Rotational dynamics of water and benzene controlled by anion field in ionic liquids: 1-butyl-3-methylimidazolium chloride and hexafluorophosphate

The rotational correlation time (tau(2R)) is determined for D(2)O (polar) and C(6)D(6) (apolar) in 1-butyl-3-methylimidazolium chloride ([bmim][Cl]) and hexafluorophosphate ([bmim][PF(6)]) by measuring (2)H (D) nuclear magnetic resonance spin-lattice relaxation time (T(1)) in the temperature range from -20 to 110 degrees C. The tau(2R) ratio of water to benzene (tau(WB)) was used as a measure of solute-solvent attraction. tau(WB) is 0.73 and 0.52 in [bmim][Cl] and [bmim][PF(6)], respectively, whereas the molecular volume ratio is as small as 0.11. The slowdown of the water dynamics compared to the benzene dynamics in ionic liquids is interpreted by the Coulombic attractive interaction between the polar water molecule and the anion. As for the anion effect, the rotational dynamics of water solvated by Cl(-) is slower than that solvated by PF(6) (-), whereas the rotational dynamics of benzene is similar in the two ionic liquids. This is interpreted as an indication of the stronger solvation by the anion with a larger surface charge density. The slowdown of the water dynamics via Coulombic solvation is actually significant only at water concentrations lower than approximately 9 mol dm(-3) at room temperature, and it is indistinguishable at temperatures above approximately 100 degrees C. The quadrupolar coupling constants determined for D(2)O and C(6)D(6) in the ionic liquids were smaller by a factor of 2-3 than those in the pure liquid state.     

Interpretation of light-scattering spectra in terms of particle displacements

Quasielastic light-scattering spectroscopy is regularly used to examine the dynamics of dilute solutions of diffusing mesoscopic probe particles in fluids. For probes in a simple liquid, the light-scattering spectrum is a simple exponential; the field correlation function g(1)(q,tau) of the scattering particles is related to their mean-square displacements X2 identical with [(delta x(tau))2] during tau via g(1)(q,tau) = exp(-1/2 q2X2). However, demonstrations of this expression refer only to identical Brownian particles in simple liquids and show that if the form is correct then it is also true for all tau that g(1)(q,tau) = exp(-gamma tau), a pure exponential in tau. In general, g(1)(q,tau) is not a single exponential in time. A correct general form for g(1)(q,tau) in terms of the X(2n), replacing the incorrect exp(-1/2 q2X2), is obtained. A simple experimental diagnostic determining when the field correlation function gives the mean-square displacement is identified, namely, g(1)(q,tau) only reveals X2 if g(1)(q,tau) is a single exponential in tau. Contrariwise, if g(1)(q,tau) is not a single exponential, then g(1)(q,tau) depends not only on X2 but on all higher moments X(2n). Corrections to the crude approximation g(1)(q,tau) = exp(-1/2 q2X2) closely resemble the higher spectral cumulants from a cumulant expansion of g(1)(q,tau).     

Rotational and translational diffusion of peptide-coated CdSe/CdS/ZnS nanorods studied by fluorescence correlation spectroscopy

CdSe/CdS/ZnS nanorods (NRs) of three aspect ratios were coated with phytochelatin-related peptides and studied using fluorescence correlation spectroscopy (FCS). Theoretical predictions of the NRs' rotational diffusion contribution to the correlation curves were experimentally confirmed. We monitored rotational and translational diffusion of NRs and extracted hydrodynamic radii from the extracted diffusion constants. Translational and rotational diffusion constants (D(trans) and D(rot)) for NRs were in good agreement with Tirado and Garcia de la Torre's as well as with Broersma's theories when accounting for the ligand dimensions. NRs fall in the size range where rotational diffusion can be monitored with higher sensitivity than translational diffusion due to a steeper length dependence, D(rot) approximately L(-)(3) versus D(trans) approximately L(-)(1). By titrating peptide-coated NRs with bovine serum albumin, we monitored (nonspecific) binding through rotational diffusion and showed that D(rot) is an advantageous observable for monitoring binding. Monitoring rotational diffusion of bioconjugated NRs using FCS might prove to be useful for observing binding and conformational dynamics in biological systems.     

Fluorescence blinking statistics from CdSe core and core/shell nanorods

We report fluorescence blinking statistics measured from single CdSe nanorods (NRs) of seven different sizes with aspect ratios ranging from 3 to 11. This study also included core/shell CdSe/ZnSe NRs and core NRs with two different surface ligands producing different degrees of surface passivation. We compare the findings for NRs to our measurements of blinking statistics from spherical CdSe core and CdSe/ZnS core/shell nanocrystals (NCs). We find that, for both NRs and spherical NCs, the off-time probability distributions are well described by a power law, while the on-time probability distributions are best described by a truncated power law, P(tau(on)) approximately tau(on)(-alpha)e((-tau)(on)/(tau)(c)). The measured crossover time, tau(c), is indistinguishable within experimental uncertainty for core and core/shell NRs, as well as for core NRs with different ligands, for the same core size, indicating that surface passivation does not affect the blinking statistics significantly. We find that, at fixed excitation intensity, 1/tau(c) increases approximately linearly with increasing NR aspect ratio; for a given sample, 1/tau(c) increases very gradually with increasing excitation intensity. Examining 1/tau(c)versus the single-particle photon absorption rate for all samples indicates that the change in NR absorption cross section with sample size can account for some but not all of the differences in crossover time. This suggests that the degree of quantum confinement may be partially responsible for the aspect ratio dependence of the crossover time.     

Quasi-classical trajectory simulations of intramolecular vibrational energy redistribution in HONO2 and DONO2

By use of an analytic potential energy surface developed in this work for nitric acid, the quasi-classical trajectory method was used to simulate intramolecular vibrational energy redistribution (IVR). A method was developed for monitoring the average vibrational energy in the OH (or OD) mode that uses the mean-square displacement of the bond length calculated during the trajectories. This method is effective for both rotating and nonrotating molecules. The calculated IVR time constant for HONO(2) decreases exponentially with increasing excitation energy, is almost independent of rotational temperature, and is in excellent agreement with the experimental determination (Bingemann, D.; Gorman, M. P.; King, A. M.; Crim, F. F. J. Chem.Phys. 1997, 107, 661). In DONO(2), the IVR time constants show more complicated behavior with increasing excitation energy, apparently due to 2:1 Fermi-resonance coupling with lower frequency modes. This effect should be measurable in experiments.     

Structural and Transport Properties of Alumina Porous Membranes from Process-Based and Statistical Reconstruction Techniques

We study the structural and transport properties of two model porous membranes made by compaction of spherical monosize gamma-alumina particles. A ballistic deposition process of spherical particles has been employed as a process-based representation method for accurately simulating the pore structure of the membranes. Comparison between the computed and experimental permeability values obtained in the Knudsen regime shows very good agreement for both membranes and indicates that sufficient representation of the original pore structure is achieved with the random sphere packs. In a further step, a medium with the same porosity and autocorrelation function as the sphere pack has been stochastically reconstructed. Comparison between the structural properties of the random sphere pack system (process-based model) and the stochastically reconstructed medium (statistical model) shows nearly identical correlation functions and pore chord length distributions but widely different mass chord length distributions. This is reflected to a significant difference in the prediction of a dynamic property like the Knudsen permeability by a factor of about 4. The results suggest that matching of the porosity and the two-point correlation function alone is not always adequate when pursuing an accurate representation of the structure of a porous material. In such cases, higher order statistical properties of the material contained in the chord length distribution of both pore and solid phase should be satisfied as well. It is also found that proper account of the formation process in the reconstruction of a porous material (process-based model) leads to representations of its structure more accurate than those of statistical reconstruction models. Copyright 2000 Academic Press.     

Ab initio molecular-dynamics study of supercritical carbon dioxide

Car-Parrinello molecular-dynamics simulations of supercritical carbon dioxide (scCO(2)) have been performed at the temperature of 318.15 K and at the density of 0.703 g/cc in order to understand its microscopic structure and dynamics. Atomic pair correlation functions and structure factors have been obtained and good agreement has been found with experiments. In the supercritical state the CO(2) molecule is marginally nonlinear, and thus possesses a dipole moment. Analyses of angle distributions between near neighbor molecules reveal the existence of configurations with pairs of molecules in the distorted T-shaped geometry. The reorientational dynamics of carbon dioxide molecules, investigated through first- and second-order time correlation functions, exhibit time constants of 620 and 268 fs, respectively, in good agreement with nuclear magnetic resonance experiments. The intramolecular vibrations of CO(2) have been examined through an analysis of the velocity autocorrelation function of the atoms. These reveal a red shift in the frequency spectrum relative to that of an isolated molecule, consistent with experiments on scCO(2). The results have also been compared to classical molecular-dynamics calculations employing an empirical potential.     

Extended model free approach to analyze correlation functions of multidomain proteins in the presence of motional coupling

Interdomain motion in proteins plays an important role in biomolecular interaction. Its presence also complicates interpretation of many spectroscopy measurements. Nuclear magnetic resonance (NMR) study of domain dynamics relies on knowledge of its rotational correlation function. The extended model free (EMF) approach has been implemented to analyze coupled domain and overall motions for calmodulin, a dual-domain protein; however, the validity of EMF treatment in coupled motion has not been tested. We performed stochastic simulations on a dual-vector system employing two simple restraints to drive hydrodynamics and domain coupling: (1) both unitary vectors diffuse randomly on the surface of a sphere and (2) vectors are correlated through user-defined intervector potential. The resulting correlation curve can be adequately fit with either a single- or double-exponential decay function. The latter is consistent with the EMF treatment. The derived order parameters S (2) range from about 0.4 to 1, while the motion separation, the ratio of overall and domain motion time scales (tau m/tau s), ranges from 1 to 4. A complete overlap between time scales occurs when S (2) is less than 0.4, and the correlation function effectively behaves as a single-exponential. The S (2) values are consistent with theoretical predictions from the given potential function, differing by no more than 0.03, suggesting EMF to be a generally valid approach. In addition, from the dependence of S (2) on tau m/tau s obtained from simulation, we found a cosine potential, favoring extended conformers, as opposed to the normally assumed cone potential, reached a better agreement to experimental data.     

In search of temporal power laws in the orientational relaxation near isotropic-nematic phase transition in model nematogens

Recent Kerr relaxation experiments by Gottke et al. have revealed the existence of a pronounced temporal power law decay in the orientational relaxation near the isotropic-nematic phase transition (INPT) of nematogens of rather small aspect ratio, kappa (kappa approximately 3-4). We have carried out very long (50 ns) molecular dynamics simulations of model (Gay-Berne) prolate ellipsoids with aspect ratio 3 in order to investigate the origin of this power law. The model chosen is known to undergo an isotropic to nematic phase transition for a range of density and temperature. The distance dependence of the calculated angular pair correlation function correctly shows the emergence of a long range correlation as the INPT is approached along the density axis. In the vicinity of INPT, the single particle second rank orientational time correlation function exhibits power law decay, (t(-alpha)) with exponent alpha approximately 2/3. More importantly, we find the sudden appearance of a pronounced power-law decay in the collective part of the second rank orientational time correlation function at short times when the density is very close to the transition density. The power law has an exponent close to unity, that is, the correlation function decays almost linearly with time. At long times, the decay is exponential-like, as predicted by Landau-de Gennes mean field theory. Since Kerr relaxation experiments measure the time derivative of the collective second rank orientational pair correlation function, the simulations recover the near independence of the signal on time observed in experiments. In order to capture the microscopic essence of the dynamics of pseudonematic domains inside the isotropic phase, we introduce and calculate a dynamic orientational pair correlation function (DOPCF) obtained from the coefficients in the expansion of the distinct part of orientational van Hove time correlation function in terms of spherical harmonics. The DOPCF exhibits power law relaxation when the pair separation length is below certain critical length. The orientational relaxation of a local director, defined in terms of the sum of unit vectors of all the ellipsoidal molecules, is also found to show slow power law relaxation over a long time scale. These results have been interpreted in terms of a newly developed mode coupling theory of orientational dynamics near the INPT. In the present case, the difference between the single particle and the collective orientational relaxation is huge which can be explained by the frequency dependence of the memory kernel, calculated from the mode coupling theory. The relationship of this power law with the one observed in a supercooled liquid near its glass transition temperature is explored.     

CH5+: chemistry's chameleon unmasked

The nuclear vibrational wave function and zero-point vibrational energy of CH5(+) are calculated using quantum diffusion Monte Carlo techniques on an interpolated potential energy surface constructed from CCSD(T)/aug'-cc-pVTZ ab initio data. From this multidimensional wave function, the vibrationally averaged rotational constants and radial distribution functions for atom-atom distances within the molecule are constructed. It is found that the distributions of all 10 H-H distances are bimodal and identical. The radial distribution functions obtained for the five C-H distances are also identical, but unimodal. The three rotational constants were found to be 3.78, 3.80, and 3.83 cm(-1). These values indicate that the ground state of CH5(+) is significantly more symmetric than its global minimum energy structure. We conclude that the zero-point motion of CH5(+) renders all five protons equivalent in the ground state and precludes the assignment of a unique structure to the molecule.     

Solvation shell dynamics studied by molecular dynamics simulation in relation to the translational and rotational dynamics of supercritical water and benzene

The solvation shell dynamics of supercritical water is analyzed by molecular dynamics simulation with emphasis on its relationship to the translational and rotational dynamics. The relaxation times of the solvation number (tau S), the velocity autocorrelation function (tau D), the angular momentum correlation function (tau J), and the second-order reorientational correlation function (tau 2R) are studied at a supercritical temperature of 400 degrees C over a wide density region of 0.01-1.5 g cm(-3). The relaxation times are decomposed into those conditioned by the solvation number n, and the effect of the short-ranged structure is examined in terms of its probability Pn of occurrence. In the low to medium-density range of 0.01-0.4 g cm(-3), the time scales of water dynamics are in the following sequence: tau D>tau S approximately or > tau J approximately or > tau 2R. This means that the rotation in supercritical water is of the "in-shell" type while the translational diffusion is not. The comparison to supercritical benzene is also performed and the effect of hydrogen bonding is examined. The water diffusion is not of the in-shell type up to the ambient density of 1.0 g cm(-3), which corresponds to the absence of the transition from the collision to the Brownian picture, whereas such transition is present in the case of benzene. The absence of the transition in water comes from the fast reorganization of the hydrogen bonds and the enhanced mobility of the solvation shell in supercritical conditions.     

Proton dynamics in lithium-ammonia solutions and expanded metals

Quasielastic neutron scattering has been used to study proton dynamics in the system lithium-ammonia at concentrations of 0, 4, 12, and 20 mole percent metal (MPM) in both the liquid and solid (expanded metal) phases. At 230 K, in the homogenous liquid state, we find that the proton self-diffusion coefficient first increases with metal concentration, from 5.6x10(-5) cm2 s(-1) in pure ammonia to 7.8x10(-5) cm2 s(-1) at 12 MPM. At higher concentrations we note a small decrease to a value of 7.0x10(-5) cm2 s(-1) at 20 MPM (saturation). These results are consistent with NMR data, and can be explained in terms of the competing influences of the electron and ion solvation. At saturation, the solution freezes to form a series of expanded metal compounds of composition Li(NH3)4. Above the melting point, at 100 K, we are able to fit our data to a jump-diffusion model, with a mean jump length (l) of 2.1 A and residence time (tau) of 3.1 ps. This model gives a diffusion coefficient of 2.3x10(-5) cm2 s(-1). In solid phase I (cubic, stable from 88.8 to 82.2 K) we find that the protons are still undergoing this jump diffusion, with l=2.0 A and tau=3.9 ps giving a diffusion coefficient of 1.8x10(-5) cm2 s(-1). Such motion gives way to purely localized rotation in solid phases IIa (from 82.2 to 69 K) and IIb (stable from 69 to 25 K). We find rotational correlation times (tau(rot)) of the order of 2.0 and 7.3 ps in phases IIa and IIb, respectively. These values can be compared with a rotational mode in solid ammonia with tau(rot) approximately 2.4 ps at 150 K.     

A simplified model of the ECD

A simplified model of the ECD is presented, which is based on the assumption that only a change in the concentration of electron is generating a signal. The model allows to determine four different time constants related to: the collection of electrons (tau(1)), the loss of electrons in the capture process by the impurity molecules (tau(2)), the loss of sample molecules by electron capture (tau(n)) and the removing rate of molecules from the detector volume by the carrier gas (tau(v)). The values of these time constants have been estimated to be in the range of micros for tau(1), ms for tau(2), a part of a second for tau(n) and a few seconds for tau(v). The electron capture efficiency coefficient (p) and the detection coefficient (S(d)) have been defined. These coefficients serve in the model for the coulometric calculation of the mass of analyzed compounds, if the detector works using the conditions described.     

The effect of the spatial nonlocality of the Kirkwood g-factor on the determination of the long wavelength dielectric functions in dipolar fluids

The Kirkwood g-factor that determines the long wavelength dielectric constant of a simple, isotropic, translationally invariant dipolar fluid is given by an integral of a dipole-dipole correlation function over a spherical region of a nonzero radius R(K) chosen such that any further increase in the radius leads to no change in the value of the integral, thereby defining a Kirkwood correlation length R(K). For radii less than the correlation length the integral defines a radius dependent (nonlocal) Kirkwood g-factor, implying a nonlocal dielectric function. The nonlocal nature of these quantities has important consequences for the determination of the long wavelength dielectric function from dipole fluctuations via the Kirkwood-Fro?hlich connection. The dipole-dipole correlation function (the volume dipole auto-correlation function) commonly used in this determination involves particles residing solely within a sphere of radius R, unlike the correct correlation function which involves either a single particle with those particles in a spherical volume of radius R(K) or those particles in a spherical volume of radius R with those residing within a spherical volume of radius R+R(K). A procedure is suggested for extracting the infinite system dipole-dipole correlation function from results of simulations performed on finite spherical samples. Using some results reported in the recent literature, relative to the accurate correlation function the commonly used correlation function ranges from 27% too small for a sphere having a radius comparable to the Kirkwood correlation length to 4% too small at a radius of seven times that correlation length. As a result, the apparent dielectric constants, as determined by the conventional procedure of using the fluctuations of the sum of dipoles in a finite fixed volume, are also too small. This suggests that a dielectric constant extracted from computer simulations using a total dipole-total dipole correlation function in a given volume with other geometries and/or boundary conditions will result in similar errors.     

Rotational dynamics account for pH-dependent relaxivities of PAMAM dendrimeric, Gd-based potential MRI contrast agents

The EPTPA5) chelate, which ensures fast water exchange in GdIII complexes, has been coupled to three different generations (5, 7, and 9) of polyamidoamine (PAMAM) dendrimers through benzylthiourea linkages (H5EPTPA = ethylenepropylenetriamine-N,N,N',N',N'-pentaacetic acid). The proton relaxivities measured at pH 7.4 for the dendrimer complexes G5-(GdEPTPA)111, G7-(GdEPTPA)253 and G9-(GdEPTPA)1157 decrease with increasing temperature, indicating that, for the first time for dendrimers, slow water exchange does not limit relaxivity. At a given field and temperature, the relaxivity increases from G5 to G7, and then slightly decreases for G9 (r1 = 20.5, 28.3 and 27.9 mM(-1) s(-1), respectively, at 37 degrees C, 30 MHz). The relaxivities show a strong and reversible pH dependency for all three dendrimer complexes. This originates from the pH-dependent rotational dynamics of the dendrimer skeleton, which was evidenced by a combined variable-temperature and multiple-field 17O NMR and 1H relaxivity study performed at pH 6.0 and 9.9 on G5-(GdEPTPA)111. The longitudinal 17O and 1H relaxation rates of the dendrimeric complex are strongly pH-dependent, whereas they are not for the [Gd(EPTPA)(H2O)]2- monomer chelate. The longitudinal 17O and 1H relaxation rates have been analysed by the Lipari-Szabo spectral density functions and correlation times have been calculated for the global motion of the entire macromolecule (tau(gO)) and the local motion of the GdIII chelates on the surface (tau(lO)), correlated by means of an order parameter S2. The dendrimer complex G5-(GdEPTPA)111 has a considerably higher tau(gO) under acidic than under basic conditions (tau(298)gO = 4040 ps and 2950 ps, respectively), while local motions are less influenced by pH (tau(298)lO = 150 and 125 ps). The order parameter, characterizing the rigidity of the macromolecule, is also higher at pH 6.0 than at pH 9.9 (S2 = 0.43 vs 0.36, respectively). The pH dependence of the global correlation time can be related to the protonation of the tertiary amine groups in the PAMAM skeleton, which leads to an expanded and more rigid dendrimeric structure at lower pH. The increase of tau(gO) with decreasing pH is responsible for the pH dependent proton relaxivities. The water exchange rate on G5-(GdEPTPA)111(k(298)ex = 150 x 10(6) s(-1)) shows no significant pH dependency and is similar to the one measured for the monomer [Gd(EPTPA)(H2O)]2-. The proton relaxivity of G5-(GdEPTPA)111 is mainly limited by the important flexibility of the dendrimer structure, and to a small extent, by a faster than optimal water exchange rate.     

Synthesis and characterization of the novel monoamide derivatives of Gd-TTDA

For this study, the N'-monoamide derivatives of TTDA (3,6,10-tri(carboxymethyl)-3,6,10-triazadodecanedioic acid), N'-methylamide (TTDA-MA), N'-benzylamide (TTDA-BA), and N'-2-methoxybenzylamide (TTDA-MOBA), were synthesized. Their protonation constants and stability constants (log K(ML)'s) formed with Ca(2+), Zn(2+), Cu(2+), and Gd(3+) were determined by potentiometric titration in 0.10 M Me(4)NCl at 25.0 +/- 0.1 degrees C. The relaxivity values of [Gd(TTDA-MA)](-), [Gd(TTDA-BA)](-), and [Gd(TTDA-MOBA)](-) remained constant with respect to pH changes over the range 4.5-12.0. The (17)O NMR chemical shift of H(2)O induced by [Dy(TTDA-MA)(H(2)O)](-) at pH 6.80 showed 0.9 inner-sphere water molecules. Water proton relaxivity values for [Gd(TTDA-MA)(H(2)O)](-), [Gd(TTDA-BA)(H(2)O)](-), and [Gd(TTDA-MOBA)(H(2)O)](-) at 37.0 +/- 0.1 degrees C and 20 MHz are 3.89, 4.21, and 4.25, respectively. The water-exchange lifetime (tau(M)) and rotational correlation time (tau(R)) of [Gd(TTDA-MA)(H(2)O)](-), [Gd(TTDA-BA)(H(2)O)](-), and [Gd(TTDA-MOBA)(H(2)O)](-) are obtained from reduced the (17)O relaxation rate and chemical shifts of H(2)(17)O. The (2)H NMR longitudinal relaxation rates of the deuterated diamagnetic lanthanum complexes for the rotational correlation time were also thoroughly investigated. The water-exchange rates (K(298)(ex) for [Gd(TTDA-MA)(H(2)O)](-), [Gd(TTDA-BA)(H(2)O)](-), and [Gd(TTDA-MOBA)(H(2)O)](-) are lower than that of [Gd(TTDA)(H(2)O)](2)(-) but significantly higher than those of [Gd(DTPA)(H(2)O)](2)(-) and [Gd(DTPA-BMA)(H(2)O)]. The rotational correlation times for [Gd(TTDA-BA)(H(2)O)](-) and [Gd(TTDA-MOBA)(H(2)O)](-) are significantly longer than those of [Gd(TTDA)(H(2)O)](2)(-) and [Gd(DTPA)(H(2)O)](2)(-) complexes. The marked increase of the relaxivity of [Gd(TTDA-BA)(H(2)O)](-) and [Gd(TTDA-MOBA)(H(2)O)](-) results mainly from their longer rotational correlation time. The noncovalent interaction between human serum albumin (HSA) and [Gd(TTDA-BA)(H(2)O)](-) and [Gd(TTDA-MOBA)(H(2)O)](-) complexes containing a hydrophobic substituent was investigated by measuring the water proton relaxation rate of the aqueous solutions. The binding association constant (K(A)) values are 1.0 +/- 0.2 x 10(3) and 1.3 +/- 0.2 x 10(3) M(-1) for [Gd(TTDA-BA)(H(2)O)](-) and [Gd(TTDA-MOBA)(H(2)O)](-), which indicates a stronger interaction of [Gd(TTDA-BA)(H(2)O)](-) and [Gd(TTDA-MOBA)(H(2)O)](-) with HSA.     

Extraction of lifetime distributions from fluorescence decays with application to DNA-base analogues

Several important aspects of fluorescence decay analysis are addressed and tested against new experimental measurements. A simulated-annealing method is described for deconvoluting the instrument response function from a measured fluorescence decay to yield the true decay, which is more convenient for subsequent fitting. The method is shown to perform well against the conventional approach, which is to fit a convoluted fitting function to the experimentally measured decay. The simulated annealing approach is also successfully applied to the determination of an instrument response function using a known true fluorescence decay (for rhodamine 6G). The analysis of true fluorescence decays is considered critically, focusing specifically on how a distribution of decay constants can be incorporated in to a fit. Various fitting functions are applied to the true fluorescence decays of 2-aminopurine in water-dioxane mixtures, in a dinucleotide, and in DNA duplexes. It is shown how a suitable combination of exponential decays and non-exponential decays (based on a Γ distribution of decay constants) can provide fits of equal quality to the conventional multi-exponential fits used in the majority of previous studies, but with fewer fitting parameters. Crucially, the new approach yields decay-constant distributions that are physically more meaningful than those corresponding to the conventional multi-exponential fit. The methods presented here should find wider application, for example to the analysis of transient-current or optical decays and in F?rster resonance energy transfer (FRET).     

Velocity dependence of polarised rotational transfer rates: close-coupled calculations on model systems

Expressions for the laboratory-frame rate constants for polarised rotational energy transfer, as a function of molecular velocity, have been derived for atom-diatom systems. These equations require the kinetic energy dependence of the collision-frame cross sections, which have been obtained by close-coupled calculations using four different N₂-rare gas potentials over the temperature range 0 to 400 K. The energy dependence of multipolar cross sections is presented as are results for spherical and cylindrical velocity distributions. These model calculations indicate strongly that information on intermolecular potentials may be obtained from polarisation ratio velocity dependence measurements.     

The interaction of MS-325 with human serum albumin and its effect on proton relaxation rates

MS-325 is a novel blood pool contrast agent for magnetic resonance imaging currently undergoing clinical trials to assess blockage in arteries. MS-325 functions by binding to human serum albumin (HSA) in plasma. Binding to HSA serves to prolong plasma half-life, retain the agent in the blood pool, and increase the relaxation rate of water protons in plasma. Ultrafiltration studies with a 5 kDa molecular weight cutoff filter show that MS-325 binds to HSA with stepwise stoichiometric affinity constants (mM(-1)) of K(a1) = 11.0 +/- 2.7, K(a2) = 0.84 +/- 0.16, K(a3) = 0.26 +/- 0.14, and K(a4) = 0.43 +/- 0.24. Under the conditions 0.1 mM MS-325, 4.5% HSA, pH 7.4 (phosphate-buffered saline), and 37 degrees C, 88 +/- 2% of MS-325 is bound to albumin. Fluorescent probe displacement studies show that MS-325 can displace dansyl sarcosine and dansyl-L-asparagine from HSA with inhibition constants (K(i)) of 85 +/- 3 microM and 1500 +/- 850 microM, respectively; however, MS-325 is unable to displace warfarin. These results suggest that MS-325 binds primarily to site II on HSA. The relaxivity of MS-325 when bound to HSA is shown to be site dependent. The Eu(III) analogue of MS-325 is shown to contain one inner-sphere water molecule in the presence and in the absence of HSA. The synthesis of an MS-325 analogue, 5, containing no inner-sphere water molecules is described. Compound 5 is used to estimate the contribution to relaxivity from the outer-sphere water molecules surrounding MS-325. The high relaxivity of MS-325 bound to HSA is primarily because of a 60-100-fold increase in the rotational correlation time of the molecule upon binding (tau(R) = 10.1 +/- 2.6 ns bound vs 115 ps free). Analysis of the nuclear magnetic relaxation dispersion (T(1) and T(2)) profiles also suggests a decrease in the electronic relaxation rate (1/T(1e) at 20 MHz = 2.0 x 10(8) s(-1) bound vs 1.1 x 10(9) s(-1) free) and an increase in the inner-sphere water residency time (tau(m) = 170 +/- 40 ns bound vs 69 +/- 20 ns free).