Parallel proton transfer pathways in aqueous acid-base reactions.

We study the mechanism of proton transfer (PT) between the photoacid 8-hydroxy-1,3, 6-pyrenetrisulfonic acid (HPTS) and the base chloroacetate in aqueous solution. We investigate both proton and deuteron transfer reactions in solutions with base concentrations ranging from 0.25 M to 4 M.

A single Caenorhabditis elegans Golgi apparatus-type transporter of UDP-glucose, UDP-galactose, UDP-N-acetylglucosamine, and UDP-N-acetylgalactosamine.

The genome of Caenorhabditis elegans encodes for 18 putative nucleotide sugar transporters even though its glycome only contains 7 different monosaccharides. To understand the biological significance of this phenomenon, we have begun a systematic substrate characterization of the above putative transporters and have determined that the gene ZK896.9 encodes a Golgi apparatus transporter for UDP-glucose, UDP-galactose, UDP- N-acetylglucosamine, and UDP- N-acetylgalactosamine.

Strong slowing down of water reorientation in mixtures of water and tetramethylurea.

We use mid-infrared pump-probe spectroscopy to study the ultrafast dynamics of HDO molecules in mixtures of tetramethylurea (TMU) and water. The composition of the studied solutions ranges from pure water to an equimolar mixture of water and TMU. We find that the vibrational relaxation of the OD-stretching vibration of HDO proceeds via an intermediate level in which the molecule is more strongly hydrogen bonded than in the ground state.

A CMP-sialic acid transporter cloned from Arabidopsis thaliana.

Sialylation of glycans is ubiquitous in vertebrates, but was believed to be absent in plants, arthropods, and fungi. However, recently evidence has been provided for the presence of sialic acid in these evolutionary clades. In addition, homologs of mammalian genes involved in sialylation can be found in the genomes of these taxa and for some Drosophila enzymes, involvement in sialic acid metabolism has been documented.

Vibrational dynamics of ice in reverse micelles.

The ultrafast vibrational dynamics of HDO:D(2)O ice at 180 K in anionic reverse micelles is studied by midinfrared femtosecond pump-probe spectroscopy. Solutions containing reverse micelles are cooled to low temperatures by a fast-freezing procedure. The heating dynamics of the micellar solutions is studied to characterize the micellar structure.

Transient absorption of vibrationally excited ice Ih.

The ultrafast dynamics of HDO:D2O ice Ih at 180 K is studied by midinfrared ultrafast pump-probe spectroscopy. The vibrational relaxation of HDO:D2O ice is observed to proceed via an intermediate state, which has a blueshifted absorption spectrum. Polarization resolved measurements reveal that the intermediate state is part of the intramolecular relaxation pathway of the HDO molecule.

Inhibition of proinflammatory genes in anti-GBM glomerulonephritis by targeted dexamethasone-loaded AbEsel liposomes.

E-selectin-directed targeted drug delivery was analyzed in anti-glomerular basement membrane glomerulonephritis. Liposomes conjugated with anti-E-selectin antibodies (Ab(Esel) liposomes) were internalized by activated endothelial cells in vitro through E-selectin-mediated endocytosis. At the onset of glomerulonephritis in mice, E-selectin was expressed on glomerular endothelial cells, which resulted in homing of Ab(Esel) liposomes to glomeruli after intravenous administration.

Far-infrared second-harmonic generation and pulse characterization with the organic salt DAST.

We generated the second harmonics of pulses in the far-infrared region (30-55 microm), using the organic salt dimethylamino-4-N-methylstilbazolium tosylate (DAST). We demonstrate that DAST can be used to characterize ultrashort pulses in a spectral region where no other materials are available. To illustrate the need for such characterizations, we show the effects of propagation through air on the shape of ultrashort far-infrared pulses.

Long-range proton transfer in aqueous Acid-base reactions.

We study the mechanism of proton transfer (PT) in the aqueous acid-base reaction between the photoacid 8-hydroxy-1,3,6-pyrenetrisulfonic acid (HPTS) and acetate by probing the vibrational resonances of HPTS, acetate, and the hydrated proton with femtosecond mid-infrared laser pulses. We find that PT takes place in a distribution of hydrogen-bound reaction complexes that differ in the number of water molecules separating the acid and the base. The number of intervening water molecules ranges from 0 to 5, which, together with a strongly distance-dependent PT rate, explains the observed highly nonexponential reaction kinetics.

Optical phonon dynamics of GaAs studied with time-resolved terahertz spectroscopy.

We investigate the reflection near the reststrahlen band of the optical phonon in bulk GaAs in the time domain, using time-resolved terahertz spectroscopy. We find that the dynamics of the reflection measured for GaAs differs strongly from the reflection dynamics that would be expected for a TO phonon with a frequency-independent dephasing time.

Generation of mid-infrared pulses by X(3) difference frequency generation in CaF(2) and BaF(2).

Tunable mid-IR pulses in the range 1300-4200 cm(-1) (7.7-2.4 microm) are generated through a phase-matched four-wave mixing process in ordinary mid-IR window materials such as CaF(2) and BaF(2) .

Liver mtDNA content increases during development: a comparison of methods and the importance of age- and tissue-specific controls for the diagnosis of mtDNA depletion.

Background: The quantitative loss of mitochondrial DNA (mtDNA) known as mtDNA depletion, often gives rise to liver disease. The diagnosis of mtDNA depletion syndrome is frequently imprecise, both for technical reasons and because of the lack of established age-adjusted normal ranges. We aimed to refine quantitative methods for diagnosing the hepatic type of mtDNA depletion syndrome, firstly by establishing an age-matched reference range for mitochondrial to nuclear DNA ratio (henceforth "mtDNA content") and secondly by investigating mtDNA in fibroblasts.

On the role of water in intermolecular proton-transfer reactions.

We study the mechanism of proton transfer (PT) between the photoacid (8-hydroxy-1,3,6-pyrenetrisulfonic acid (HPTS)) and the base acetate in aqueous solution using femtosecond vibrational spectroscopy. By probing the vibrational resonances of the photoacid, the accepting base, and the hydrated proton we find that intermolecular PT in this model system involves the transfer of the proton across several water molecules linking the donor-acceptor pair by hydrogen bonds (H-bonds). We find that at high base concentration the rate of PT is not determined by the mutual diffusion of acid and base but rather by the rate of Grotthuss-like conduction of the proton between molecules.

Observation of immobilized water molecules around hydrophobic groups.

We have used femtosecond midinfrared spectroscopy to study the orientational mobility of water molecules in the hydration shells of hydrophobic groups. Our results show that hydrophobic groups are surrounded by a number of water molecules that display much slower orientational dynamics than the bulk liquid and that are therefore effectively immobilized. It turns out that each methyl group is surrounded by four immobilized water OH groups.

Distinct contributions of beta 4GalNAcTA and beta 4GalNAcTB to Drosophila glycosphingolipid biosynthesis.

Drosophila melanogaster has two beta4-N-acetylgalactosaminyltransferases, beta4GalNAcTA and beta4GalNAcTB, that are able to catalyse the formation of lacdiNAc (GalNAcbeta,4GlcNAc). LacdiNAc is found as a structural element of Drosophila glycosphingolipids (GSLs) suggesting that beta4GalNAcTs contribute to the generation of GSL structures in vivo. Mutations in Egghead and Brainaic, enzymes that generate the beta4GalNAcT trisaccharide acceptor structure GlcNAcbeta,3Manbeta,4GlcbetaCer, are lethal.

Development of postural control in typically developing children and children with cerebral palsy: possibilities for intervention?

The basic level of postural control is functionally active from early infancy onwards: young infants possess a repertoire of direction-specific postural adjustments. Whether or not direction-specific adjustments are used depends on the child's age and the nature of the postural task. The second level of control emerges after 3 months: children start to develop the capacity to adapt postural activity to environmental constraints.

Steady-state pharmacokinetics of pravastatin in children with familial hypercholesterolaemia.

Objective: To determine pharmacokinetic data for pravastatin in children, since current data are insufficient in this age group.

Subjects And Methods: A 2-week, multiple-dose, steady-state pharmacokinetic study was carried out with pravastatin 20mg daily in 24 children with familial hypercholesterolaemia (aged 8-16 years; 12 prepubertal, 12 pubertal). A plasma concentration-time curve was performed on day 14.

Postural adjustments and reaching in 4- and 6-month-old infants: an EMG and kinematical study.

Adequate postural control is a prerequisite for daily activities such as reaching for an object. However, knowledge on the relationship between postural adjustments and the quality of reaching movements during human ontogeny is scarce. Therefore we evaluated the development of the relationship between the kinematic features of reaching movements and the accompanying postural adjustments in young infants.

A phase I/IIa study with succinylated human serum albumin (Suc-HSA), a candidate HIV-1 fusion inhibitor.

Background: Succinylated human serum albumin (Suc-HAS) is a negatively charged neo-glycoprotein that binds to the positively charged V3-loop of HIV-1 gp120, acting as HIV-1-fusion inhibitor in vitro (IC50: 0.5-5.0 microg/ml).

Water as a molecular hinge in amidelike structures.

The authors have studied the reorientational dynamics of isolated water molecules in a solution of N,N-dimethylacetamide (DMA). From linear spectra, the authors find that the water in this solution forms double hydrogen bond connections to the DMA molecules, resulting in the formation of DMA-water-DMA complexes. The authors use polarization-resolved mid-infrared pump-probe spectroscopy on the water in these complexes to measure the depolarization of three distinct transition dipole moments, each with a different directionality relative to the molecular frame (OH stretch in HDO, symmetric and asymmetric stretch normal modes in H(2)O).

Site-specific inhibition of glomerulonephritis progression by targeted delivery of dexamethasone to glomerular endothelium.

Glomerulonephritis represents a group of renal diseases with glomerular inflammation as a common pathologic finding. Because of the underlying immunologic character of these disorders, they are frequently treated with glucocorticoids and cytotoxic immunosuppressive agents. Although effective, use of these compounds has limitations as a result of toxicity and systemic side effects.

Ultrafast dynamics of water in cationic micelles.

The effect of confinement on the dynamical properties of liquid water is investigated for water enclosed in cationic reverse micelles. The authors performed mid-infrared ultrafast pump-probe spectroscopy on the OH-stretch vibration of isotopically diluted HDO in D(2)O in cetyltrimethylammonium bromide (CTAB) reverse micelles of various sizes. The authors observe that the surfactant counterions are inhomogeneously distributed throughout the reverse micelle, and that regions of extreme salinity occur near the interfacial Stern layer.

Efficient introduction of a bisecting GlcNAc residue in tobacco N-glycans by expression of the gene encoding human N-acetylglucosaminyltransferase III.

In this study, we show that introduction of human N-acetylglucosaminyltransferase (GnT)-III gene into tobacco plants leads to highly efficient synthesis of bisected N-glycans. Enzymatically released N-glycans from leaf glycoproteins of wild-type and transgenic GnT-III plants were profiled by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) in native form. After labeling with 2-aminobenzamide, profiling was performed using normal-phase high-performance liquid chromatography with fluorescence detection, and glycans were structurally characterized by MALDI-TOF/TOF-MS and reverse-phase nano-liquid chromatography-MS/MS.

Effect of urea on the structural dynamics of water.

We use polarization-resolved mid-infrared pump-probe spectroscopy to study the effect of urea on the structure and dynamics of water. Surprisingly, we find that, even at high concentrations of urea (8 M), the orientational dynamics of most water molecules are the same as in pure liquid water, showing that urea has a negligible effect on the hydrogen-bond dynamics of these molecules. However, a small fraction of the water molecules (approximately one water molecule per urea molecule) turns out to be strongly immobilized by urea, displaying orientational dynamics that are more than six times slower than in bulk water.