Electron spin polarization in a three-electron spin system. An application to bacterial photosynthesis

Calculations on a system consisting of three electron spins and one nuclear spin are presented and their implications for bacterial photosynthesis discussed. Comparison with experimental measurements of electron spin polarization in pre-reduced photosynthetic reaction centres leads to conclusion that the exchange interaction within the primary radical pair is positive and less than 0.8 mT when the g values of the photoinduced radicals are taken to be those measured for the isolated radical species.     

Effects of surfactants on the photosensitized production of tyrosine radicals studied by photo-CIDNP

The influence of the surfactants sodium dodecyl sulphate, cetyltrimethyl-ammonium bromide and triton X-100 on the photochemically induced dynamic nuclear polarization (CIDNP) of N-acetyl tyrosine has been investigated. Three photosensitizers were used to generate polarization: thionin, eosin Y and flavin mononucleotide. 600 MHz 1H photo-CIDNP experiments, supported by laser flash photolysis transient absorption measurements, indicate that the neutral triton surfactant has no influence on the nuclear polarization, but that the other two, charged, amphiphiles affect the photochemistry in a variety of ways, depending on the surfactant concentration and the identity of the sensitizer.     

The potential role of ultrasound in differentiating solid and cystic swellings of the true vocal fold

This study was designed to investigate the potential role of ultrasound in the diagnosis of cysts of the true vocal fold. Materials and Methods: Grayscale ultrasound of the larynx was carried out in 29 patients with a swelling of the true vocal fold and dysphonia. The findings were then compared with those at subsequent microlaryngoscopy, in the majority of cases. Results and Conclusions: Whereas preoperative laryngeal ultrasound correctly predicted the surgical findings of a cystic lesion in only 5 of 11 cases, it correctly identified that no cyst was present in 15 of 16 instances when this had been queried. This study suggests that ultrasound may have some role in investigation of unilateral vocal fold pathology, but that further fine-tuning of the technique may be necessary.     

19F NMR studies of the native and denatured states of green fluorescent protein

Biosynthetic preparation and (19)F NMR experiments on uniformly 3-fluorotyrosine-labeled green fluorescent protein (GFP) are described. The (19)F NMR signals of all 10 fluorotyrosines are resolved in the protein spectrum with signals spread over 10 ppm. Each tyrosine in GFP was mutated in turn to phenylalanine. The spectra of the Tyr --> Phe mutants, in conjunction with relaxation data and results from (19)F photo-CIDNP (chemically induced dynamic nuclear polarization) experiments, yielded a full (19)F NMR assignment. Two (19)F-Tyr residues (Y92 and Y143) were found to yield pairs of signals originating from ring-flip conformers; these two residues must therefore be immobilized in the native structure and have (19)F nuclei in two magnetically distinct positions depending on the orientation of the aromatic ring. Photo-CIDNP experiments were undertaken to probe further the structure of the native and denatured states. The observed NMR signal enhancements were found to be consistent with calculations of the HOMO (highest occupied molecular orbital) accessibilities of the tyrosine residues. The photo-CIDNP spectrum of native GFP shows four peaks corresponding to the four tyrosine residues that have solvent-exposed HOMOs. In contrast, the photo-CIDNP spectra of various denatured states of GFP show only two peaks corresponding to the (19)F-labeled tyrosine side chains and the (19)F-labeled Y66 of the chromophore. These data suggest that the pH-denatured and GdnDCl-denatured states are similar in terms of the chemical environments of the tyrosine residues. Further analysis of the sign and amplitude of the photo-CIDNP effect, however, provided strong evidence that the denatured state at pH 2.9 has significantly different properties and appears to be heterogeneous, containing subensembles with significantly different rotational correlation times.     

Mechanisms of reactions of flavin mononucleotide triplet with aromatic amino acids

Chemical reactions between the photoexcited triplet state of flavin mononucleotide and the aromatic amino acids, N-acetyl tryptophan (TrpH), N-acetyl tyrosine (TyrOH), and N-acetyl histidine (HisH) in aqueous solution have been studied in the pH range 2-12. Across the whole pH range, the principal mechanism of reaction of both TrpH and TyrOH is shown to be electron transfer. For HisH, the mechanism and rate of the reaction depend on the protonation state of the reactants. In acidic conditions (pH < 4), reaction does not occur. At 4 < pH < 11, the reaction proceeds via hydrogen atom abstraction with a rate constant varying from 3.0 x 10(6) to 2.5 x 10(8) M(-1) s(-1). In extremely basic solution (pH > 12) the mechanism switches to electron transfer.     

1H and 13C hyperfine coupling constants of the tryptophanyl cation radical in aqueous solution from microsecond time-resolved CIDNP

Relative values of the 1H and 13C isotropic hyperfine couplings in the cationic oxidized tryptophan radical TrpH*+ in aqueous solution are determined. The data are obtained from the photo-CIDNP (chemically induced dynamic nuclear polarization) enhancements observed in the microsecond time-resolved NMR spectra of the diamagnetic products of photochemical reactions in which TrpH*+ is a transient intermediate. The method is validated using the tyrosyl neutral radical Tyr*, whose 1H and 13C hyperfine couplings have previously been determined by electron paramagnetic resonance spectroscopy. Good agreement is found with hyperfine coupling constants for TrpH*+ calculated using density functional theory methods but only if water molecules are explicitly included in the calculation.     

Microphase separation induced by interfacial segregation of isotropic, spherical nanoparticles

In a recent experiment by Chung et al. [Nano Lett. 5, 1878 (2005)] and simulation by Stratford et al. [Science 309, 2198 (2005)] on immiscible blends containing nanoscale particles, it was shown that the phase separation of the two polymers can be prevented as a result of the aggregation of the nanoparticles at the interfaces between the two polymers. Motivated by these studies, we performed large scale systematic simulations, based on the dissipative particle dynamics approach, on immiscible binary (A-B) fluids containing moderate volume fractions of isotropic nanoscale spherical particles N. The nanoparticles preferentially segregate at the interfaces between the two fluids if the pairwise interactions between the three components are such that chi(AB)>/chi(AN)-chi(BN)/. We find that at later times, the average domain size saturates to a value, L approximately R(N)/phi(N), where R(N) and phi(N) are the radius and volume fraction of the nanoparticles, respectively. For small nanoparticles, however, full phase separation is observed.     

Palladium‐Catalyzed Direct CH Functionalization of Benzoquinone

A direct Pd‐catalyzed C? H functionalization of benzoquinone (BQ) can be controlled to give either mono‐ or disubstituted BQ, including the installation of two different groups in a one‐pot procedure. BQ can now be directly functionalized with aryl, heteroaryl, cycloalkyl, and cycloalkene groups and, moreover, the reaction is conducted in environmentally benign water or acetone as solvents.     

Overtone spectroscopy of some benzaldehyde derivatives

Overtone spectrum of o, m and p-nitrobenzaldehydes and p-chlorobenzaldehyde has been studied in 2000–12000 cm⁻¹ region. Vibrational frequencies and anharmonicity constants for aryl as well as alkyl CH stretch vibrations have been determined. We have also determined the internuclear distances for the aryl CH bond in the different molecules. The small variation observed in these distances is an indication of the substitution effect. It is observed that in the case of p-disubstituted benzens, the shift in aryl CH bond is proportional to sum of the Hammet σ of the substituents. However in the case of o-disubstituted benzenes it is only 80% of the para-substituted shift.     

Spinach--a software library for simulation of spin dynamics in large spin systems

We introduce a software library incorporating our recent research into efficient simulation algorithms for large spin systems. Liouville space simulations (including symmetry, relaxation and chemical kinetics) of most liquid-state NMR experiments on 40+ spin systems can now be performed without effort on a desktop workstation. Much progress has also been made with improving the efficiency of ESR, solid state NMR and Spin Chemistry simulations. Spinach is available for download at http://spindynamics.org.