Molecular structures of M(Bu(t))3 (M = Al, Ga, In) using gas-phase electron diffraction and ab initio calculations: experimental and computational evidence for charge-transfer processes leading to photodissociation

The gas-phase structures of AI(Bu')3 and Ga(Bu')3 have been investigated by electron diffraction and are shown to consist of monomeric units with very slightly pyramidal geometries. Salient structural parameters (r(hl)) include r(A1-C) = 2.008(2) A and r(Ga-C) = 2.032(2) A. For both compounds the ligand orientations and geometries are controlled by interligand interactions. The structures of M(Bu(t))3 (M = Al, Ga, In) have been calculated ab initio and those for the aluminium and gallium derivatives are in good agreement with the electron-diffraction structures. Comparison of the ab initio calculated structure of In(Bu')3 with those of Al(Bu(t))3 and Ga(Bu(t))3 suggests that the significantly different photochemistry exhibited by the former does not result from structural factors. In fact the compounds undergo a charge-transfer process in the UV region, with the wavelength required calculated to be slightly longer for the indium compound than for the other two.     

Effective diffusion coefficients for methanol in sulfuric acid solutions measured by Raman spectroscopy

The diffusion of methanol into 0-96.5 wt % sulfuric acid solutions was followed using Raman spectroscopy. Because methanol reacts to form protonated methanol (CH 3OH 2 (+)) and methyl hydrogen sulfate in H 2SO 4 solutions, the reported diffusion coefficients, D, are effective diffusion coefficients that include all of the methyl species diffusing into H 2SO 4. The method was first verified by measuring D for methanol into water. The value obtained here, D = (1.4 +/- 0.6) x 10 (-5) cm (2)/s, agrees well with values found in the literature. The values of D in 39.2-96.5 wt % H 2SO 4 range from (0.11-0.3) x 10 (-5) cm (2)/s, with the maximum value of D occurring for 61.6 wt % H 2SO 4. The effective diffusion coefficients do not vary systematically with the viscosity of the solutions, suggesting that the speciation of both methanol and sulfuric acid may be important in determining these transport coefficients.     

The role of surface defects in multi-exciton generation of lead selenide and silicon semiconductor quantum dots

Multi-exciton generation (MEG), the creation of more than one electron-hole pair per photon absorbed, occurs for excitation energies greater than twice the bandgap (E(g)). Imperfections on the surface of quantum dots, in the form of atomic vacancies or incomplete surface passivation, lead to less than ideal efficiencies for MEG in semiconductor quantum dots. The energetic onset for MEG is computed with and without surface defects for nanocrystals, Pb(4)Se(4), Si(7), and Si(7)H(2). Modeling the correlated motion of two electrons across the bandgap requires a theoretical approach that incorporates many-body effects, such as post-Hartree-Fock quantum chemical methods. We use symmetry-adapted cluster with configuration interaction to study the excited states of nanocrystals and to determine the energetic threshold of MEG. Under laboratory conditions, lead selenide nanocrystals produce multi-excitons at excitation energies of 3 E(g), which is attributed to the large dielectric constant, small Coulomb interaction, and surface defects. In the absence of surface defects the MEG threshold is computed to be 2.6 E(g). For lead selenide nanocrystals with non-bonding selenium valence electrons, Pb(3)Se(4), the MEG threshold increases to 2.9 E(g). Experimental evidence of MEG in passivated silicon quantum dots places the onset of MEG at 2.4 E(g). Our calculations show that the lowest multi-exciton state has an excitation energy of 2.5 E(g), and surface passivation enhances the optical activity of MEG. However, incomplete surface passivation resulting in a neutral radical on the surface drives the MEG threshold to 4.4 E(g). Investigating the mechanism of MEG at the atomistic level provides explanations for experimental discrepancies and suggests ideal materials for photovoltaic conversion.     

Structure and noncanonical chemistry of nonribosomal peptide biosynthetic machinery

Covering up to January 2012Structural biology has provided significant insights into the complex chemistry and macromolecular organization of nonribosomal peptide synthetases. In addition, novel pathways are continually described, expanding the knowledge of known biosynthetic chemistry.     

High-performance liquid chromatographic analysis of lacosamide in canine serum using ultraviolet detection: application to pre-clinical pharmacokinetics in dogs

A method for analysis of lacosamide [(R)‐2‐acetamido‐N‐benzyl‐3‐methoxypropionamide] is needed for both human and veterinary pharmacokinetic investigations. While lacosamide is currently used to manage partial‐onset seizures in humans suffering from epilepsy, it is also presently being investigated for use in the treatment of canine epilepsy in veterinary medicine. Currently, no dosing regimen for the drug exists in dogs. A novel and simple high‐performance liquid chromatography method was developed for determination of lacosamide in dog serum. Serum proteins (0.1 mL) were precipitated with ?20.0°C acetonitrile after addition of the internal standard, daidzein. Separation was achieved with a Phenomenex® Luna® C₁₈ (2) (5 µm, 250 × 4.60 mm) column with ultraviolet detection at 210 nm. The calibration curves were linear ranging from 0.5 to 25 µg/mL. Precision of the assay was <13% (RSD) and was within 12% for all points in the calibration curve. The limit of quantitation for this method was 0.5 µg/mL. The assay was applied successfully to a pre‐clinical study of lacosamide pharmacokinetics in dogs. Copyright © 2011 John Wiley & Sons, Ltd.     

Nature of the chemical bond in transition: dissection of radical-molecule reactivity

A complete method for quantifying the Born-Oppenheimer barriers of radical--molecule abstraction reactions is derived from first principles with the dual objectives of analytical prediction and conceptual understanding. Expanding upon the work of Donahue et al. (J. Phys. Chem. A 1998, 102, 3923-3933) this treatment uses the strategic construction of reactant-like and product-like wave functions to evaluate the coupling between crossing diabatic states. The overall reaction coordinate is evaluated in a modular fashion, whereby each region is analyzed within the context of its governing physics.     

Selective patterning of Si-based biosensor surfaces using isotropic silicon etchants

Ultra-sensitive, label-free biosensors have the potential to have a tremendous impact on fields like medical diagnostics. For the majority of these Si-based integrated devices, it is necessary to functionalize the surface with a targeting ligand in order to perform specific biodetection. To do this, silane coupling agents are commonly used to immobilize the targeting ligand. However, this method typically results in the bioconjugation of the entire device surface, which is undesirable. To compensate for this effect, researchers have developed complex blocking strategies that result in selective patterning of the sensor surface. Recently, silane coupling agents were used to attach biomolecules to the surface of silica toroidal biosensors integrated on a silicon wafer. Interestingly, only the silica biosensor surface was conjugated. Here, we hypothesize why this selective patterning occurred. Specifically, the silicon etchant (xenon difluoride), which is used in the fabrication of the biosensor, appears to reduce the efficiency of the silane coupling attachment to the underlying silicon wafer. These results will enable future researchers to more easily control the bioconjugation of their sensor surfaces, thus improving biosensor device performance.     

Conjugation of siRNA with Comb‐Type PEG Enhances Serum Stability and Gene Silencing Efficiency

A thiol‐modified siRNA targeting the enhanced green fluorescence protein (eGFP) gene was conjugated with RAFT‐synthesized, pyridyl disulfide‐functional poly(PEG methyl ether acrylate)s (p(PEGA)s). siRNA‐p(PEGA) conjugates demonstrated significantly enhanced in vitro serum stability and nuclease resistance compared to the unmodified and thiol‐modified siRNA. The complexes of siRNA‐p(PEGA) conjugates with a fusogenic peptide, KALA ((+)/(–) = 2) inhibited the protein expression approximately 28‐fold more than the KALA complex of the unmodified siRNA. The protein inhibition caused by siRNA‐p(PEGA)‐KALA complexes (56 ± 5%–58 ± 3% of the fluorescence expressed in non‐treated cells) was comparable to the effect of the unmodified siRNA‐lipofectamine complex (77 ± 7%).

     

Experimental verification of minima in excited long-range Rydberg states of Rb2

Recent theoretical studies with alkali atoms A* excited to high Rydberg states predicted the existence of ultra-long-range molecular bound states. Such excited dimers have large electric dipole moments which, in combination with their long radiative lifetimes, make them excellent candidates for manipulation in applications. This Letter reports on experimental investigations of the self-broadening of Rb principal series lines, which revealed multiple satellites in the line wings. The positions of the satellites agree quantitatively with theoretically predicted minima in the excited long-range Rydberg states of Rb2.