Synthesis,Spectroscopy, Crystal Structure Determination,and Quantum Chemical Calculations of BODIPY Dyes with Increasing Conformational Restriction and Concomitant Red‐Shifted Visible Absorption and Fluorescence Spectra

Starting from the conformationally unconstrained compound 3,5‐di‐(2‐bromophenoxy)‐4,4‐difluoro‐8‐(4‐methylphenyl)‐4‐bora‐3a,4a‐diaza‐s‐indacene ( 1 ), two BODIPY dyes ( 2 and 3 ) with increasingly rigid conformations were synthesized in outstanding total yields through palladium catalyzed intramolecular benzofuran formation. Restricted bond rotation of the phenoxy fragments leads to dyes 2 and 3 , which absorb and fluoresce more intensely at longer wavelengths relative to the unconstrained dye 1 . Reduction of the conformational flexibility in 2 and 3 leads to significantly higher fluorescence quantum yields compared to those of 1 . X‐ray diffraction analysis shows the progressively more extended planarity of the chromophore in line with the increasing conformational restriction in the series 1 → 2 → 3 , which explains the larger red shifts of the absorption and emission spectra. These conclusions are confirmed by quantum chemical calculations of the lowest electronic excitations in 1 , 1a , 2 , 2a , 3 and dyes of related chemical structures. The effect of the molecular structure on the visible absorption and fluorescence emission properties of 1 , 1a , 2 , 2a , 3 has been examined as a function of solvent by means of the new, generalized treatment of the solvent effect (J. Phys. Chem. B 2009 , 113, 5951–5960). Solvent polarizability is the primary factor responsible for the small solvent‐dependent shifts of the visible absorption and fluorescence emission bands of these dyes.     

Development of novel flexible black silicon

We report a new type of black silicon: flexible black silicon. A silicon-on-insulator (SOI) wafer is irradiated by automatically scanning a femtosecond laser and then split by etching out the SOI silica middle layer. Large-area, uniform micro spikes on the surface of a very thin flexible silicon layer are obtained. The black silicon shows good flexibility and optical properties. The absorption spectrum of the flexible black silicon is as high as 97% in the visible and insensitive to the change of the incident angle of the light, which makes it a potential good candidate as an absorber for the solar-thermo generator.     

Pulse compression and fiber delivery of 45 fs Fourier transform limited pulses at 830 nm

A specific scheme is used for fiber delivery of ultrashort pulses using conventional elements. Starting from a standard femtosecond Ti:Al(2)O(3) oscillator (150 fs @ 830 nm), perfectly compressed ultrashort pulses with a duration of 45 fs are produced at the output of a standard two meter long single-mode fiber. The setup allows compensating independently and simultaneously second and third orders of chromatic dispersion as well as management of self-phase modulation in the fiber. It includes an optimized dispersion compensation line made of the assembly of diffraction gratings and prisms. The unsurpassed performances of the device are experimentally and numerically highlighted. Fiber delivery of sub-30 fs multinanojoule pulses is discussed.     

Accelerated ageing and degradation in poly-l-lactide/hydroxyapatite nanocomposites

Dry, compression molded films of medical grade poly-l-lactide (PLLA) showed a marked reduction in tensile strength and strain after accelerated ageing in aqueous NaOH at 50 °C, accompanied by mass loss, surface erosion, increased hydrophilicity and, in the case of the initially amorphous films, cold crystallization owing to the plasticizing effect of the ageing medium. Addition of well dispersed nanosized hydroxyapatite (nHA) particles resulted in increases in the rate of mass loss during ageing, identified with accelerated degradation at the matrix/particle interfaces. However, the associated decreases in tensile strength and strain to fail with ageing time were far less marked in the presence of the nHA than in the unmodified films. This implied that nHA acts as an effective toughener of the bulk material, consistent with TEM observations of the deformed films, which indicated failure of the particle-matrix interfaces to promote plastic deformation of the PLLA.     

Development of a practical solid-phase synthesis approach to 1,3,5-triazepan-2,6-diones

1,3,5-Triazepan-2,6-diones are a class of conformationally restricted heterocycles derived from dipeptides. With the aim to develop a general and practical method useful for library production, three polymer-assisted syntheses, all based on a catch and release approach, have been evaluated and compared. The method involving a Hofmann rearrangement of N-Boc dipeptide carboxamides and subsequent trapping of the isocyanate on polymer-supported N-hydroxysuccinimide (PS-HOSu) was found to be the most reliable and versatile, allowing rapid access to the 1,3,5-triazepan-2,6-dione skeleton.     

Capillary electrophoresis for rapid identification of monoclonal antibodies for routine application in hospital

mAbs are widely used in cancer therapy. Their compounding, performed just before their administration to patients, is executed in a production unit of the hospital. Identification of these drugs, individually prepared in bags for infusion before patient administration, is of paramount importance to detect potential mistakes during compounding stage. A fast and reliable analytical method based on CZE combined to a cationic capillary coating (hexadimethrine bromide) was developed for identification of the most widely used compounded therapeutic for cancer therapy (bevacizumab, cetuximab, rituximab, and trastuzumab). Considering the high structural and physico‐chemical similarities of these mAbs, an extensive optimization of the BGE composition has been performed. The addition of perchlorate ions and polysorbate in the BGE greatly increased the resolution. To validate the method, an internal standard was used and the relative migration times (RTm) were estimated. Very satisfactory RSDs of the RTm for rituximab (0.76%), cetuximab (0.46%), bevacizumab (0.31%), and trastuzumab (0.60%) were obtained. The intraday and interday RSD of the method were less than 0.32 and 1.3%, respectively for RTm. Significant differences between theses RTms have been demonstrated allowing mAbs identification. Finally, accurate mAbs identification has been demonstrated by a blind test.