Frequency-modulation-mode-locked optical parametric oscillator

We demonstrate a novel technique for the generation of mode-locked pulses from a continuous-wave (cw) optical parametric oscillator (OPO). The technique is based on the deployment of a phase modulator in combination with an antiresonant ring interferometer internal to a cw OPO, simultaneously providing spectral broadening and phase-to-amplitude feedback modulation. The scheme is implemented in a doubly-resonant cw OPO based on MgO:sPPLT, configured in a standing-wave cavity and pumped at 532 nm. With the phase modulator activated and the cavity length synchronized, a stable train of 800 ps pulses is generated at a repetition rate of 160 MHz. Using single-pass second harmonic generation (SHG) of the OPO output, we observe a four times enhancement in SHG compared with cw operation, confirming the real achievement of energy concentration as a result of mode-locked operation.     

High-power, Yb-fiber-laser-pumped, picosecond parametric source tunable across 752-860 nm

We report a stable, high-power source of picosecond pulses in the near-infrared based on intracavity second harmonic generation (SHG) of a MgO:PPLN optical parametric oscillator synchronously pumped at 81 MHz by a mode-locked Yb-fiber laser. By exploiting the large spectral acceptance bandwidth for Type I (oo→e) SHG in β-BaB2O4 and a 5 mm crystal, we have generated picosecond pulses over 752-860 nm spectral range under minimal angle tuning, with as much as 3.5 W of output power at 778 nm and >2 W over 73% of the tuning range, in good beam quality with TEM00 spatial profile and M2<1.4. The SHG output pulses have durations of 15.2 ps, with a spectral bandwidth of ～3.4 nm at 784 nm. In addition, the oscillator simultaneously provides a signal power of >1 W over 1505-1721 nm (25 THz) and idler power >1.8 W over 2787-3630 nm (25 THz), corresponding to a total (signal plus idler) tuning range of 1059 nm. The SHG, signal, and idler output exhibit passive long-term power stability better than 1.6%, 1.3%, and 1.6% rms, respectively, over 14 h.     

Structure, bonding, and lowest energy transitions in unsymmetrical squaraines: a computational study

Natural resonance theory (NRT) and natural bond orbital (NBO) analysis have been carried out on a simple symmetrical and an unsymmetrical substituted squaraine with a view of understanding the structure of the latter type of squaraines. It is found that there are some fundamental differences in the structure and bonding between these two types of squaraines particularly in the resonance weights and delocalization energies. These differences are expected to reflect in the low energy transitions and charge transfer in these squaraines. To investigate this, the nature of the lowest energy transitions occurring on excitation in unsymmetrical squaraines has been studied using high-level symmetry adapted cluster-configuration interaction method (SAC/SAC-CI) and compared with reported experimental observations. In general the agreement with the experimental data is very good. The transition dipole moment always lies on the pi-backbone and is quite large in magnitude. The ground state dipole moment in some cases does not change in the excited state upon excitation while in some other cases there is a large reduction/enhancement in the magnitude indicative of some charge rearrangement in this direction. Inclusion of the solvent using the IEFPCM model, a slightly better agreement with the experiment is found in some cases. Studies are carried out with a different basis set and it is found that the change in basis set has very little effect on the transition energies. In the case of weak side donor groups attached to the central ring the larger charge transfer to the central acceptor ring in general takes place from the O- atoms of the squarylium moiety while in the case of strong donors the charge transfer from the O- atoms to the central rings drop down. We have not observed any correlation between the charge transfer in the excited state to the central ring from the side donor groups and the lowest energy excitation in the molecules. Reduction of the HOMO-LUMO gap (an indication of increase of the diradicaloid character) always leads to a bathochromic shift.     

Planar tetracoordinate carbon atoms centered in bare four-membered rings of late transition metals

Planar tetracoordinate carbons (ptC's) can be stabilized by four-membered ring perimeters composed of four bare transition metal atoms. DFT analyses of the molecular orbitals, electronic structures, energies, and magnetic properties of these CM4 species (where M represents isoelectronic combinations of Cu, Ni, Ag, and Pd) reveal striking similarities with main group metal ptC analogues (e.g., CAl2Si2, CAl4Na-, and C5Li2). While the CCu4(2+), CAg4(2+), and CNiCu3+ ions have the largest HOMO-LUMO separations, CCu4(2+) is the best candidate for detection by gas-phase photoelectron spectroscopy.     

Photonenergy‐Controlled Symmetry Breaking with Circularly Polarized Light

Circularly polarized light (CPL) is known to be a true chiral entity capable of generating absolute molecular asymmetry. However, the degree of inducible optical activity depends on the λ of the incident CPL. Exposure of amorphous films of rac‐alanine to tunable CPL led to enantiomeric excesses (ee) which not only follow the helicity but also the energy of driving electromagnetic radiation. Postirradiation analyses using enantioselective multidimensional GC revealed energy‐controlled ee values of up to 4.2 %, which correlate with theoretical predictions based on newly recorded anisotropy spectra g(λ). The tunability of asymmetric photochemical induction implies that both magnitude and sign can be fully controlled by CPL. Such stereocontrol provides novel insights into the wavelength and polarization dependence of asymmetric photochemical reactions and are highly relevant for absolute asymmetric molecular synthesis and for understanding the origins of homochirality in living matter.     

Efficient Synthesis of Novel 3-[5-(1H-Benzimidazol-2-Ylmethanesulfonyl)-4-Phenyl-4H-(1,2,4)Triazol-3-Yl]-1H-(1,8)Naphthyridin-4-One Derivatives

Abstract

of 1,4-dihydro-4-oxo-1,8-naphthyridine-3-carbohydrazide (4) with substituted phenyl isothiocyanates (5) in ethanol under reflux for 30 min gave thiosemicarbazide derivatives 6, which on cyclization in 2N NaOH under refluxing conditions for 1 h resulted in 3-(5-mercapto- 4-phenyl-4H-1,2,4-triazol-3-yl)-1,8-naphthyridin-4(1H)-one (7). Alternatively, 7 could also be prepared from following sequence of reactions, i.e., 4 → 8 → 7. In another sequence of reactions, condensation of 7 with chloroacetic acid in dimethylformamide (DMF) and K₂CO₃ as a mild base at 120 °C for 2 h resulted in 2-((5-(1,4-dihydro-4-oxo-1,8-naphthyridin-3-yl)-4-phenyl-4H-1,2,4-triazol-3-yl)sulfanyl)acetic acid (10). The latter, on reaction with substituted o-phenylenediamine (11) in 6N HCl for 4 h yielded 3-(5-((1H-benzo[d]imidazol-2-yl)methylthio)-4-phenyl-4H-1,2,4-triazol-3-yl)-1,8-naphthyridin-4(1H)-one (12). Alternatively, 12 could also be prepared by reacting 7 with 13 in DMF and K₂CO₃ as a mild base at 120 °C for 2 h, followed by oxidation with H₂O₂ resulting in the corresponding sulfonyl derivatives 14.     

Modulation-frequency encoded multi-color fluorescent DNA analysis in an optofluidic chip

We introduce a principle of parallel optical processing to an optofluidic lab-on-a-chip. During electrophoretic separation, the ultra-low limit of detection achieved with our set-up allows us to record fluorescence from covalently end-labeled DNA molecules. Different sets of exclusively color-labeled DNA fragments-otherwise rendered indistinguishable by spatio-temporal coincidence-are traced back to their origin by modulation-frequency-encoded multi-wavelength laser excitation, fluorescence detection with a single ultrasensitive, albeit color-blind photomultiplier, and Fourier analysis decoding. As a proof of principle, fragments obtained by multiplex ligation-dependent probe amplification from independent human genomic segments, associated with genetic predispositions to breast cancer and anemia, are simultaneously analyzed.     

Synthesis of functionalized ellipticinium and ellipticine derivatives via electrophilic cyclization

An efficient methodology for the synthesis of highly functionalized ellipticinium and ellipticine derivatives starting from the corresponding 2-bromocarbazoles via an AgOTf or CuI catalyzed electrophilic cyclization of 2-alkynyl-3-carbazolylaldimines is reported.     

All-numerical noise filtering of fluorescence signals for achieving ultra-low limit of detection in biomedical applications

We present an all-numerical method for post-processing of the fluorescent signal as obtained from labeled molecules by capillary electrophoresis (CE) in an optofluidic chip, on the basis of data filtering in the Fourier domain. It is shown that the method outperforms the well-known lock-in amplification during experiments in the reduction of noise by a factor of (square root)2. The method is illustrated using experimental data obtained during CE separation of molecules from a commercial DNA ladder with 17 fluorescently labeled molecules having different base-pair sizes. An improvement in signal-to-noise ratio by a factor of ～10 is achieved, resulting in a record-low limit of detection of 210 fM.     

Optimally-output-coupled, 17.5 W,fiber-laser-pumped continuous-wave optical parametric oscillator

We present a stable, high-power, fiber-laser-pumped, continuous-wave (cw), singly resonant optical parametric oscillator (SRO) for the mid-infrared in an output-coupled (OC) configuration, providing 17.5 W of total output power at 61% extraction efficiency. Using a single-frequency, cw Yb fiber laser at 1064 nm and a 50-mm-long MgO:PPLN crystal, through optimization of signal output coupling we generate up to 9.8 W of signal power in the near-infrared together with 7.7 W of idler power for 28.6 W of pump, while in the absence of output coupling, 8.6 W of idler power is generated for the same pump power at 30% efficiency. The SRO is tunable over 360 nm in the idler range. The deployment of signal output coupling results in a total tuning of 513 nm (120 nm of signal, 393 nm of idler) over which watt-level output power can be extracted. Through careful control of thermal effects we achieve a long-term peak-to-peak idler power stability of 5% over 14 hours near room temperature. The output beams have TEM₀₀ spatial profile with M ²<1.28 for the idler and M ²<1.37 for the signal.