Strong oscillations in molecular valence photoemission intensities

Photoemission from the two outermost ionizations [highest occupied molecular orbitals (HOMO and HOMO-1)] of Mg(eta(5)-C(5)H(5))(2) has been studied with synchrotron radiation in the gas phase. Strong oscillations in the HOMO-1/HOMO ratio, qualitatively similar to those well-known for fullerenes, are found. Excellent agreement with the experimental ratio is provided by accurate cross section calculations both at the density-functional theory and time-dependent density-functional theory level, indicating that a many electron response has a minor role for this effect. A comparison with the calculated values for other metal sandwich compounds indicate that the presence of oscillations is a widespread phenomenon, and a potential source of interesting information on the structural and electronic properties of the target molecule.     

Study of tryptophan assisted synthesis of gold nanoparticles by combining UV–Vis, fluorescence, and SERS spectroscopy

We developed a rapid and non-toxic method for the preparation of colloidal gold nanoparticles (GNPs) by using tryptophan (Trp) as reducing/stabilizing agent. We show that the temperature has a major influence on the kinetics of gold ion reduction and the crystal growth, higher temperatures favoring the synthesis of anisotropic nanoparticles (triangles and hexagons). The as-synthesized nanostructures were characterized by UV–Vis absorption spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD), fluorescence, and surface-enhanced Raman scattering (SERS) spectroscopy. The UV–Vis measurements confirmed that temperature is a critical factor in the synthesis process, having a major effect on the shape of the synthesized GNPs. Moreover, fluorescence spectroscopy was able to monitor the quenching of the Trp fluorescence during the in situ synthesis of GNPs. Using Trp as molecular analyte to evaluate the SERS efficiency of as-prepared GNPs at different temperatures, we demonstrated that the Raman enhancement of the synthesized gold nanoplates is higher than that of the gold spherical nanoparticles.     

Columnar bis(pyridinium) ionic liquid crystals derived from 4-hydroxypyridine: synthesis,mesomorphism and emission properties

A series of flexibly linked bis(pyridinium) salts with various counterions (Br^?, PF₆^?, BF₄^? and OTf-) was designed and prepared starting from corresponding N-alkylated 4-pyridones precursors with mesogenic 3,4,5-tris(alkyloxy)benzyl moieties (alkyl = dodecyl or tetradecyl). These salts were investigated for their liquid crystalline properties by a combination of differential scanning calorimetry, polarising optical microscopy and temperature-dependent powder X-ray diffraction (XRD). Their thermal stability was checked by thermogravimetric analysis. All bis(pyridinium) salts, except the triflate salt with shorter terminal carbon chain, display an enantiotropic liquid crystalline behaviour with a hexagonal columnar (Col_h) phase assigned on the basis of its characteristic texture and XRD studies. It was found that these luminescent bis(pyridinium) salts show weak emission in dichloromethane solutions at room temperature and a pronounced red-shifted emission in solid state. The emission properties of these bis(pyridinium) salts do not depend significantly on the nature of counterion employed.     

A Novel [OSSO]-Type Chromium(III) Complex as a Versatile Catalyst for Copolymerization of Carbon Dioxide with Epoxides

A new chromium(III) complex, bearing a bis-thioether-diphenolate [OSSO]-type ligand, was found to be an efficient catalyst in the copolymerization of CO₂ and epoxides to achieve poly(propylene carbonate), poly(cyclohexene carbonate), poly(hexene carbonate) and poly(styrene carbonate), as well as poly(propylene carbonate)(cyclohexene carbonate) and poly(propylene carbonate)(hexene carbonate) terpolymers.     

Krull’s theory for the double gamma function

The Barnes’ G-function G(x) = 1/Γ₂, satisfies the functional equation logG(x + 1) − logG(x) = logΓ(x). We complement W. Krull’s work in Bemerkungen zur Differenzengleichung g(x + 1) − g(x) = φ(x), Math. Nachrichten 1 (1948), 365-376 with additional results that yield a different characterization of the function G, new expansions and sharp bounds for G on x > 0 in terms of Gamma and Digamma functions, a new expansion for the Gamma function and summation formulae with Polygamma functions.     

Electrochemically controlled formation/dissociation of phosphonate-cavitand/methylpyridinium complexes

The phosphorus-bridged cavitand 1 self-assembles very efficiently in CH2Cl2 with either the monopyridinium guest 2+ or the bispyridinium guest 3(2+). In the first case a 1:1 complex is obtained, whereas in the second case both 1:1 and 2:1 host-guest complexes are observed. The association between 1 and either one of the guests causes the quenching of the cavitand fluorescence; in the case of the adduct between 1 and 3(2+), the fluorescence of the latter is also quenched. Cavitand complexation is found to affect the reduction potential values of the electroactive guests. Voltammetric and spectroelectrochemical measurements show that upon one-electron reduction both guests are released from the cavity of 1. Owing to the chemical reversibility of such redox processes, the supramolecular complexes can be re-assembled upon removal of the extra electron from the guest. Systems of this kind are promising for the construction of switchable nanoscale devices and self-assembling supramolecular materials, the structure and properties of which can be reversibly controlled by electrochemical stimuli.     

Controlling the electrophoretic mobility of single-walled carbon nanotubes: a comparison of theory and experiment

The electrophoretic mobilities of single-walled carbon nanotubes (SWNTs) in agarose gels subjected to negatively charged covalent functionalization and noncovalent anionic surfactant adsorption are compared using a simplified hydrodynamic model. Net charges are calculated on the basis of estimated friction coefficients for cylindrical rodlike particles. The effects of functionalization with negatively charged 4-hydroxybenzene diazonium and anionic sodium cholate are quantified and compared with model predictions. The adsorption of Na+ counterions into the nonionic surfactant layer adsorbed on SWNTs (Triton-X-405) is shown to induce a positive charge and reverse the mobility under select conditions. This effect has not been identified or quantified for nanoparticle systems and may be important in the processing of these systems.     

Effect of bending and torsion rigidity on self-diffusion in polymer melts: a molecular-dynamics study

Extensive molecular-dynamics simulations have been performed to study the effect of chain conformational rigidity, controlled by bending and torsion potentials, on self-diffusion in polymer melts. The polymer model employs a novel torsion potential that avoids computational singularities without the need to impose rigid constraints on the bending angles. Two power laws are traditionally used to characterize the dependence of the self-diffusion coefficient on polymer length: D proportional to N(-nu) with nu=1 for NNe (reptation regime), Ne being the entanglement length. Our simulations, at constant temperature and density, up to N=250 reveal that, as the chain rigidity increases, the exponent nu gradually increases towards nu=2.0 for NNe. The value of Ne is slightly increased from 70 for flexible chains, up to the point where the crossover becomes undefined. This behavior is confirmed also by an analysis of the bead mean-square displacement. Subsequent investigations of the Rouse modes, dynamical structure factor, and chain trajectories indicate that the pre-reptation regime, for short stiff chains, is a modified Rouse regime rather than reptation.     

Supramolecular architectures of streptavidin on biotinylated self-assembled monolayers. Tracking biomolecular reorganization after bioconjugation

In this work we have studied the supramolecular bioconjugation of streptavidin (SAv) on biotinylated self-assembled monolayers. By using the quartz crystal microbalance technique with dissipation we were able to follow in real time the biomolecular reorganization within the film. The overall process could be described as an early stage involving a significant increase in surface coverage followed by another stage where the SAv layer slowly reached the asymptotic coverage. Finally, a reorganization process takes place in the bioconjugated film. These results on the kinetics of biomolecular reorganization can be described in terms of the Lifshitz-Slyozov law. These are the first experimental results demonstrating the complexity and the different time scales involved on the bioconjugation of SAv at solid-liquid interfaces. We consider that these findings could have strong implications on the molecular design of biosensing platforms.     

Target-templated de novo design of macrocyclic d-/l-peptides: discovery of drug-like inhibitors of PD-1

Peptides are a rapidly growing class of therapeutics with various advantages over traditional small molecules, especially for targeting difficult protein–protein interactions. However, current structure-based methods are largely limited to natural peptides and are not suitable for designing bioactive cyclic topologies that go beyond natural l-amino acids. Here, we report a generalizable framework that exploits the computational power of Rosetta, in terms of large-scale backbone sampling, side-chain composition and energy scoring, to design heterochiral cyclic peptides that bind to a protein surface of interest. To showcase the applicability of our approach, we developed two new inhibitors (PD-i3 and PD-i6) of programmed cell death 1 (PD-1), a key immune checkpoint in oncology. A comprehensive biophysical evaluation was performed to assess their binding to PD-1 as well as their blocking effect on the endogenous PD-1/PD-L1 interaction. Finally, NMR elucidation of their in-solution structures confirmed our de novo design approach.

In silico design of heterochiral cyclic peptides that bind to a specific surface patch on the target protein (PD-1, in this case) and disrupt protein–protein interactions.