Air-liquid interfaces of aqueous solutions containing ammonium and sulfate: spectroscopic and molecular dynamics studies

Investigations of the air-liquid interface of aqueous salt solutions containing ammonium (NH(4)(+)) and sulfate (SO(4)(2-)) ions were carried out using molecular dynamics simulations and vibrational sum frequency generation spectroscopy. The molecular dynamics simulations show that the predominant effect of SO(4)(2-) ions, which are strongly repelled from the surface, is to increase the thickness of the interfacial region. The vibrational spectra reported are in the O-H stretching region of liquid water. Isotropic Raman and ATR-FTIR (attenuated total reflection Fourier transform infrared) spectroscopies were used to study the effect of ammonium and sulfate ions on the bulk structure of water, whereas surface sum frequency generation spectroscopy was used to study the effect of these ions on the interfacial structure of water. Analysis of the interfacial and bulk vibrational spectra reveal that aqueous solutions containing SO(4)(2-) perturb the interfacial water structure differently than the bulk and, consistent with the molecular dynamics simulations, reveal an increase in the thickness of the interfacial region.     

Spectroscopic and computational studies of aqueous ethylene glycol solution surfaces

The combination of Monte Carlo, ab initio, and DFT computational studies of ethylene glycol (EG) and EG-water hydrogen-bonding complexes indicate that experimental vibrational spectra of EG and EG-water solution surfaces have contributions from numerous conformations of both EG and EG-water. The computed spectra, derived from harmonic vibrational frequency calculations and a theoretical Boltzmann distribution, show similarity to the experimental surface vibrational spectra of EG taken by broad-bandwidth sum frequency generation (SFG) spectroscopy. This similarity suggests that, at the EG and aqueous EG surfaces, there are numerous coexisting conformations of stable EG and EG-water complexes. A blue shift of the CH2 symmetric stretch peak in the SFG spectra was observed with an increase in the water concentration. This change indicates that EG behaves as a hydrogen-bond acceptor when solvated by additional water molecules. This also suggests that, in aqueous solutions of EG, EG-EG aggregates are unlikely to exist. The experimental blue shift is consistent with the results from the computational studies.     

One-step synthesis of low polydispersity, biotinylated poly(N-isopropylacrylamide) by ATRP

Low polydispersity poly(N-isopropylacrylamide) with a biotin end-group was obtained in one step from a biotinylated initiator for atom transfer radical polymerization and interacted with streptavidin to generate the thermosensitive polymer-protein conjugate.     

Chlorides, oxochlorides, and oxoacids of 1,8-diphosphanaphthalene: a system with imposed close p...p interaction

Several new 1,8-diphosphanaphthalene oxochloro compounds and oxoacids were prepared and fully characterized. The new compounds are discussed in the broader context with other known congeners to demonstrate the variability of the diphosphanaphthalene scaffolding's bonding patterns. Three principal modes of interaction of the phosphorus moieties were observed in the series: bonding, bridging, and repulsive, resulting respectively in none, moderate, and substantial crowding and distortions. The unexpected dimeric diphosphaacenaphthene anion has been obtained from disproportionative hydrolysis of Nap(PCl(2))(2) (Nap = naphthalene-1,8-diyl).     

Structural characterization of the zinc site in protein farnesyltransferase

X-ray absorption spectroscopy has been used to determine the structure of the Zn site in protein farnesyltransferase. Extended X-ray absorption fine structure (EXAFS) data are consistent with a Zn site that is ligated to three low-Z (oxygen or nitrogen) ligands and one cysteine sulfur, as predicted from the crystal structures that are available for farnesyltransferase. However, in contrast with the crystallographic results the EXAFS data do not show evidence for significant distortions in the Zn-ligand distances. The average Zn-(N/O) and Zn-S distances are 2.04 and 2.31 A, respectively. Addition of a farnesyl diphosphate analogue causes no detectable change in the structure of the Zn site. However, addition of peptide substrate causes a change in ligation from ZnS(N/O)(3) to ZnS(2)(N/O)(2), consistent with ligation of the C-terminal cysteine to the Zn. There is no significant change in Zn-ligand distances when a substrate binds, demonstrating that the Zn remains four-coordinate. Addition of both peptide and farnesyl diphosphate to give the product complex causes the Zn to return to ZnS(N/O)(3) ligation, indicating that the product thioether is not tightly coordinated to the Zn. These spectroscopic experiments provide insight into the catalytic mechanism of FTase.     

Preparation of protected photoinitiator nanodepots by the miniemulsion process

The solid photoinitiator Lucirin TPO was encapsulated within a polymer shell by using the miniemulsion process. A solution of Lucirin TPO in methyl methacrylate (MMA) or butyl acrylate (BA)/MMA mixture was miniemulsified in water followed by a polymerization process in which phase separation of the Lucirin TPO and the formed polymer led to amorphously solidified Lucirin TPO nanoparticles encapsulated by polymer. These nanocapsules were freeze-dried and could be redispersed in acidic monomers, which are applied in polymeric dental adhesives. It is shown by ¹H nuclear magnetic resonance spectroscopy that the shell separates the Lucirin TPO, which is sensitive to degradation in acidic media, from an ambient acidic monomer phase and protects it from fast decomposition. Investigations of the release kinetics of Lucirin TPO from the nanocapsules reveal that the kinetics are strongly dependent on the composition of the surrounding continuous phase.     

Coassembly of amphiphiles with opposite peptide polarities into nanofibers

The design, synthesis, and characterization of "reverse" peptide amphiphiles (PAs) with free N-termini is described. Use of an unnatural amino acid modified with a fatty acid tail allows for the synthesis of this new class of PA molecules. The mixing of these molecules with complementary ones containing a free C-terminus results in coassembled structures, as demonstrated by circular dichroism and NOE/NMR spectroscopy. These assemblies show unusual thermal stability when compared to assemblies composed of only one type of PA molecule. This class of reverse PAs has made it possible to create biologically significant assemblies with free N-terminal peptide sequences, which were previously inaccessible, including those derived from phage display methodologies.     

Quantum mechanical models of the resting state of the vanadium-dependent haloperoxidase

Density functional theory has been used to investigate structural and electronic properties of complexes related to the resting form of the active site of vanadium haloperoxidase as a function of environment and protonation state. Results obtained by studying models of varying size and complexity highlight the influence of environment and protonation state on the structure and stability of the metal cofactor. The study shows that, in the trigonal bipyramidal active site, where one axial position is occupied by a key histidine, the trans position cannot contain a terminal oxo group. Further, a highly negatively charged vanadate unit is not stable. Protonation of at least one equatorial oxo ligand appears necessary to stabilize the metal cofactor. The study also indicates that, while at rest within the protein, the vanadate unit is most likely an anion with an axial hydroxide and an equatorial plane containing two oxos and a hydroxide. For the neutral, protonated state of the vanadate unit, there were two minima found. The first structure is characterized by an axial water with two oxo and one hydroxo group in the equatorial plane. The second structure contains an axial hydroxo group and an equatorial plane composed of one oxo and two hydroxo oxygen atoms. These two species are not significantly different in energy, indicating that either form may be important during the catalytic cycle. These data support the initial crystallographic assignment of an axially bound hydroxide, but an axial water is also a possibility. This study also shows that the protonation state of the vanadate ion is most likely greater than previously proposed.     

Solvent effects in tandem mass spectrometry: mechanistic studies indicating how a change in solvent conditions and pH can dramatically alter CID spectra

Dramatically different CID (collision-induced dissociation) spectra are obtained when the complex [Zn(dien-glucose)](+) is electrosprayed from acidic and basic solutions. To understand this peculiar phenomenon, an in-depth mechanistic study was performed on one of the product ions that is present when the initial complex is diluted in basic solution but absent when the complex is diluted with acidic solution. On the basis of the results of this study, the differences in the CID spectra can be rationalized by the fact that the complex electrosprayed from basic solution was kinetically trapped, with the deprotonation site distal from the metal center. Under acidic conditions, the deprotonation site is at a hydroxyl group coordinated to the metal ion. A variety of experiments support this hypothesis. The studies herein underscore the importance of using identical solvent conditions when comparing sets of CID spectra. The data also highlight a very interesting phenomenon involving deprotonation of a hydroxyl group, which was several atoms away from the Zn(II) metal center.     

Enhanced stability to decomposition of a cobalt-dioxygen adduct supported in a copolymer matrix

Summary The decomposition of the Co^II complex of a macrocyclic cyclidene ligand is reported both in solution and when bound to a copolymer support. E.s.r. studies show that the decomposition of the complex in pyridine solution, under an atmosphere of O₂, has an estimated half-life of ca. 36 h at 295 K. This suggests that decomposition of the O₂ adduct is the second step observed in earlier electronic spectroscopic studies, and infers that the cyclidene O₂ adducts are much longer lived than originally thought. The Co^II cyclidene complex forms a coordinate bond to the pyridine group of n-butyl methacrylate/4-vinyl pyridine copolymers and the resulting five-coordinate complexes undergo reversible oxygenation. The polymer-supported O₂ adducts are much more stable to decomposition than those in the solution phase and have an estimated half-life of ca. 30 days at 295 K. The enhanced stability to decomposition of the complexes in the polymer matrix is attributed to the low mobility of the complexes in the glassy polymer.