Sensitized phosphorescence as detection method for the enantioseparation of bupropion by capillary electrophoresis.

A new CE detection method was developed for the chiral drug bupropion (a second-generation antidepressant), based on phosphorescence both in the direct and in the sensitized mode using pulsed laser excitation at 266 nm. Electrokinetic chromatography using 5 mM sulfated-α-CD as chiral selector in 25 mM phosphate buffer at pH 3 allowed the separation of bupropion enantiomers with a high chiral resolution (Rs>3). In the sensitized phosphorescence detection mode, excitation energy is transferred from the analyte to an acceptor (1-bromo-4-napthhalenesulfonic acid or biacetyl) followed by time-resolved phosphorescence detection under deoxygenated buffer conditions.

Time-resolved spatially offset Raman spectroscopy for depth analysis of diffusely scattering layers.

The objective of this study is to use time-resolved (TR) Raman spectroscopy, spatially offset Raman spectroscopy (SORS), and a combination of these approaches to obtain high quality Raman spectra from materials hidden underneath an opaque layer. Both TR Raman and SORS are advanced techniques that allow for an increased relative selectivity of photons from deeper layers within a sample. Time-resolved detection reduces fluorescence background, and the selectivity for the second layer is improved.

Phosphorescence for sensitive enantioselective detection in chiral capillary electrophoresis.

Enantioselective phosphorescence lifetime detection was combined with chiral cyclodextrin-based electrokinetic chromatography for the analysis of camphorquinone (CQ). A time-gated detection system based on a pulsed light-emitting diode for excitation at 465 nm was developed for the online lifetime determination. The background electrolyte for the chiral separation consisted of 20 mM alpha-cyclodextrin (alpha-CD), 10 mM carboxymethyl-beta-CD, and 25 mM borate buffer at pH 9.

Excited state processes of 2-butylamino-6-methyl-4-nitropyridine N-oxide in nonpolar solvents. A transient absorption spectroscopy study.

Earlier steady-state fluorescence studies showed that 2-butylamino-6-methyl-4-nitropyridine N-oxide (2B6M) can undergo fast excited-state intramolecular proton transfer (ESIPT). In a nonpolar solvent such as n-octane, both normal and tautomeric fluorescence was observed. Strikingly, the relative ratio of those two emission bands and the fluorescence quantum yield of the normal emission were found to depend on the excitation wavelength in violation of the Kasha-Vavilov rule.

Testing the time-invariance of fundamental constants using microwave spectroscopy on cold diatomic radicals.

The recently demonstrated methods to cool and manipulate neutral molecules offer new possibilities for precision tests of fundamental physics theories. We here discuss the possibility of testing the time-invariance of fundamental constants using near degeneracies between rotational levels in the fine structure ladders of molecular radicals. We show that such a degeneracy occurs between the J = 6, Q2 1 and the J = 8, Q = 0 levels of the various natural isotopomers of carbon monoxide in its a 3pi state.

Analysis of hybrid mode-locking of two-section quantum dot lasers operating at 1.5 microm.

For the first time a detailed study of hybrid mode-locking in two-section InAs/InP quantum dot Fabry-Pérot-type lasers is presented. The output pulses have a typical upchirp of approximately 8 ps/nm, leading to very elongated pulses. The mechanism leading to this typical pulse shape and the phase noise is investigated by detailed radio-frequency and optical spectral studies as well as time-domain studies.

Direct frequency comb spectroscopy of trapped ions.

Direct frequency comb spectroscopy of trapped ions is demonstrated for the first time. It is shown that the 4s ;{2}S_{1/2}-4p ;{2}P_{3/2} transition in calcium ions can be excited directly with a frequency comb laser that is up-converted to 393 nm. Detection of the transition is performed using a shelving scheme to suppress the background signal from nonresonant comb modes.

Picosecond Raman spectroscopy with a fast intensified CCD camera for depth analysis of diffusely scattering media.

A spectroscopic depth profiling approach is demonstrated for layers of non-transparent, diffusely scattering materials. The technique is based on the temporal discrimination between Raman photons emitted from the surface and Raman photons originating from a deeper layer. Excitation was carried out with a frequency-doubled, 3 ps Ti:sapphire laser system (398 nm; 76 MHz repetition rate).

Excited-state double proton transfer in 1H-pyrazolo[3,4-b]quinoline dimers.

Pyrazoloquinolines are highly fluorescent, both in liquid solutions and in the solid state, which makes them good candidates for various optical devices. The aim of the current work is to understand the photochemical behavior of pyrazolo[3,4-b]quinoline (PQ), which is quite complicated since in n-alkane solvents PQ tends to form strong complexes with protic solvent constituents (often present as minor impurities), as well as dimers. Both types of H-bond complexes were studied systematically by temperature-dependent conventional absorption and fluorescence spectroscopy; the effect of protic solvent constituents was mimicked by varying the ethanol concentration in n-octane in the range from 0.

Cryogenic fluorescence and absorption spectroscopy studies on monomeric and dimeric species of 2-butylamino-6-methyl-4-nitropyridine N-oxide.

2-Butylamino-6-methyl-4-nitropyridine-N-oxide (2B6M) belongs to a group of compounds that can undergo not only excited-state intra-, but also intermolecular proton transfer. The latter of course requires the presence of dimeric species. Previously, we have shown that for 2B6M in aprotic non-polar solvents in the liquid state such dimers play no role.

Ultrafast double-pulse parametric amplification for precision Ramsey metrology.

We demonstrate phase stable, mJ-level parametric amplification of pulse pairs originating from a Ti:Sapphire frequency comb laser. The amplifier-induced phase shift between the pulses has been determined interferometrically with an accuracy of approximately 10 mrad. Typical phase shifts are on the order of 50-200 mrad, depending on the operating conditions.

Achievements in resonance Raman spectroscopy review of a technique with a distinct analytical chemistry potential.

In an extended introduction, key aspects of resonance Raman spectroscopy (RRS) such as enhanced sensitivity and selectivity are briefly discussed in comparison with normal RS. The analytical potential is outlined. Then achievements in different fields of research are highlighted in four sections, with emphasis on recent breakthroughs: (1) The use of visible RRS for analyzing carotenoids in biological matrices, for pigments and dyes as dealt with in art and forensics, and for characterizing carbon nanotubes.

Phase stability of terawatt-class ultrabroadband parametric amplification.

The phase stability of broadband (280 nm bandwidth) terawatt-class parametric amplification was measured, for the first time to our knowledge, with a combination of spatial and spectral interferometry. Measurements at four different wavelengths from 750 to 900 nm were performed in combination with numerical modeling. The phase stability is better than 1/23 rms of an optical cycle for all the measured wavelengths, depending on the phase-matching conditions in the amplifier.

Fluorescence rejection in resonance Raman spectroscopy using a picosecond-gated intensified charge-coupled device camera.

A Raman instrument was assembled and tested that rejects typically 98-99% of background fluorescence. Use is made of short (picosecond) laser pulses and time-gated detection in order to record the Raman signals during the pulse while blocking most of the fluorescence. Our approach uses an ultrafast-gated intensified charge-coupled device (ICCD) camera as a simple and straightforward alternative to ps Kerr gating.

Intramolecular proton-transfer processes starting at higher excited states: a fluorescence study on 2-butylamino-6-methyl-4-nitropyridine N-oxide in nonpolar solutions.

This article describes the exceptional photophysics of 2-butylamino-6-methyl-4-nitropyridine N-oxide (2B6M). It is known from the literature that this compound may undergo excited-state intra- or intermolecular proton-transfer reactions. In nonpolar solvents, 2B6M exhibits an unusual fluorescence behavior: there is a substantial difference between the relative band intensities of the excitation and absorption spectra.

Comparison of the Hanbury Brown-Twiss effect for bosons and fermions.

Fifty years ago, Hanbury Brown and Twiss (HBT) discovered photon bunching in light emitted by a chaotic source, highlighting the importance of two-photon correlations and stimulating the development of modern quantum optics. The quantum interpretation of bunching relies on the constructive interference between amplitudes involving two indistinguishable photons, and its additive character is intimately linked to the Bose nature of photons. Advances in atom cooling and detection have led to the observation and full characterization of the atomic analogue of the HBT effect with bosonic atoms.

High-power parametric amplification of 11.8-fs laser pulses with carrier-envelope phase control.

Phase-stable parametric chirped-pulse amplification of ultrashort pulses from a carrier-envelope phase-stabilized mode-locked Ti:sapphire oscillator (11.0 fs) to 0.25 mJ/pulse at 1 kHz is demonstrated.

Simultaneous magneto-optical trapping of a boson-fermion mixture of metastable helium atoms.

We simultaneously confine fermionic metastable 3He atoms and bosonic metastable 4He atoms in a magneto-optical trap. The trapped clouds, containing up to 1.5 x 10(8) atoms of each isotope, are characterized by measuring ions and metastable helium atoms escaping from the trap.