Bio‐Inspired Formal Synthesis of Hirsutellones A–C Featuring an Electrophilic Cyclization Triggered by Remote Lewis Acid‐Activation

A bio‐inspired strategy was used to complete the formal synthesis of the antitubercular hirsutellone B and congeners A and C, through construction of its decahydrofluorene core from a linear polyene strand activated at both ends by a silyl enol ether and an allyl acetate. Our synthesis features a key electrophilic cyclization, starting with the remote activation (by [Yb(OTf)₃] or BF₃ ? OEt₂) of the allyl acetate and stereoselectively affording the C ring. This was followed by an intramolecular Diels–Alder reaction to get the tricyclic core of the natural product. The stereoselective reduction of the resulting ketone towards the formal intermediate was critical to the success of this strategy.     

Green light generation in a periodically poled Zn-doped LiNbO3 planar waveguide fabricated by He+ implantation

An optical planar waveguide is investigated in ZnO-doped periodically poled lithium niobate formed by He⁺ implantation. Optical losses were found to be 2 dB/cm. Second-harmonic generation is used to produce a green laser beam by quasi-phase matching in the obtained waveguide. The conversion efficiency was found to be 10^-2%/W. Photorefractive resistance properties are reported and discussed relating to un-doped periodically poled lithium niobate. PACS 42.65.-k; 42.65.Wi; 42.82.-m     

Formation of planar optical waveguides in the new nonlinear gadolinium calcium oxoborate, Ca(4)GdO(BO(3))(3), crystal by 2-MeV He(+) implantation

A planar waveguide composed of the new nonlinear material, Ca(4)GdO(BO(3))(3) (GdCOB), is reported. This crystal belongs to the calcium oxoborate family. It has attractive nonlinear properties that can be of great interest in integrated optics applications. We used a method of He(+) implantation to fabricate waveguides in GdCOB crystals by creating a buried layer of lowered refractive index a few micrometers beneath the surface. Both TE and TM modes were observed. Therefore, according to the Y cut of the crystal, refractive-index values of n(x) , n(y) , and n(z) were obtained. Index profiles were reconstructed by an improved inverse WKB method. The profiles showed a steplike index behavior, indicating that the guiding region obtained was of good optical quality.     

Channel waveguides in Ca4GdO(BO3)3 fabricated by He+ implantation for blue-light generation

Blue light at 405 nm is generated by frequency doubling of a Ti:sapphire tunable laser in He(+)-implanted channel waveguides in gadolinium calcium oxoborate crystal. A conversion efficiency of approximately 2% W(-1) cm(-2) is achieved between TM00 fundamental and TE01 harmonic modes.     

Competitive adsorption of anionic dyes onto DMOA modified MCM-41

Research on Chemical Intermediates - The single and binary adsorption of two anionic dyes Acid Yellow 17 (AY17) and Naphtol Green B (NGB) onto N–N–Dimethyl-n-octylamine (DMOA) modified...     

A green route to enantioenriched (S)-arylalkyl carbinols by deracemization via combined lipase alkaline-hydrolysis/Mitsunobu esterification

Herein we report results of the chemoenzymatic deracemization of a range of secondary benzylic acetates 1a–9a via a sequence of hydrolysis with CAL-B lipase in non-conventional media, combined with esterification of the recovered alcohol according to the Mitsunobu protocol following an enzymatic kinetic resolution (KR). The KR of racemic acetates 1a–9a via an enzymatic hydrolysis, with CAL-B lipase and Na₂CO₃, in non-aqueous media was optimized and gave high selectivities (E ? 200) at good conversions (C >49%) for all of the substrates studied. This method competes well with the traditional one performed in a phosphate buffer solution. The deracemization using Mitsunobu inversion gave the (S)-acetates in moderate to excellent enantiomeric excess 75% < ee < 99%, in acceptable isolated yields 70% < yield < 89%, and with some variations according to the acetate structure.     

Electronic structure and spectroscopic properties of 6‐aminophenanthridine and its derivatives: Insights from density functional theory

6‐Aminophenanthridine (6AP) and its derivatives show important biological activities as antiprion compounds and inhibitors of the protein folding activity of the ribosome. Both of these activities depend on the RNA binding property of these compounds, which has been recently characterized by fluorescence spectroscopy. Hence, fundamental insights into the photophysical properties of 6AP compounds are highly important to understand their biological activities. In this work, we have calculated electronic structures and optical properties of 6AP and its three derivatives 6AP8CF₃, 6AP8Cl, and 6APi by density functional theory (DFT) and time‐dependent density functional theory (TDDFT). Our calculated spectra show a good agreement with the experimental absorption and fluorescence spectra, and thus, provide deep insights into the optical properties of the compounds. Furthermore, comparing the results obtained with four different hybrid functionals, we demonstrate that the accuracy of the functionals varies in the order B3LYP > PBE0 > M062X > M06HF. © 2015 Wiley Periodicals, Inc.     

Simultaneous collinear and non-collinear parametric generation in 1D single grating periodically poled lithium tantalate

We report a detailed study of multiple wavelengths optical parametric generation in a single grating one-dimensional periodically poled lithium tantalate crystal. Simultaneous collinear and non-collinear generations are observed around the pump collinear direction. Similar spectra are found in continuous spatial positions symmetrical to the collinear direction, with decreasing signal and increasing idler wavelengths, associated with decreasing powers when the far-field angle increases. A phase matching scheme is proposed to describe these interactions. Numerical simulations emphasize the agreement of our phase matching scheme with the experimental results. Single-pass gain and high pump power density are very likely at the origin of the simultaneous collinear and non-collinear QPM interactions.     

Analysis of polarization mode dispersion fluctuations in single mode fibres due to temperature

We have studied the effect of temperature on the birefringence and polarization mode dispersion PMD in standard single mode fibre (SSMF) with elliptical core cross section by using numerical computations. On the basis of simulation we have concluded that PMD fluctuates more rapidly than the stress-induced birefringence. In addition, DGD is inversely proportional to temperature.