Investigating the Red Shift between in vitro and in vivo Urocanic Acid Photoisomerization Action Spectra

Abstract— Trans-urocanic acid (UCA) is found in the upper layer of the skin and UV irradiation induces its photoisomerization to cis -UCA. Cis -UCA mimics some of the immunosuppressive properties of UV exposure. The wavelength dependence for in vitro photoisomerization of trans-UCA (15 μM) over the spectral range 250 nm-340 nm (10 nm intervals) was determined. The action spectrum revealed that maximal cis-UCA production occurred at 280 nm, which is red-shifted by 10-12 nm from its absorption peak at 268 nm and differs markedly from the reported action spectra for cis-UCA production in mouse skin in vivo , which peaks at 300-310 nm. The reasons for the red shift between the in vitro and in vivo action spectra are not clear. There is limited evidence suggesting that the UV absorption maximum of trans- UCA red shifts from 268 nm in vitro to 310 nm on interaction with stratum corneum proteins in vivo. This phenomenon was investigated by applying trans-UCA (2.5 mg/cm²) in an oil emulsion to isolated human stratum corneum. After incubation at 37°C for 1 h, the absorption spectra of stratum corneum with UCA and with oil only were compared using a Xe arc source and a spectrora-diometer. A moderate red shift in trans-UCA absorption from ∼268 nm to 280 nm was observed. In summary, we suggest that the 10-12 nm red shift between the UCA absorption spectrum peak and the action spectrum peak in vitro may be accounted for by the wavelength dependence of quantum yields reported over the 254-313 nm range. The red shift between the in vitro and in vivo photoisomerization action spectra may result from the 10 to 12 nm red shift in the absorption of UCA in association with stratum corneum proteins, combined with increasing quantum yields over the 254-313 nm range.     

Sodium hydrogen telluride as a useful nucleophilic reagent for the cleavage of epoxides and of quaternary ammonium salts

Sodium hydrogen telluride opens many epoxides cleanly by an SN₂ process to give telluro-alcohols, which by reduction with nickel boride afford alcohols. An intermediate telluro-alcohol was converted to olefin in high yield by treatment with $\text{p}$-toluene-sulphonyl chloride in pyridine. Quaternary ammonium salt are also cleaved efficiently by sodium hydrogen telluride.     

Photochemical ring opening of barbital

Photolysis of barbital yields derivatives of urea and biuret. The mechanism of ring opening involves an isocyanate intermediate.     

Selective reduction of the N-O bond in n-oxides and in nitrones by sodium hydrogen telluride

Sodium hydrogen telluride reduces $\text{tert}$.-amine $\text{N}$-oxides to the corresponding amines in very high yield, but does not reduce sulphoxides. This reagent also reduces nitrones to $\text{sec}$.-amines at pH6 and to imines at alkaline pH (10–11).     

Oxoammonium salts as oxidizing agents: 2,2,6,6-tetramethyl-1-oxopiperidinium chloride

A study of the scope of the oxidizing ability of the oxoammonium chloride (1) revealed that phenols, enolizable ketones, phosphines, amines and anilines were reactive but that olefins, aromatic ethers, sulfides, and sulfones did not react.     

Synthesis of nanoscale NbSe2 materials from molecular precursors

This communication describes a new synthetic approach to one- (1D) and two-dimensional (2D) NbSe2 nanoscale materials using soft chemical methods. Our one-pot synthesis provides a direct route to control the morphology of nanostructures that can exhibit complex electronic properties, and can produce layered, nanocrystalline materials in high yield.     

Passive mixing control of plane parallel jets

An experimental study on the mixing of two plane, unventilated, parallel jets reveals an instability characterized by sinuous flapping of the jets and enhanced mixing of the jets with the ambient fluid. The frequency and amplitude of the instability is shown to be a function of the jets spacing and momentum flux ratios, with the maximum mixing occurring for cases with matched momentum flux. When the momentum flux of the two jets is mismatched by as much as a factor of three, the flow becomes steady. Schlieren flow visualization and hot-wire anemometry demonstrate and quantify the large-scale mixing. The instability has a strong frequency and amplitude dependence on the momentum ratio of the jets. The Strouhal number is also found to decrease with the spacing between the jets. The instability described provides a means to passively control the jet mixing with the ambient.