Luminescence Spectroscopy of Rhodamine Homodimer Dications in Vacuo Reveals Strong Dye-Dye Interactions

Being alone or together makes a difference for the photophysics of dyes but for ionic dyes it is difficult to quantify the interactions due to solvent screening and nearby counter ions. Gas-phase luminescence experiments are desirable and now possible based on recent developments in mass spectrometry. Here we present results on tailor-made rhodamine homodimers where two dye cations are separated by methylene linkers, (CH₂)_n. In solution the fluorescence is almost identical to that from the monomer whereas the emission from bare cation dimers redshifts with decreasing n. In the absence of screening, the electric field from the charge on one dye is strong enough to polarize the other dye, both in the ground state and in the excited state. An electrostatic model based on symmetric dye responses (equal induced-dipole moments in ground state) captures the underlying physics and demonstrates interaction even at large distances. Our results have possible implications for gas-phase Förster Resonance Energy Transfer.     

Cytotoxic flavonoids from two Lonchocarpus species

A new isoflavone, 4′-prenyloxyvigvexin A (1) and a new pterocarpan, (6aR,11aR)-3,8-dimethoxybitucarpin B (2) were isolated from the leaves of Lonchocarpus bussei and the stem bark of Lonchocarpus eriocalyx, respectively. The extract of L. bussei also gave four known isoflavones, maximaisoflavone H, 7,2′-dimethoxy-3′,4′-methylenedioxyisoflavone, 6,7,3′-trimethoxy-4′,5′-methylenedioxyisoflavone, durmillone; a chalcone, 4-hydroxylonchocarpin; a geranylated phenylpropanol, colenemol; and two known pterocarpans, (6aR,11aR)-maackiain and (6aR,11aR)-edunol. (6aR,11aR)-Edunol was also isolated from the stem bark of L. eriocalyx. The structures of the isolated compounds were elucidated by spectroscopy. The cytotoxicity of the compounds was tested by resazurin assay using drug-sensitive and multidrug-resistant cancer cell lines. Significant antiproliferative effects with IC₅₀ values below 10 μM were observed for the isoflavones 6,7,3′-trimethoxy-4′,5′-methylenedioxyisoflavone and durmillone against leukemia CCRF-CEM cells; for the chalcone, 4-hydroxylonchocarpin and durmillone against its resistant counterpart CEM/ADR5000 cells; as well as for durmillone against the resistant breast adenocarcinoma MDA-MB231/BCRP cells and resistant gliobastoma U87MG.ΔEGFR cells.     

Existence and analytical predictions of periodic motions in a periodically forced,nonlinear friction oscillator

The grazing bifurcation, stick phenomena and periodic motions in a periodically forced, nonlinear friction oscillator are investigated. The nonlinear friction force is approximated by a piecewise linear, kinetic friction model with the static force. The total forces for the input and output flows to the separation boundary are introduced, and the force criteria for the onset and vanishing of stick motions are developed through such input and output flow forces. The periodic motions of such an oscillator are predicted analytically through the corresponding mapping structure. Illustrations of the periodic motions in such a piecewise friction model are given for a better understanding of the stick motion with the static friction. The force responses are presented, which agreed very well with the force criteria. If the fully nonlinear friction force is modeled by several portions of piecewise linear functions, the periodically forced, nonlinear friction oscillator can be predicted more accurately. However, for the fully nonlinear friction force model, only the numerical investigation can be carried out.     

Nonlinear filtering and beam shaping with χ nonlinear polarization interferometer

Novel χ⁽³⁾-based nonlinear polarization interferometer is theoretically and experimentally investigated. It enables efficient spatial and temporal filtering of femtosecond pulses via generation of cross-polarized wave. By changing the interferometer parameters different beam shapes can be obtained.     

Tip-enhanced Raman spectroscopy and microscopy on single dye molecules with 15 nm resolution

Our recently developed approach of UHV-tip-enhanced Raman spectroscopy permits us to acquire Raman spectra of a few single brilliant cresyl blue (BCB) molecules and even a single one adsorbed on a Au(111) surface. This is substantiated by simultaneously recorded STM images. Furthermore, because of the reduced photobleaching in UHV, the time frame for spectral acquisition is sufficiently extended to allow tip-enhanced Raman imaging of a single BCB molecule with a lateral resolution of 15 nm.     

Distributed feedback fiber laser pumped by multimode laser diodes

A distributed feedback fiber laser made of highly Er-Yb codoped phosphate glass fiber has been demonstrated experimentally. Efficient pump absorption allows for multimode pumping into the cladding of the active fiber. Output powers up to 160 mW have been achieved. The 35 mm long fiber laser device emits with >50 dB side mode suppression ratio.     

Optical measurement of neural activity using surface plasmon resonance

We demonstrate that surface plasmon resonance (SPR) is applicable to the optical detection of neural signals. A low-noise SPR sensor was developed as a label- and artifact-free method for the extracellular recording of neural activity. The optical responses obtained from a rat sciatic nerve were highly correlated with simultaneously recorded electrical responses. Additional studies with stimulation intensity and lidocaine further confirmed that the optically measured signals originated from neural activities.     

Coherent transients in the femtosecond photoassociation of ultracold molecules

We demonstrate the photoassociation of ultracold rubidium dimers using coherent femtosecond pulses. Starting from a cloud of ultracold rubidium atoms, electronically excited rubidium molecules are formed with shaped photoassociation pump pulses. The excited state molecules are projected with a time-delayed probe pulse onto molecular ion states which are detected in a mass spectrometer. Coherent transient oscillations of the excited state population are observed in the wings of the pump pulse, in agreement with the time-dependent solution of the Schr?dinger equation of the excitation process.     

Dynamic contrast-enhanced MRI and MR diffusion imaging to distinguish between glandular and stromal prostatic tissues

Purpose

To compare peak enhancement (PE), determined from dynamic contrast-enhanced (DCE) magnetic resonance imaging (MRI) and the magnetic resonance (MR) directionally-averaged apparent diffusion coefficient () in glandular versus stromal prostatic tissues and, with this comparison, to infer if the hypothesis that gadolinium-DTPA (Gd-DTPA) does not enter healthy glands or ducts is plausible.

Materials and Methods

MRI, MR spectroscopic imaging, DCE MRI and MR diffusion were evaluated in 17 untreated subjects with suspected or proven prostate cancer. PE and were compared in glandular-ductal tissues [normal peripheral zone and glandular benign prostatic hyperplasia (BPH)] and stromal-low ductal tissues (central gland/mixed BPH and stromal BPH).

Results

The glandular-ductal tissues had lower PE [125±6.4 (% baseline)] and higher [1.57±0.15 (s/10⁻³ mm²)] than the stromal-low ductal tissues [PE=132±5.5 (% baseline) (P<.0008), =1.18±0.20 (s/10⁻³ mm²) (P<1×10⁻⁸)]. A statistical model based upon stepwise regression was generated and completely separated the tissue types: ductal Measure = 448+669× (s/10⁻³ mm²)−10.7×PE (1/%), R²=1.0 and P<8×10⁻¹⁰.

Conclusions

The very different MR results in the glandular-ductal versus stromal-low ductal tissues suggest that these tissues have different underlying structure. These results support the hypothesis that Gd-DTPA does not enter healthy prostatic glands or ducts. This may explain the higher PE and lower that previously have been reported in prostate cancer versus healthy tissue.     

Influence of spectral phase on cross-polarized wave generation with short femtosecond pulses

In this paper we present the first comprehensive study of the role of spectral phase on cross-polarized wave (XPW) generation using sub-30 femtosecond (fs) laser pulses. XPW generation improves the temporal contrast and shortens the pulse duration of fs chirped pulse amplification (CPA) lasers. For Ti:Sa lasers, compression below 30?fs is non-trivial and therefore never perfect. We therefore systematically analyze the effect of an arbitrary input spectral phase on the output spectrum and efficiency of the XPW process, both theoretically and experimentally. We derive the maximum acceptable value of residual phase for a given initial pulse duration in order to efficiently drive the XPW process for pulse shortening and contrast improvement.