Novel air-stable and volatile bis(pyridylalkenolato)palladium(II) and -platinum(II) derivatives

Six novel homoleptic palladium(II) and platinum(II) complexes of donor-substituted alkenol ligands [PyCHC(R)OH; Py = pyridine, R = CH(3), CF(3), C(2)F(5), C(3)F(7)] of the general formula M[PyCHC(R)O](2) (M = Pd, Pt) were synthesized by reacting the deprotonated ligands with PdCl(2) and K(2)PtCl(4), respectively. Molecular structures, revealed by single-crystal X-ray diffraction analyses, showed a square-planar arrangement of ligands around palladium and platinum centers, with the pyridine-ring nitrogen atoms situated in a mutually trans position. The monomeric nature of the compounds in the solution state was confirmed by multinuclear ((1)H, (13)C, and (19)F) NMR spectroscopy. Thermal decomposition profiles recorded under a nitrogen atmosphere suggested their potential as volatile precursors to palladium and platinum materials. The volatility was increased upon elongation of the perfluoroalkyl chain, which suppressed the intermolecular interactions, as is evident in crystal packings. The volatility of these compounds was attributed to bidentate chelation of the alkenol units and cooperativity among the electron-back-donating nitrogen atom and interplay of electron-withdrawing C(x)F(y) groups, resulting in an effective steric shielding of the metal atoms.     

A facile method of producing femtoliter metal cups by pulsed laser ablation

Cuplike structures of Au, Ag, Cu, Zn, Nb, Cd, Al, In, and Sn in the size range of 300 nm to a few micrometers with an internal volume of a few femtoliters have been produced by the laser ablation of metal targets in a vacuum, by optimizing, in each case, the laser fluence and the substrate temperature. The metal droplets impinging on the substrate seem to undergo a hydraulic jump driven by the surface tension forces before solidifying into cups. The cups are robust and can be functionalized with biomarkers, filled with nanoparticle sols, oxidized to crucibles, or detached from the substrate without causing any deformation. We envisage their potential applications as femtoliter metal containers.     

Energy pooling in multiple ionization and Coulomb explosion of clusters by nanosecond-long, megawatt laser pulses

We report the results of experiments that establish the possibility of bringing about multiple ionization and Coulomb explosion of molecular clusters with nanosecond laser pulses at intensities as small as 10(9) W cm(-2). We demonstrate several new facets of the laser-cluster interaction in the low-intensity, long-pulse domain: (i) The choice of laser wavelength for a given cluster species is very crucial. (ii) Excited electronic states play a very important role in the ionization dynamics. (iii) When field ionization is insignificant and ponderomotive energies are very small, it is energy pooling rather than inverse bremsstrahlung that determines how clusters absorb energy from the optical field.     

Intense two-cycle laser pulses induce time-dependent bond hardening in a polyatomic molecule

A time-dependent bond-hardening process is discovered in a polyatomic molecule (tetramethyl silane, TMS) using few-cycle pulses of intense 800 nm light. In conventional mass spectrometry, symmetrical molecules such as TMS do not exhibit a prominent molecular ion (TMS(+)) as unimolecular dissociation into [Si(CH(3))(3)](+) proceeds very fast. Under a strong field and few-cycle conditions, this dissociation channel is defeated by time-dependent bond hardening: a field-induced potential well is created in the TMS(+) potential energy curve that effectively traps a wave packet. The time dependence of this bond-hardening process is verified using longer-duration (≥100 fs) pulses; the relatively slower falloff of optical field in such pulses allows the initially trapped wave packet to leak out, thereby rendering TMS(+) unstable once again.     

Nanoencapsulation and characterization of Albizia chinensis isolated antioxidant quercitrin on PLA nanoparticles

The plant isolated antioxidant quercitrin has been encapsulated on poly-d,l-lactide (PLA) nanoparticles by solvent evaporation method to improve the solubility, permeability and stability of this molecule. The size of quercitrin-PLA nanoparticles is 250 ± 68 nm whereas that PLA nanoparticles is 195 ± 55 nm. The encapsulation efficiency of nanoencapsulated quercitrin evaluated by HPLC and antioxidant assay is 40%. The in vitro release kinetics of quercitrin under physiological condition reveals initial burst release followed by sustained release. Less fluorescence quenching is observed with equimolar concentration of PLA encapsulated quercitrin than free quercitrin. The presence of quercitrin specific peaks on FTIR of five times washed quercitrin loaded PLA nanoparticles provides an extra evidence for the encapsulation of quercitrin into PLA nanoparticles. These properties of quercitrin nanomedicine provide a new potential for the use of such less useful highly active antioxidant molecule towards the development of better therapeutic for intestinal anti-inflammatory effect and nutraceutical compounds.