Frequency-Comb Spectrum of Periodic-Patterned Signals.

Using arbitrary periodic pulse patterns we show the enhancement of specific frequencies in a frequency comb. The envelope of a regular frequency comb originates from equally spaced, identical pulses and mimics the single pulse spectrum. We investigated spectra originating from the periodic emission of pulse trains with gaps and individual pulse heights, which are commonly observed, for example, at high-repetition-rate free electron lasers, high power lasers, and synchrotrons. The ANKA synchrotron light source was filled with defined patterns of short electron bunches generating coherent synchrotron radiation in the terahertz range. We resolved the intensities of the frequency comb around 0.258 THz using the heterodyne mixing spectroscopy with a resolution of down to 1 Hz and provide a comprehensive theoretical description. Adjusting the electron's revolution frequency, a gapless spectrum can be recorded, improving the resolution by up to 7 and 5 orders of magnitude compared to FTIR and recent heterodyne measurements, respectively. The results imply avenues to optimize and increase the signal-to-noise ratio of specific frequencies in the emitted synchrotron radiation spectrum to enable novel ultrahigh resolution spectroscopy and metrology applications from the terahertz to the x-ray region.

Similar appearance, different mechanisms: xerosis in HIV, atopic dermatitis and ageing.

Xerosis is one of the most common dermatologic disorders occurring in the elderly and in patients with atopic dermatitis (AD) and human immunodeficiency virus (HIV) infection. Xerosis has been linked to an impaired skin barrier function of the stratum corneum. Using Raman microspectroscopy, we concentrated on deeper skin layers, viable epidermis and dermis of 47 volunteers and associated molecular alterations to the evolution of xerosis and the skin barrier, for example, lipid, water and antioxidant content. A decrease in lipids within the viable epidermis is found for elderly and HIV-patients. Lipid and water values of AD patients and their healthy reference group are similar. Decreases in lipids and simultaneous increases in water are found in the dermis for HIV and AD patients in comparison to their healthy reference groups. Excessive levels of epidermal carotenoids, mainly lycopene, in HIV-patients were found potentially leading to adverse effects such as premature skin ageing.

Polarized 3D Raman and nanoscale near-field optical microscopy of optically inscribed surface relief gratings: chromophore orientation in azo-doped polymer films.

We have used polarized confocal Raman microspectroscopy and scanning near-field optical microscopy with a resolution of 60 nm to characterize photoinscribed grating structures of azobenzene doped polymer films on a glass support. Polarized Raman microscopy allowed determining the reorientation of the chromophores as a function of the grating phase and penetration depth of the inscribing laser in three dimensions. We found periodic patterns, which are not restricted to the surface alone, but appear also well below the surface in the bulk of the material. Near-field optical microscopy with nanoscale resolution revealed lateral two-dimensional optical contrast, which is not observable by atomic force and Raman microscopy.

Revealing the dynamics of ultrarelativistic non-equilibrium many-electron systems with phase space tomography.

The description of physical processes with many-particle systems is a key approach to the modeling of numerous physical systems. For example in storage rings, where ultrarelativistic particles are agglomerated in dense bunches, the modeling and measurement of their phase-space distribution is of paramount importance: at any time the phase-space distribution not only determines the complete space-time evolution but also provides fundamental performance characteristics for storage ring operation. Here, we demonstrate a non-destructive tomographic imaging technique for the 2D longitudinal phase-space distribution of ultrarelativistic electron bunches. For this purpose, we utilize a unique setup, which streams turn-by-turn near-field measurements of bunch profiles at MHz repetition rates. To demonstrate the feasibility of our method, we induce a non-equilibrium state and show that the phase-space distribution microstructuring as well as the phase-space distribution dynamics can be observed in great detail. Our approach offers a pathway to control ultrashort bunches and supports, as one example, the development of compact accelerators with low energy footprints.

Introducing cymantrene labels into scattering scanning near-field infrared microscopy.

In this paper we investigate metal-organic compounds as infrared (IR) active labels by scattering scanning near-field infrared microscopy (IR s-SNOM, often also abbreviated as s-SNIM) with a lateral resolution of 90 × 90 nm(2). Tailor-made IR spectroscopic probes based on cymantrene (CpMn(CO)(3) with Cp = η(5)-C(5)H(5)) conjugated to a cysteine-modified pseudoneurotensin (pNT-Cys-OH) peptide were prepared by automated microwave-assisted solid phase peptide synthesis (SPPS) and characterized by HPLC, ESI-MS and IR. Well-defined patterned self-assembled monolayers on a gold surface were prepared by microcontact printing of 1-octadecanethiol (ODT) followed by additional incubation in ethanolic solution of the cymantrene-peptide derivative. The self-assembled monolayers have been evidenced by infrared reflection absorption spectroscopy (IRRAS) and AFM. CO laser source radiation was tuned (1944, 1900, 1798 and 1658 cm(-1)) for imaging contrast with good matching correlation between spectroscopic and topographic patterns at specific characteristic metal carbonyl and amide bands (1944 cm(-1) (λ = 5.14 µm) and 1658 cm(-1) (λ = 6.03 µm)). Cymantrene probes provide an attractive method to tag a unique spectroscopic feature on any bio(macro)molecule. Introducing such probes into super-resolution IR s-SNOM will enable molecular tracking and distribution studies even in complex biological systems.

Dielectric property measurement of human sweat using attenuated total reflection terahertz time domain spectroscopy.

Sweat is one of the essential biofluids produced by the human body, and it contains various physiological biomarkers. These biomarkers can indicate human health conditions such as disease and illness. In particular, imbalances in the concentration of electrolytes can indicate the onset of disease. These same imbalances affect the dielectric properties of sweat. In this study, we used attenuated total reflection terahertz time domain spectroscopy to obtain the frequency-dependent dielectric properties of human sweat in a frequency range from 200 GHz to 2.5 THz. We have investigated the variation of dielectric properties of sweat collected from different regions of the human body, and we have observed that the real and imaginary part of dielectric permittivity decreases with the increase in frequency. A combination of left-hand Jonscher and Havriliak-Negami processes is used to model the results and reveal the presence of relaxation processes related to sodium and calcium ions concentrations. This information may help design novel biosensors to understand the human health condition and provide a hydration assessment.

Scanning near-field IR microscopy of proteins in lipid bilayers.

We use infrared near-field microscopy to chemically map the morphology of biological matrices. The investigated sample is built up from surface-tethered membrane proteins (cytochrome c oxidase) reconstituted in a lipid bilayer. We have carried out infrared near-field measurements in the frequency range between 1600 and 1800 cm(-1). By simultaneously recording the topography and chemical fingerprint of the protein-tethered lipid bilayer with a lateral resolution of 80 nm × 80 nm, we were able to probe locally the chemical signature of this membrane and to provide a local map of its surface morphology.

Confocal Raman microspectroscopy as an analytical tool to assess the mitochondrial status in human spermatozoa.

Confocal Raman microspectroscopy was used to investigate human sperm cells. Raman mapping with a 532 nm excitation laser allowed to unambiguously characterize the nucleus, the neck, and, in particular, the mitochondria-rich middle piece of a human sperm cell. The effect of ultraviolet radiation on different organelles of the sperm was quantified by localized spectral Raman signatures obtained within milliseconds. Chemical changes within the sub-cellular structure of the sperm cells were recorded as a function of ultraviolet light exposure time, showing the proof-of-principle that Raman microspectroscopy can be a fast diagnostic method for detecting the mitochondrial and motility status of human spermatozoa.

Communications: Polarity fluctuations of the protic ionic liquid ethylammonium nitrate in the terahertz regime.

We have measured the complex dielectric function of the protic ionic liquid ethylammonium nitrate in the frequency range between 0.15 and 1.8 THz with a terahertz time domain spectrometer. The experiments reveal a terahertz mode which can be described as a damped harmonic oscillator with a central frequency of 1.3 THz. The terahertz mode is assigned to an intermolecular vibration, presumably associated with hydrogen-bond dynamics. The data are combined with microwave data to represent the dielectric spectrum from quasistatic conditions up to 1.8 THz.

Solvation dynamics of model peptides probed by terahertz spectroscopy. Observation of the onset of collective network motions.

We have studied the solvation of model peptides at low hydration levels by terahertz absorption spectroscopy. We have recorded the concentration-dependent terahertz absorption coefficients of N-acetyl-glycine-amide (NAGA), N-acetyl-glycine-methylamide (NAGMA), N-acetyl-leucine-amide (NALA), N-acetyl-leucine-methylamide (NALMA), and N-acetyl-tryptophan-amide (NATA) in aqueous solution. We find a dramatic decrease in the THz absorption, if the number of water molecules per solute is less than 18-20. This change is taken as a signature for the breakdown of peptide-water network motions, which supports the hypothesis that a minimum number of hydration waters is required to activate these motions. This is well below a monolayer coverage of the model peptides. It is interesting to note that the required hydration level corresponds to the number of water molecules which are required for biological functionality.

From self-organization in relativistic electron bunches to coherent synchrotron light: observation using a photonic time-stretch digitizer.

In recent and future synchrotron radiation facilities, relativistic electron bunches with increasingly high charge density are needed for producing brilliant light at various wavelengths, from X-rays to terahertz. In such conditions, interaction of electron bunches with their own emitted electromagnetic fields leads to instabilities and spontaneous formation of complex spatial structures. Understanding these instabilities is therefore key in most electron accelerators. However, investigations suffer from the lack of non-destructive recording tools for electron bunch shapes. In storage rings, most studies thus focus on the resulting emitted radiation. Here, we present measurements of the electric field in the immediate vicinity of the electron bunch in a storage ring, over many turns. For recording the ultrafast electric field, we designed a photonic time-stretch analog-to-digital converter with terasamples/second acquisition rate. We could thus observe the predicted link between spontaneous pattern formation and giant bursts of coherent synchrotron radiation in a storage ring.

Nanoscale depth resolution in scanning near-field infrared microscopy.

We have recorded nanoscale topography and infrared chemical fingerprints of attomole layered lipids consisting of dimyristoylpho-sphatidylcholine on silicon and mica. Lipids deposited on mica built stacks consisting of up to 25 bilayers, each approximately 5 nm thick, spanning a range from 5-125 nm in height. Contrast evaluation as a function of layer thickness provides the near-field depth resolution.

Turn-key compact high temperature terahertz quantum cascade lasers: imaging and room temperature detection.

Terahertz quantum cascade lasers have been investigated as a turn-key terahertz source for widespread applications. Two lasers were mounted in a small liquid nitrogen-cooled dewar and combined with a sophisticated pulse driver. We present a detailed analysis in respect to current-voltage characteristics, emission wavelengths, polarization, pulse lengths and repetition rates. We have measured the laser power with a germanium photoconductor and compared the results to a Golay detector evaluating potential artifacts. We have studied mode profiles in the far-field which mirror the internal mode structure. Potential applications have been illustrated by imaging optical elements and a simple test object. Video rate room temperature imaging has been demonstrated in concept.

Unraveling the interactions between cold atmospheric plasma and skin-components with vibrational microspectroscopy.

Using infrared and Raman microspectroscopy, the authors examined the interaction of cold atmospheric plasma with the skin's built-in protective cushion, the outermost skin layer stratum corneum. Following a spectroscopic analysis, the authors could identify four prominent chemical alterations caused by plasma treatment: (1) oxidation of disulfide bonds in keratin leading to a generation of cysteic acid; (2) formation of organic nitrates as well as (3) of new carbonyl groups like ketones, aldehydes and acids; and (4) reduction of double bonds in the lipid matter lanolin, which resembles human sebum. The authors suggest that these generated acidic and NO-containing functional groups are the source of an antibacterial and regenerative environment at the treatment location of the stratum corneum. Based upon the author's results, the authors propose a mechanistic view of how cold atmospheric plasmas could modulate the skin chemistry to produce positive long-term effects on wound healing: briefly, cold atmospheric plasmas have the potential to transform the skin itself into a therapeutic resource.

Synergistic effects of atmospheric pressure plasma-emitted components on DNA oligomers: a Raman spectroscopic study.

Cold atmospheric-pressure plasmas have become of increasing importance in sterilization processes especially with the growing prevalence of multi-resistant bacteria. Albeit the potential for technological application is obvious, much less is known about the molecular mechanisms underlying bacterial inactivation. X-jet technology separates plasma-generated reactive particles and photons, thus allowing the investigation of their individual and joint effects on DNA. Raman spectroscopy shows that particles and photons cause different modifications in DNA single and double strands. The treatment with the combination of particles and photons does not only result in cumulative, but in synergistic effects. Profilometry confirms that etching is a minor contributor to the observed DNA damage in vitro. Schematics of DNA oligomer treatment with cold atmospheric-pressure plasma.

Setup of a scanning near field infrared microscope (SNIM): imaging of sub-surface nano-structures in gallium-doped silicon.

We have realized a scanning near-field infrared microscope in the 3-4 microm wavelength range. As a light source, a tunable high power continuous wave infrared optical parametric oscillator with an output power of up to 2.9 W in the 3-4 microm range has been set up. Using scanning near field infrared microscopy (SNIM) imaging we have been able to obtain a lateral resolution of < or =30 nm at a wavelength of 3.2 microm, which is far below the far-field resolution limit of lambda/2. Using this "chemical nanoscope" we could image a sub-surface structure of implanted gallium ions in a topographically flat silicon wafer giving evidence for a near-field contrast. The observed contrast is explained in terms of the effective infrared reflection as a function of the sub-surface gallium doping concentration. The future use of the setup for nm imaging in the chemically important OH, N-H and C-H stretching vibration is discussed.

Fast quantification of water in single living cells by near-infrared microscopy.

We have set up a near-infrared microscope using a tuneable diode laser in the range from 1530 to 1570 nm. This spectral range is close to the peak of the water overtone absorption. We used this new microscope to study liver cells, hepatocytes, showing that quantitative information of the intracellular water concentration in living cells can be extracted.