TIRF microscopy as a screening method for non-specific binding on surfaces

We report a method for studying nanoparticle-biosensor surface interactions based on total internal reflection fluorescence (TIRF) microscopy. We demonstrate that this simple technique allows for high throughput screening of non-specific adsorption (NSA) of nanoparticles on surfaces of different chemical composition. Binding events between fluorescent nanoparticles and functionalized Zeonor? surfaces are observed in real-time, giving a measure of the attractive or repulsive properties of the surface and the kinetics of the interaction. Three types of coatings have been studied: one containing a polymerized aminosilane network with terminal -NH(2) groups, a second film with a high density of -COOH surface groups and the third with sterically restraining branched poly(ethylene)glycol (PEG) functionality. TIRF microscopy revealed that the NSA of nanoparticles with negative surface charge on such modified coatings decreased in the following order -NH(2)>-branched PEG>-COOH. The surface specificity of the technique also allows discrimination of the degree of NSA of the same surface at different pH.     

Communication: uncovering molecule-TiO2 interactions with nonlinear spectroscopy

Femtosecond transient grating experiments are used to investigate electronic structures and transport mechanisms in dye-sensitized nanocrystalline TiO(2) films. This study examines two molecular sensitizers spanning the weak (a phosphonated Ruthenium complex) and strong (catechol) molecule-TiO(2) coupling regimes. It is shown that strong molecule-TiO(2) interactions give rise to photoinduced vibrational coherences at the interface between species. We suggest that the amplitudes of these coherences reflect the molecule-TiO(2) coupling strength and signify the delocalization of excited state wavefunctions.     

Colloidal rotation near the colloidal glass transition

We compare, using single-particle optical imaging, trajectories of rotation and translation for micron-sized spheres in index-matched colloidal suspensions near their glass transition. Rotational trajectories, while they show intermittent caged behavior associated with supercooled and glassy behavior, explore a sufficiently wider phase space such that in the averaged mean-square angular displacement there appears no plateau regime, but instead sub-Fickian angular diffusion that follows an apparent power law in time. We infer translation and rotation time constants, the former being the time to diffuse a particle diameter and the latter being the time to rotate a full revolution. Correlation between time constants increases with increasing volume fraction, but unlike the case for molecular glasses, the rotation time constant slows more weakly than the translation time.     

Photoelectron angular distributions from autoionizing 4s¹4p⁶6p¹ states in atomic krypton probed with femtosecond time resolution

Photoelectron angular distributions (PADs) are obtained for a pair of 4s(1)4p(6)6p(1) (a singlet and a triplet) autoionizing states in atomic krypton. A high-order harmonic pulse is used to excite the pair of states and a time-delayed 801 nm ionization pulse probes the PADs to the final 4s(1)4p(6) continuum with femtosecond time resolution. The ejected electrons are detected with velocity map imaging to retrieve the time-resolved photoelectron spectrum and PADs. The PAD for the triplet state is inherently separable by virtue of its longer autoionization lifetime. Measuring the total signal over time allows for the PADs to be extracted for both the singlet state and the triplet state. Anisotropy parameters for the triplet state are measured to be β(2)=0.55 ± 0.17 and β(4)=-0.01 ± 0.10, while the singlet state yields β(2)=2.19 ± 0.18 and β(4)=1.84 ± 0.14. For the singlet state, the ratio of radial transition dipole matrix elements, X, of outgoing S to D partial waves and total phase shift difference between these waves, Δ, are determined to be X=0.56 ± 0.08 and Δ=2.19 ± 0.11 rad. The continuum quantum defect difference between the S and D electron partial waves is determined to be -0.15 ± 0.03 for the singlet state. Based on previous analyses, the triplet state is expected to have anisotropy parameters independent of electron kinetic energy and equal to β(2)=5∕7 and β(4)=-12∕7. Deviations from the predicted values are thought to be a result of state mixing by spin-orbit and configuration interactions in the intermediate and final states; theoretical calculations are required to quantify these effects.     

Electron ionization of SiCl4

Relative partial ionization cross sections (PICS) for the formation of fragment ions following electron ionization of SiCl(4), in the electron energy range 30-200 eV, have been determined using time-of-flight mass spectrometry coupled with an ion coincidence technique. By this method, the contributions to the yield of each fragment ion from dissociative single, double, and triple ionization, are distinguished. These yields are quantified in the form of relative precursor-specific PICS, which are reported here for the first time for SiCl(4). For the formation of singly charged ionic fragments, the low-energy maxima appearing in the PICS curves are due to contributions from single ionization involving predominantly indirect ionization processes, while contributions to the yields of these ions at higher electron energies are often dominated by dissociative double ionization. Our data, in the reduced form of relative PICS, are shown to be in good agreement with a previous determination of the PICS of SiCl(4). Only for the formation of doubly charged fragment ions are the current relative PICS values lower than those measured in a previous study, although both datasets agree within combined error limits. The relative PICS data presented here include the first quantitative measurements of the formation of Cl(2) (+) fragment ions and of the formation of ion pairs via dissociative double ionization. The peaks appearing in the 2D ion coincidence data are analyzed to provide further information concerning the mechanism and energetics of the charge-separating dissociations of SiCl(4) (2+). The lowest energy dicationic precursor state, leading to SiCl(3) (+) + Cl(+) formation, lies 27.4 ± 0.3 eV above the ground state of SiCl(4) and is in close agreement with a calculated value of the adiabatic double ionization energy (27.3 eV).     

Halide, amide, cationic, manganese carbonylate, and oxide derivatives of triamidosilylamine uranium complexes

Treatment of the complex [U(Tren(TMS))(Cl)(THF)] [1, Tren(TMS) = N(CH(2)CH(2)NSiMe(3))(3)] with Me(3)SiI at room temperature afforded known crystalline [U(Tren(TMS))(I)(THF)] (2), which is reported as a new polymorph. Sublimation of 2 at 160 °C and 10(-6) mmHg afforded the solvent-free dimer complex [{U(Tren(TMS))(μ-I)}(2)] (3), which crystallizes in two polymorphic forms. During routine preparations of 1, an additional complex identified as [U(Cl)(5)(THF)][Li(THF)(4)] (4) was isolated in very low yield due to the presence of a slight excess of [U(Cl)(4)(THF)(3)] in one batch. Reaction of 1 with one equivalent of lithium dicyclohexylamide or bis(trimethylsilyl)amide gave the corresponding amide complexes [U(Tren(TMS))(NR(2))] (5, R = cyclohexyl; 6, R = trimethylsilyl), which both afforded the cationic, separated ion pair complex [U(Tren(TMS))(THF)(2)][BPh(4)] (7) following treatment of the respective amides with Et(3)NH·BPh(4). The analogous reaction of 5 with Et(3)NH·BAr(f)(4) [Ar(f) = C(6)H(3)-3,5-(CF(3))(2)] afforded, following addition of 1 to give a crystallizable compound, the cationic, separated ion pair complex [{U(Tren(TMS))(THF)}(2)(μ-Cl)][BAr(f)(4)] (8). Reaction of 7 with K[Mn(CO)(5)] or 5 or 6 with [HMn(CO)(5)] in THF afforded [U(Tren(TMS))(THF)(μ-OC)Mn(CO)(4)] (9); when these reactions were repeated in the presence of 1,2-dimethoxyethane (DME), the separated ion pair [U(Tren(TMS))(DME)][Mn(CO)(5)] (10) was isolated instead. Reaction of 5 with [HMn(CO)(5)] in toluene afforded [{U(Tren(TMS))(μ-OC)(2)Mn(CO)(3)}(2)] (11). Similarly, reaction of the cyclometalated complex [U{N(CH(2)CH(2)NSiMe(2)Bu(t))(2)(CH(2)CH(2)NSiMeBu(t)CH(2))}] with [HMn(CO)(5)] gave [{U(Tren(DMSB))(μ-OC)(2)Mn(CO)(3)}(2)] [12, Tren(DMSB) = N(CH(2)CH(2)NSiMe(2)Bu(t))(3)]. Attempts to prepare the manganocene derivative [U(Tren(TMS))MnCp(2)] from 7 and K[MnCp(2)] were unsuccessful and resulted in formation of [{U(Tren(TMS))}(2)(μ-O)] (13) and [MnCp(2)]. Complexes 3-13 have been characterized by X-ray crystallography, (1)H NMR spectroscopy, FTIR spectroscopy, Evans method magnetic moment, and CHN microanalyses.     

Room temperature aryl trifluoromethylation via copper-mediated oxidative cross-coupling

A method for the room temperature copper-mediated trifluoromethylation of aryl and heteroaryl boronic acids has been developed. This protocol is amenable to normal benchtop setup and reactions typically require only 1-4 h. Proceeding under mild conditions, the method tolerates a range of functional groups, allowing access to a variety of trifluoromethylarenes.     

Stereoselective total synthesis of aminoiminohexitols via carbamate annulation

New methodology for the preparation of a variety of aminoiminohextitols is described. Key in the synthesis is the application of a diastereoselective Strecker reaction and the extension of our carbamate annulation methodology to protected and functionalized alkenylamines. Insight into the effects that the substitution patterns of the alkenylamines have on the diastereoselectivity of the iodocyclization and carbamate annulation is discussed. An evaluation of the glycosidase inhibitory activity of the aminoiminohexitols and derivatives is also presented, with the previously undisclosed D-talo isomer showing good selective inhibition of β-D-glucosidase.