Coherence-converted population transfer FTMW-IR double resonance spectroscopy of CH3OD in the OD-stretch region

Rotationally selected infrared spectra of jet-cooled CH₃OD have been recorded and analyzed in the OD-stretch region (2710-2736 cm⁻¹). The observed spectra are obtained by monitoring three E-species microwave transitions (1₋₁ ← 1₀ at 18.957 GHz, 2₋₁ ← 2₀ at 18.991 GHz, and 3₋₁ ← 3₀ at 19.005 GHz) in a narrowband cavity Fourier transform microwave spectrometer, using the background-free coherence-converted population transfer technique. Of the four upper state subbands observed, two (K′ = 0 and −2) are split by perturbations. The E-species deperturbed band origin is at 2718.1 cm⁻¹. The deperturbed reduced term values follow a pattern similar to the ground state. This allows the J′ = 0 torsional tunneling splitting to be estimated as 2.1 cm⁻¹, which can be compared to 2.6 cm⁻¹ in the ground state.     

Enhanced Photoinduced Electron Transfer at the Surface of Charged Lipid Bilayers

Photocatalytic systems often suffer from poor quantum yields due to fast charge recombination: The energy‐wasting annihilation of the photochemically created charge‐separated state. In this report, we show that the efficiency of photoinduced electron transfer from a sacrificial electron donor to positively charged methyl viologen, or to negatively charged 5,5′‐dithiobis(2‐nitrobenzoate), increases dramatically upon addition of charged phospholipid vesicles if the charge of the lipids is of the same sign as that of the electron acceptor. Centrifugation and UV/Vis titration experiments showed that the charged photosensitizers adsorb at the liposome surface, that is, where the photocatalytic reaction takes place. The increased photoelectron transfer efficiency in the presence of charged liposomes has been ascribed to preferential electrostatic interactions between the photosensitizer and the membrane, which prevents the formation of photosensitizer–electron‐acceptor complexes that are inactive towards photoreduction. Furthermore, it is shown that the addition of liposomes results in a decrease in photoproduct inhibition, which is caused by repulsion of the reduced electron acceptor by the photocatalytic site. Thus, liposomes can be used as a support to perform efficient photocatalysis; the charged photoproducts are pushed away from the liposomes and represent “soluble electrons” that can be physically separated from the place where they were generated.     

The 3-Methyl-1,3-butadienyl Phenyl Sulfoxide II. Utilization as a Michael Acceptor of Lithiated Protected Cyanohydrins. Syntheses of Tagetones and Ocimenones

In contradistinction to the α, β-unsaturated sulfoxides, few reports have been published on the Michael reactivity of the α,β-γ,δ-diunsaturated sulfoxides¹. We present here the details of our investigation on the title sulfoxide 5 as a reagent for the synthesis of terpenoid polyenones.     

Reaction of 1, 1-Bis(Methylthio)-3-Methyl-1, 3-Butadiene with Lithiated 3-Methyl-2-Butenyl Phenyl Sulfide. A Special Case of Cyclopropane Formation

Abstract

The conjugated ketene dithioacetal 2 is now available by three different procedures¹. This electrophilic isoprene compound has been shown to add smoothly some simple lithio derivatives, but the addition of 3-methyl-2-butenyl-lithium gave a product with total inversion of the starting allylic chain^1a.     

Femtosecond laser ablation of gold in water: influence of the laser-produced plasma on the nanoparticle size distribution

We have demonstrated that a thick polymer cover layer can significantly improve UV laser micromachining. The polymer cover layer acts as a wave-guide, concentrating the incoming laser beam onto the underlying substrate to be machined. With this method very low laser fluences can be used to drill fine, high aspect ratio holes in quartz, glass and other materials that are generally difficult to machine. We show that despite the improvements recorded, our experimental conditions are not optimized and the contribution of the cover layers in our experiments is less than what it could be. We suggest improvements to the cover layer material to improve the micomachining. The method has important advantages over conventional methods since a mask is not required and common laser equipment can be used to quickly and inexpensively form desired holes within the substrate. PACS 89.20.Bb     

Supercontinuum generation by nanosecond dual-pumping near the two zero-dispersion wavelengths of a photonic crystal fiber

Supercontinuum generation by dual-wavelength nanosecond pumping in the vicinity of both zero-dispersion wavelengths of a photonic crystal fiber (PCF) is experimentally demonstrated. It is shown in particular that two pumps at 1535 nm and 767 nm simultaneously pumping near the two zero-dispersion wavelengths of a specially designed PCF yields a combined visible and infrared supercontinuum spectrum spanning from 0.55 μm to 1.9 μm. We discuss the generation mechanisms underlying the continuum formation in terms of modulation instability and cascaded Raman generation.     

Homoleptic zinc(II) complexes with first and second coordination shells of 5-tert-butylpyrazole

Reaction of hydrated Zn[NO3]2 or Zn[BF4]2 with four or more equivalents of 3{5}-tert-butylpyrazole (L(tBu)) yields [Zn(L(tBu))4]X2 (X- = NO3- or BF4-). The nitrate complex contains C2-symmetric four-coordinate zinc(II) centers with a slightly flattened tetrahedral geometry, and each nitrate anion hydrogen bonds to two pyrazole N-H groups. Similar reactions with Zn[ClO4]2 or ZnCl2 in the presence of 2 equiv of AgPF6 or AgSbF6 yield instead [{Zn(L(tBu))4}(L(tBu))4][ClO4]2 and [{Zn(L(tBu))4}(L(tBu))2]Y2 (Y- = PF6- or SbF6-). Crystals of [{Zn(L(tBu))4}(L(tBu))4][ClO4]2 are composed of discrete [{Zn(L(tBu))4}(L(tBu))4]2+ supramolecules that are formed from N-H...N hydrogen bonding between zinc-bound and uncoordinated pyrazole rings. The [{Zn(L(tBu))4}(L(tBu))4]2+ moieties are linked into planar 4(4) nets by hydrogen bonding to bridging ClO4- anions. The ClO4- ions are almost perfectly encapsulated in near-spherical cavities of approximate dimensions 5.0 x 5.0 x 4.5 A that are formed by two interlocked supramolecular dications. Similarly, [{Zn(L(tBu))4}(L(tBu))2][PF6]2 crystallizes as discrete supramolecules in the crystal with the PF6- anions occupying a shallow bowl-shaped cavity on the surface of the complex that is formed by two zinc-bound and one uncoordinated pyrazole ligands. (1)H NMR and IR studies of [{Zn(L(tBu))4}(L(tBu))4][ClO4]2 in CD2Cl2 imply that the second-sphere L(tBu) ligands dissociate from the [Zn(L(tBu))4]2+ center in this solvent and that free and metal-bound L(tBu) are in rapid chemical exchange.     

Generation of multicolor vector Kerr solitons by cross-phase modulation, four-wave mixing, and stimulated Raman scattering

We numerically and experimentally show the existence of multicolor vector spatial solitons in a Kerr planar waveguide through the combined effects of cross-phase modulation, four-wave mixing, and stimulated Raman scattering. Mutual spatial guiding of the Raman-Stokes, anti-Stokes, and pump waves is achieved in the high-conversion regime mainly by cross-phase modulation and phase-matched four-wave mixing induced by a power imbalance between Stokes and anti-Stokes components, leading to the generation of a clear-cut sech-shape three-frequency spatial soliton.     

Induction of a Four‐Way Junction Structure in the DNA Palindromic Hexanucleotide 5′‐d(CGTACG)‐3′ by a Mononuclear Platinum Complex

Four‐way junctions (4WJs) are supramolecular DNA assemblies comprising four interacting DNA strands that in biology are involved in DNA‐damage repair. In this study, a new mononuclear platinum(II) complex 1 was prepared that is capable of driving the crystallization of the DNA oligomer 5′‐d(CGTACG)‐3′ specifically into a 4WJ‐like motif. In the crystal structure of the 1 –CGTACG adduct, the distorted‐square‐planar platinum complex binds to the core of the 4WJ‐like motif through π–π stacking and hydrogen bonding, without forming any platinum–nitrogen coordination bonds. Our observations suggest that the specific molecular properties of the metal complex are crucially responsible for triggering the selective assembly of this peculiar DNA superstructure.