Effect of molecule-substrate interaction on thin-film structures and molecular orientation of pentacene on silver and gold

Evaporated pentacene thin films with thicknesses from several nm to 150 nm on gold and silver substrates have been studied by ultraviolet photoelectron spectroscopy (UPS), near-edge X-ray absorption fine structure (NEXAFS), scanning tunneling microscopy (STM), and atomic force microscopy (AFM). It was found that pentacene thin-film structures, particularly their molecular orientations, are strongly influenced by the metal substrates. UPS measurements revealed a distinct change in the valence band structures of pentacene on Au compared to those on Ag, which is attributed to the different packing between adjacent molecules. Using NEXAFS, we observed 74+/-5 degrees and 46+/-5 degrees molecular tilt angles on Ag and Au, respectively, for all measured thicknesses. We propose that pentacene molecules stand up on the surface and form the "thin-film phase" structure on Ag. On Au, pentacene films grow in domains with molecules either lying flat or standing up on the substrate. Such a mixture of two crystalline phases leads to an average tilt angle of 46 degrees for the whole film and the change in valence band structures. STM and distance-voltage (z-V) spectroscopy studies confirm the existence of two crystalline phases on Au with different conducting properties. z-V spectra on the low conducting phase clearly indicate its nature as "thin-film phase".     

Broadband 10 Gb/s operation of graphene electro‐absorption modulator on silicon

High performance integrated optical modulators are highly desired for future optical interconnects. The ultra‐high bandwidth and broadband operation potentially offered by graphene based electro‐absorption modulators has attracted a lot of attention in the photonics community recently. In this work, we theoretically evaluate the true potential of such modulators and illustrate this with experimental results for a silicon integrated graphene optical electro‐absorption modulator capable of broadband 10 Gb/s modulation speed. The measured results agree very well with theoretical predictions. A low insertion loss of 3.8 dB at 1580 nm and a low drive voltage of 2.5 V combined with broadband and athermal operation were obtained for a 50 μm‐length hybrid graphene‐Si device. The peak modulation efficiency of the device is 1.5 dB/V. This robust device is challenging best‐in‐class Si (Ge) modulators for future chip‐level optical interconnects.     

Spectral Vorticity and Lagrangian Velocity Measurements in Turbulent Jets

In this paper we report an experimental investigation of various statistical properties of the spatial Fourier modes of the vorticity field in turbulent jets for a large range of Reynolds numbers (530 ≤R _λ≤ 6100). The continuous time evolution of a spatial Fourier mode of the vorticity distribution, characterized by a well-defined wavevector, is obtained from acoustic scattering measurements. The spatial enstrophy spectrum, as a function of the spatial wave-vector, is determined by scanning the incoming sound frequencies. Time-frequency analysis of the turbulent vorticity fluctuations is also performed for different length scales of the flows. Vorticity time-correlations show that the characteristic time of a Fourier mode behaves as the sweeping time. Finally, we report preliminary Lagrangian velocity measurements obtained using acoustic scattering by soap bubbles inflated with helium. Gathering a large number of passages of isolated bubbles in the scattering volume, one is able to compute the Lagrangian velocity PDF and velocity spectrum. Despite the spatial filtering due to the finite size of the bubble, the latter exhibits a power law, with the -2 exponent predicted by the Kolmogorov theory, over one decade of frequencies.     

A General Entry to Antifeedant Sesterterpenoids: Total Synthesis of (+)‐Norleucosceptroid A, (−)‐Norleucosceptroid B,and (−)‐Leucosceptroid K

The first asymmetric total synthesis of the antifeedant terpenoids (+)‐norleucosceptroid A, (−)‐norleucosceptroid B, and (−)‐leucosceptroid K has been accomplished. This highly concise synthetic route was guided by our efforts to develop a platform for the collective synthesis of a whole family of antifeedant natural products. The synthesis features a Hauser–Kraus‐type annulation followed by an unprecedented, highly efficient intramolecular dilactol aldol‐type condensation reaction to produce the 5,6,5 skeleton. The developed synthetic route proceeds for norleucosceptroid A and B in 16 steps (longest linear sequence) from known compounds.     

Recent developments in methodology for the direct oxyamination of olefins

1,2-Amino alcohols are high-value, versatile functional groups that are found in scores of biologically active molecules and other interesting synthetic targets such as ligands and auxiliaries. Given their prominent position within organic compounds of import, it is no surprise to note that many routes have been developed to access this motif and there are many different starting points from which a synthetic chemist might embark on a synthesis. However, one particular approach stands out from the others, and this is the direct conversion of an alkene to a vicinal amino alcohol derivative (oxyamination). Research in this field has been particularly active in recent years and many interesting new methodologies have been reported. The purpose of this review is to give the reader a tour of the methods that have emerged in the last few years so one can appreciate the myriad of different metals and reagents that can accomplish the oxyamination of alkenes. There are still many challenges to be overcome and, herein, we also outline the areas that are ripe for further development and which bode well for the future.     

Synthesis of the azaphilones (+)-sclerotiorin and (+)-8-O-methylsclerotiorinamine utilizing (+)-sparteine surrogates in copper-mediated oxidative dearomatization

Enantioselective syntheses of the azaphilone natural products (+)-sclerotiorin and (+)-8-O-methylsclerotiorinamine that possess the natural R-configuration at the quaternary center are reported. The syntheses were accomplished using copper-mediated asymmetric dearomatization employing bis-μ-oxo copper complexes prepared from readily available (+)-sparteine surrogates. Of note, site-selective O-methylation of a vinylogous pyridone was used to access the isoquinolin-6(7H)-one core of (+)-8-O-methylsclerotiorinamine.     

Photophysics of the galvinoxyl free radical revisited

The photophysical properties of the free neutral radical galvinoxyl were studied by a combination of femtosecond time-resolved spectroscopy and quantum chemical calculations. The electronic absorption spectrum is dominated by an intense band at 430 nm that is ascribed to the D(9,10)← D(0) transitions. Upon photoexcitation at 400 nm, the population of the D(9,10) states decays within less than 200 fs to the electronic ground state. This ultrafast internal conversion does not involve intramolecular modes with large amplitude motion as the measured dynamics does not show any significant dependence on the environment, but is most probably facilitated by a high density of electronic states of different character. Depending on the solvent, a weak transient band due to the galvinoxylate anion is also observed. This closed-shell species, which is fluorescent although its deactivation is also dominated by non-radiative decay, is generated upon biphotonic ionization of the solvent and electron capture. The ultrashort excited-state lifetime of the galvinoxyl radical precludes photoinduced disproportionation previously claimed to be at the origin of the formation of both anion and cation.     

CdTe quantum dots functionalized with 4-amino-2,2,6,6-tetramethylpiperidine-N-oxide as luminescent nanoprobe for the sensitive recognition of bromide ion

A novel bromide ion-selective modified nanoprobe sensor based on 4-amino-2,2,6,6-tetramethylpiperidine-N-oxide (4AT)-functionalized CdTe quantum dots (QDs-4AT) has been developed. Fluorescence quenching of the QDs by 4AT was observed. The functionalized QDs-4AT nanoprobe allowed a highly sensitive determination of bromide ion via analyte-induced change in the photoluminescence (fluorescence recovery) of the modified QDs. A detection limit of 0.6 nM of bromide ion was obtained, while the interfering effect of other inorganic cations and anions was investigated to examine the selectivity of the nanoprobe. The linear range was between 0.01 and 0.13 μM. Combined fluorescence lifetime and electron paramagnetic resonance measurements confirmed electron transfer processes between bromide ion and QDs-4AT.