was subsequently used for pumping the ZnGeP(2) OPO, which was tunable between 3.3 and 5.2 microm. Pulse energies of 170 microJ and pump depletion close to 70% were obtained in the ZnGeP(2) OPO. To our knowledge this is the first time the output from a near-degenerate type I PPKTP OPO has been used for ZnGeP(2) OPO pumping.     

Polygons on a rotating fluid surface

We report a novel and spectacular instability of a fluid surface in a rotating system. In a flow driven by rotating the bottom plate of a partially filled, stationary cylindrical container, the shape of the free surface can spontaneously break the axial symmetry and assume the form of a polygon rotating rigidly with a speed different from that of the plate. With water, we have observed polygons with up to 6 corners. It has been known for many years that such flows are prone to symmetry breaking, but apparently the polygonal surface shapes have never been observed. The creation of rotating internal waves in a similar setup was observed for much lower rotation rates, where the free surface remains essentially flat [J. M. Lopez, J. Fluid Mech. 502, 99 (2004). We speculate that the instability is caused by the strong azimuthal shear due to the stationary walls and that it is triggered by minute wobbling of the rotating plate.     

Efficient and selective sulfoxidation by hydrogen peroxide, using a recyclable flavin--[BMIm]PF6 catalytic system

A new flavin catalyst 2 immobilized in an ionic liquid ([BMIm]PF6) was used for the highly selective oxidation of sulfides to sulfoxides by hydrogen peroxide. The sulfoxides were obtained in good to high yields and high selectivity without any detectable overoxidation to sulfone. The catalyst in the ionic liquid was recycled up to seven times without loss of activity or selectivity.     

Synthesis and reactivity of laquinimod, a quinoline-3-carboxamide: intramolecular transfer of the enol proton to a nitrogen atom as a plausible mechanism for ketene formation

5-Chloro-N-ethyl-1,2-dihydro-4-hydroxy-1-methyl-2-oxo-N-phenyl-3-quinolinecarboxamide (laquinimod, 2) is an oral drug in clinical trials for the treatment of multiple sclerosis. The final step in the synthesis of 2 is a high-yielding aminolysis reaction of ester 1 with N-ethylaniline. An equilibrium exists between 1 and 2, and removal of formed methanol during the reaction is a prerequisite for obtaining high yields of 2 from 1. The reactivity of 1 and 2 is explained by a mechanistic model that involves a transfer of the enol proton to the exocyclic carbonyl substituent with concomitant formation of ketene 3. This proton transfer is especially facilitated for 2 because the intramolecular hydrogen bond to the carbonyl oxygen is weakened due to steric interactions. Both 1 and 2 undergo solvolosis reactions that obey first-order reaction kinetics, further supporting the theory that these two molecules are able to decompose unimolecularly into ketene 3. The solvent-dependent spectroscopic features of 2 indicate that the molecule mainly resides in two conformations. One conformation is favored in nonpolar solvents and is likely the result of intramolecular hydrogen bonding. The other conformation is favored in polar solvents and probably exhibits less intramolecular hydrogen bonding.