Wir danken Robert Berger (Philipps-Universität Marburg, Deutschland) für anregende Diskussionen über die Interpretation der Daten und molekularen Chiralität im Allgemeinen. Wir sind dankbar, Julia Kiedrowski, Alexander Schießer und Michael Reggelin der TU Darmstadt (Deutschland), sowie Benjamin Spenger, Manuel Mazenauer und Jürgen Stohner von ZHAW Wädenswil (Schweiz) für die Bereitstellung der Probe.
Das Projekt wurde von der Landesinitiative Hessen für wissenschaftliche und wirtschaftliche Exzellenz unter den Fokus ELCH (Elektron Dynamik chiralen Systeme) und das Bundesministerium für Bildung und Forschung (BMBF) unterstützt. MS erkennt finanziellen Unterstützung durch die Adolf Messer Stiftung.

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H., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Imaging+the+Absolute+Configuration+of+a+Chiral+Epoxide+in+the+Gas+Phase.">Imaging the Absolute Configuration of a Chiral Epoxide in the Gas Phase.</a> Science. 342 (6162), 1084-1186 (2013).</li><li>D&#246;rner, R., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Cold+Target+Recoil+Ion+Momentum+Spectroscopy:+a+'momentum+microscope'+to+view+atomic+collision+dynamics.">Cold Target Recoil Ion Momentum Spectroscopy: a 'momentum microscope' to view atomic collision dynamics.</a> Physics Reports. 330, 95-192 (2000).</li><li>Ullrich, J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Recoil-ion+and+electron+momentum+spectroscopy:+reaction-microscopes.">Recoil-ion and electron momentum spectroscopy: reaction-microscopes.</a> Rep. 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Phys. 13, 7024-7036 (2010).</li><li>Ablikim, U., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Identification+of+absolute+geometries+of+cis+and+trans+molecular+isomers+by+Coulomb+Explosion+Imaging.">Identification of absolute geometries of cis and trans molecular isomers by Coulomb Explosion Imaging.</a> Sci. Rep. 6, 38202 (2016).</li></ol>

Die Autoren erklären keinen Interessenkonflikt.

Aufgrund der Vielzahl von Komponenten erfordert eine COLTRIMS-Setup ein ziemlich hohes Maß an Fachkompetenz, vor allem in den Bereichen Vakuumtechnik, Partikeldetektoren, schnelle Elektronik und Datenanalyse. Bevor er sich der Untersuchung von komplexen Arten, sollten daher gründlich überprüft werden, ob das Setup korrekt, z. B. durch die Durchführung und Analyse einer Messung auf ein zweiatomiges oder dreiatomigen Arten ausgeführt wird.
Optimierung der Intensität und Dauer der...

Chiralität ist ein Bestandteil unserer Natur, der faszinierenden Forscher mehr als 150 Jahren seit. In den 19th entdeckte Jahrhundert, Pasteur und van't Hoff, dass Moleküle in zwei Spiegelbild Strukturen auftreten können, die nicht Super-Eingliederungsmaßnahme - wie unsere linken und rechten Hand sind. Diese Eigenschaft wurde "chirale", aus dem griechischen Wort für "Hand" bezeichnet.
Bisher wurde kein Unterschied in thermodynamischen Eigenschaften oder Energie-Ebenen der linken und rechtshändigen Formen (die beiden "Enantiomere") gefunden. Um die Händigkeit von einer Probe zu analysieren und die Enantiomere trennen, kann Wechselwirkung mit anderen chiralen Molekülen verwendet werden, wie zum Beispiel in verschiedenen chromatographical Ansätze. 1 Chiroptical Methoden wie (Schwingung) kreisförmigen Dichroismus, (V) CD und Optik rotatorischen Dispersion, ORD, werden routinemäßig eingesetzt, um Enantiomere unterscheiden. 2
Wenn es um die Bestimmung der mikroskopischen Struktur geht, erfordern diese Techniken zusätzliche Angaben, z. B. von Quanten-physikalischen Berechnungen. Die einzige Technik, die allgemein akzeptiert wird, um direkt die absolute Konfiguration bestimmen ist anomale Röntgenbeugung. 3
Vor kurzem hat sich gezeigt, dass die absolute Konfiguration einfach chiralen Arten von Coulomb Explosion Imaging ermittelt werden kann. 4 , 5 bei diesem Ansatz Moleküle in der Gasphase sind multiplizieren ionisierten so dass die verbleibenden Kerne stark gegenseitig abstoßen. Diese Abstoßung führt zu schnellen Fragmentierung ("Explosion") der Moleküle. Die Richtung und das Ausmaß des Fragments Momenta korrelieren, die Struktur des Moleküls – für kleine Moleküle, entsprechen die Dynamik Richtungen überraschend gut zu den Bond-Achsen. Coulomb-Explosion für molekulare Strukturbestimmung hat mit molekularen Ion Beams von einer Zugriffstaste Pionierarbeit geleistet wurde. 6 dieser Beam-Folie-Technik hat vor kurzem auch chirale Anerkennung beantragt. 7
Entgegen der anomalen Röntgendiffraktometrie muss die Probe nicht kristalline aber in der Gasphase vorgesehen sein. Dies macht den Coulomb Explosion Ansatz ideal für flüchtige Arten und somit komplementär zur Röntgenbeugung. In bestimmten Fällen kann der Händigkeit auch für einzelne Moleküle bestimmt werden.
In der Praxis hat die genaue Rekonstruktion der molekularen Struktur selbst für Methan-Derivate, z. B. Moleküle mit einem zentralen Kohlenstoff und verschiedene Substituenten schwierig erwiesen. Dies ist zurückzuführen auf die Tatsache, dass die Interaktion zwischen den Fragmenten nicht genau Coulombsche und gleichzeitig nicht alle Bindungen aufzubrechen. Um stereochemische informieren, vor allem zu unterscheiden, Enantiomere, ist diese Rekonstruktion glücklicherweise nicht notwendig. Stattdessen können die Dynamik Vektoren aus verschiedenen Fragmenten um eine Menge zu liefern, die für die linken und rechtshändigen Moleküle unterscheidet korreliert werden. Um zuverlässige Ergebnisse zu erhalten, müssen mindestens vier Fragment Momenta erfasst werden.
Um diese Dynamik-Informationen zu messen, müssen die Fragmente aus ein – und einzige – molekularer Zerfall in einer einzigen Messung Schritt erkannt werden. Diese Bedingung wird in der Regel als "koinzident Detection" bezeichnet. Darüber hinaus haben die Emission Richtungen analysiert werden, die Beträge in der Praxis zum Aufzeichnen von die Zeit und die Position des Fragments in einem List-Modus-Datenformat auswirken.
Atomare und molekulare Physik haben Techniken entwickelt, die Umsetzung dieses Ansatzes der Messung durch den Einsatz von elektrostatischen Spektrometer für die Masse Trennung und zeitkritische und Position Multi-hit-Detektoren. Das prominenteste Beispiel ist die COLTRIMS (kalte Target Recoil Ion Momentum Spektroskopie) Setup – auch bekannt als Reaktion Mikroskop. 8 , 9 eine Skizze für ein solches Experiment ist in Abbildung 1aufgeführt. Im Gegensatz zu einem standard COLTRIMS, die Elektronen als auch aufzeichnen können, erfordert das Coulomb Explosion Imaging nur die Ionen-Detektor.
Spektrometer und Detektor werden im Ultra-Hochvakuum montiert (&#60; 1 x 10-9 hPa), Schaffung von Ionen aus Restgas zu vermeiden. Einzelne Moleküle der Probe sind über eine gasförmige molekulare Freistrahl erstellt von Überschall Erweiterung bereitgestellt: aufgrund der Dampfdruck, erweitern die Moleküle durch eine kleine Düse (rund 50 µm Durchmesser) in das Vakuum. Dieser Teil des Experiments, die Quelle-Kammer ist aus der Interaktion Region durch in der Regel zwei Skimmer und differenziell gepumpten Phasen getrennt. Eine zusätzliche differentiell gepumpt Abschnitt befindet sich hinter der Interaktion Region dump den Gasstrahl und somit Hintergrund Gas im Bereich Interaktion zu vermeiden.
Die ionisierende Strahlung überschneidet sich mit der molekularen Jet unter 90°. Die meisten Labors verwenden heutzutage Femtosekunden-Laserpulse, obwohl Synchrotronstrahlung, schnellen Ionen oder Elektronen Auswirkungen sind möglich "Geschosse" Coulomb-Explosion zu induzieren.
Das folgende Protokoll macht die Annahme, dass eine laufende Setup für die deckungsgleiche Darstellung von Ionen und ein Femtosekunden-Laser sind im Labor zur Verfügung. Die Peak-Intensität induzieren Coulomb Explosion in vier oder sogar fünf Fragmente benötigt muss in der Größenordnung von 6 x 1014 W/cm2. Um überaus lange Messungen zu vermeiden, sollte die Wiederholrate des Lasers 10 kHz oder mehr sein. Dies ist entscheidend, denn auf der einen Seite koinzident Erkennung nur festgestellt werden kann, ist die Wahrscheinlichkeit, dass Fragmentierung im Laserfokus deutlich unter 1 pro Laserpuls (idealerweise nicht mehr als 10 %). Die totale Fragmentierungsrate sollte auf der anderen Seite nicht niedriger als ein paar kHz sein, weil der Anteil der relevanten multifragmentation Wege in der Regel weniger als 10-4. So ermutigende Tatsache, es sollte erwähnt werden, dass im Prinzip bereits ein einzelnes Fragmentierung Ereignis ausreichend ist, um die Konfiguration einer Enantiopure Probe zu identifizieren, und die Erkennung von ein paar hundert erlaubt um zu bestimmen, die Fülle der Enantiomere in eine Stichprobe von Enantiomeren unbekannter Zusammensetzung.

<table><tbody><tr><td>CHBrCl2</td><td>SigmaAldrich</td><td>139181-10G</td><td>or other suitable sample</td></tr><tr><td>femtosecond laser system</td><td>KMLabs</td><td>Wyvern500</td><td></td></tr><tr><td>High-reflective mirrors</td><td>EKSMA</td><td>042-0800</td><td></td></tr><tr><td>mirror mounts</td><td>Newport</td><td>U100-A-LH-2K&amp;nbsp;&amp;nbsp;</td><td></td></tr><tr><td>focusing mirror (protected silver, f = 75 mm)</td><td>Thorlabs&amp;nbsp;</td><td>CM254-075-P01</td><td>(if available: f = 60 mm)</td></tr><tr><td>COLTRIMS spectrometer, including electronics and data acquisition system</td><td>RoentDek</td><td>custom</td><td>contrary to the standard COLTRIMS, only one detector is needed</td></tr></tbody></table>

coulomb explosion imaging as a tool to distinguish between stereoisomers

Dieser Artikel zeigt, wie die COLTRIMS (kalte Target Recoil Ion Momentum Spektroskopie) oder die "Reaktion Mikroskop" Technik verwendet werden, um Enantiomere (Stereoisomere) einfache chiralen Arten auf der Ebene der einzelnen Moleküle unterscheiden. Bei diesem Ansatz ein gasförmiger molekulare Jet der Probe in eine Vakuumkammer erweitert und schneidet mit Laserpulsen Femtosekunden (fs). Die hohe Intensität der Impulse führt um zu schnell mehrere Ionisation, zünden eine sogenannte Coulomb-Explosion, die mehrere kationisch (positiv geladenen) Fragmente produziert. Ein elektrostatisches Feld führt diese kationen auf zeitkritische und Position Detektoren. Ähnlich wie bei einem Time-of-Flight-Massenspektrometer, die Ankunftszeit jedes Ion liefert Informationen über seine Masse. Ein Überschuss ist das elektrostatische Feld so eingestellt, dass die Abstrahlrichtung und der kinetischen Energie nach Fragmentierung zu Variationen in der Time-of-Flight und Auswirkungen auf den Detektor führen.
Jedes Ion Auswirkungen erzeugt ein elektronisches Signal im Detektor; Dieses Signal wird von Hochfrequenz-Elektronik behandelt und durch Veranstaltung von einem Computer aufgezeichnet. Die gespeicherten Daten entsprechen den Auswirkungen Zeiten und Positionen. Mit diesen Daten können die Energie und die Abstrahlrichtung des jedes Fragment berechnet werden. Diese Werte beziehen sich auf strukturelle Eigenschaften des Moleküls ermittelt, d. h. auf die Bindungslängen und relativen Positionen der Atome, Molekül von Molekül bestimmen die Händigkeit von einfachen chiralen Arten und anderen Isomeren Funktionen ermöglichen.

In diesem Teil zeigen wir Ergebnisse für Trihalomethane. Diese Arten sind ideal für Proof of Principle Experimenten aufgrund ihrer Einfachheit und hohen Dampfdruck. In der Zwischenzeit ist die komplexeren Arten Halothan untersucht worden mit einzelnen Soft-X-Ray Photonen aus einem Synchrotron-Quelle mehrere Ionisation zu induzieren. 14
CHBrClF
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Watch this Scientific Journal Video about Coulomb Explosion Imaging as a Tool to Distinguish Between Stereoisomers at JoVE.com

Coulomb Explosion Imaging as a Tool to Distinguish Between Stereoisomers

Coulomb Explosion Imaging als Instrument zur Unterscheidung zwischen Stereoisomere

Für kleine chiralen Arten bietet Coulomb Explosion Imaging einen neuen Ansatz um die Händigkeit einzelner Moleküle bestimmen.

This article shows how the COLTRIMS (Cold Target Recoil Ion Momentum Spectroscopy) or the "reaction microscope" technique can be used to distinguish ...

coulomb-explosion-imaging-as-tool-to-distinguish-between

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Organic Chemistry

Chemistry

Unit 1

Transition Metals and Coordination Complexes

Stereoisomerism

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9.0K Aufrufe.  Goethe-Universität Frankfurt am Main. Für kleine chiralen Arten bietet Coulomb Explosion Imaging einen neuen Ansatz um die Händigkeit einzelner Moleküle bestimmen.

Serie: Coulomb Explosion Imaging as a Tool to Distinguish Between Stereoisomers

Spatial Separation of Molecular Conformers and Clusters

Gas-phase molecular physics and physical chemistry experiments commonly use supersonic expansions through pulsed valves for the production of cold molecular beams. However, these beams often contain multiple conformers and clusters, even at low rotational temperatures. We present an experimental methodology that allows the spatial separation of these constituent parts of a molecular beam expansion. Using an electric deflector the beam is separated by its mass-to-dipole moment ratio, analogous to a bender or an electric sector mass spectrometer spatially dispersing charged molecules on the basis of their mass-to-charge ratio. This deflector exploits the Stark effect in an inhomogeneous electric field and allows the separation of individual species of polar neutral molecules and clusters. It furthermore allows the selection of the coldest part of a molecular beam, as low-energy rotational quantum states generally experience the largest deflection. Different structural isomers (conformers) of a species can be separated due to the different arrangement of functional groups, which leads to distinct dipole moments. These are exploited by the electrostatic deflector for the production of a conformationally pure sample from a molecular beam. Similarly, specific cluster stoichiometries can be selected, as the mass and dipole moment of a given cluster depends on the degree of solvation around the parent molecule. This allows experiments on specific cluster sizes and structures, enabling the systematic study of solvation of neutral molecules.

We present a technique that allows the spatial separation of different conformers or clusters present in a molecular beam. An electrostatic deflector is used to separate species by their mass-to-dipole moment ratio, leading to the production of gas-phase ensembles of a single conformer or cluster stoichiometry.

Räumliche Trennung von molekularen Konformen und Clustern

Gas-phase molecular physics and physical chemistry experiments commonly use supersonic expansions through pulsed valves for the production of cold ...

Forschung

Ingenieurwesen

Direct Imaging of Laser-driven Ultrafast Molecular Rotation

We present a method for visualizing laser-induced, ultrafast molecular rotational wave packet dynamics. We have developed a new 2-dimensional Coulomb explosion imaging setup in which a hitherto-impractical camera angle is realized. In our imaging technique, diatomic molecules are irradiated with a circularly polarized strong laser pulse. The ejected atomic ions are accelerated perpendicularly to the laser propagation. The ions lying in the laser polarization plane are selected through the use of a mechanical slit and imaged with a high-throughput, 2-dimensional detector installed parallel to the polarization plane. Because a circularly polarized (isotropic) Coulomb exploding pulse is used, the observed angular distribution of the ejected ions directly corresponds to the squared rotational wave function at the time of the pulse irradiation. To create a real-time movie of molecular rotation, the present imaging technique is combined with a femtosecond pump-probe optical setup in which the pump pulses create unidirectionally rotating molecular ensembles. Due to the high image throughput of our detection system, the pump-probe experimental condition can be easily optimized by monitoring a real-time snapshot. As a result, the quality of the observed movie is sufficiently high for visualizing the detailed wave nature of motion. We also note that the present technique can be implemented in existing standard ion imaging setups, offering a new camera angle or viewpoint for the molecular systems without the need for extensive modification.

We present a protocol for creating a real-time movie of a molecular rotational wave packet using a high-resolution Coulomb explosion imaging setup.

Direct Imaging von lasergetriebenen Ultrakurz Molecular Rotation

We present a method for visualizing laser-induced, ultrafast molecular rotational wave packet dynamics. We have developed a new 2-dimensional Coulomb ...

Chemie

Photoelectron Imaging of Anions Illustrated by 310 Nm Detachment of F&#8722;

Anion photoelectron imaging is a very efficient method for the study of energy states of bound negative ions, neutral species and interactions of unbound electrons with neutral molecules/atoms. State-of-the-art in vacuo anion generation techniques allow application to a broad range of atomic, molecular, and cluster anion systems. These are separated and selected using time-of-flight mass spectrometry. Electrons are removed by linearly polarized photons (photo detachment) using table-top laser sources which provide ready access to excitation energies from the infra-red to the near ultraviolet. Detecting the photoelectrons with a velocity mapped imaging lens and position sensitive detector means that, in principle, every photoelectron reaches the detector and the detection efficiency is uniform for all kinetic energies. Photoelectron spectra extracted from the images via mathematical reconstruction using an inverse Abel transformation reveal details of the anion internal energy state distribution and the resultant neutral energy states. At low electron kinetic energy, typical resolution is sufficient to reveal energy level differences on the order of a few millielectron-volts, i.e., different vibrational levels for molecular species or spin-orbit splitting in atoms. Photoelectron angular distributions extracted from the inverse Abel transformation represent the signatures of the bound electron orbital, allowing more detailed probing of electronic structure. The spectra and angular distributions also encode details of the interactions between the outgoing electron and the residual neutral species subsequent to excitation. The technique is illustrated by the application to an atomic anion (F&#8722;), but it can also be applied to the measurement of molecular anion spectroscopy, the study of low lying anion resonances (as an alternative to scattering experiments) and femtosecond (fs) time resolved studies of the dynamic evolution of anions.

Here, we present a protocol for photoelectron imaging of anionic species. Anions generated in vacuo and separated by mass spectrometry are probed using velocity mapped photoelectron imaging, providing details of anion and neutral energy levels, anion and neutral structure and the nature of the anion electronic state.

Photoelektronen Bildgebung von Anionen illustriert von 310 Nm Ablösung der F−

Anion photoelectron imaging is a very efficient method for the study of energy states of bound negative ions, neutral species and interactions of unbound ...

Using a Cyclic Ion Mobility Spectrometer for Tandem Ion Mobility Experiments

Accurate characterization of chemical structures is important to understand their underlying biological mechanisms and functional properties. Mass spectrometry (MS) is a popular tool but is not always sufficient to completely unveil all structural features. For example, although carbohydrates are biologically relevant, their characterization is complicated by numerous levels of isomerism. Ion mobility spectrometry (IMS) is an interesting complement because it is sensitive to ion conformations and, thus, to isomerism. 
Furthermore, recent advances have significantly improved the technique: the last generation of Cyclic IMS instruments offers additional capabilities compared to linear IMS instruments, such as an increased resolving power or the possibility to perform tandem ion mobility (IMS/IMS) experiments. During IMS/IMS, an ion is selected based on its ion mobility, fragmented, and reanalyzed to obtain ion mobility information about its fragments. Recent work showed that the mobility profiles of the fragments contained in such IMS/IMS data can act as a fingerprint of a particular glycan and can be used in a molecular networking strategy to organize glycomics datasets in a structurally relevant way. 
The goal of this protocol is thus to describe how to generate IMS/IMS data, from sample preparation to the final Collision Cross Section (CCS) calibration of the ion mobility dimension that yields reproducible spectra. Taking the example of one representative glycan, this protocol will show how to build an IMS/IMS control sequence on a Cyclic IMS instrument, how to account for this control sequence to translate IMS arrival time into drift time (i.e., the effective separation time applied to the ions), and how to extract the relevant mobility information from the raw data. This protocol is designed to clearly explain the critical points of an IMS/IMS experiment and thus help new Cyclic IMS users perform straightforward and reproducible acquisitions.

Ion mobility spectrometry (IMS) is an interesting complement to mass spectrometry for the characterization of biomolecules, notably because it is sensitive to isomerism. This protocol describes a tandem IMS (IMS/IMS) experiment, which allows the isolation of a molecule and the generation of the mobility profiles of its fragments.

Verwendung eines zyklischen Ionenmobilitätsspektrometers für Tandemionen-Mobilitätsexperimente

Accurate characterization of chemical structures is important to understand their underlying biological mechanisms and functional properties. Mass ...

Direct Comparison of Hyperspectral Stimulated Raman Scattering and Coherent Anti-Stokes Raman Scattering Microscopy for Chemical Imaging

Stimulated Raman scattering (SRS) and coherent anti-Stokes Raman scattering (CARS) microscopy are the most widely used coherent Raman scattering imaging technologies. Hyperspectral SRS and CARS imaging offer Raman spectral information at every pixel, which enables better separation of different chemical compositions. Although both techniques require two excitation lasers, their signal detection schemes and spectral properties are quite different. The goal of this protocol is to perform both hyperspectral SRS and CARS imaging on a single platform and compare the two microscopy techniques for imaging different biological samples. The spectral focusing method is employed to acquire spectral information using femtosecond lasers. By using standard chemical samples, the sensitivity, spatial resolution, and spectral resolution of SRS and CARS in the same excitation conditions (i.e., power at the sample, pixel dwell time, objective lens, pulse energy) are compared. The imaging contrasts of CARS and SRS for biological samples are juxtaposed and compared. The direct comparison of CARS and SRS performances would allow for optimal selection of the modality for chemical imaging.

This paper directly compares the resolution, sensitivity, and imaging contrasts of stimulated Raman scattering (SRS) and coherent anti-Stokes Raman scattering (CARS) integrated into the same microscope platform. The results show that CARS has a better spatial resolution, SRS gives better contrasts and spectral resolution, and both methods have similar sensitivity.

Direkter Vergleich der hyperspektralen stimulierten Raman-Streuung und der kohärenten Anti-Stokes-Raman-Streumikroskopie für die chemische Bildgebung

Stimulated Raman scattering (SRS) and coherent anti-Stokes Raman scattering (CARS) microscopy are the most widely used coherent Raman scattering imaging ...

Differential Imaging of Biological Structures with Doubly-resonant Coherent Anti-stokes Raman Scattering (CARS)

Coherent Raman imaging techniques have seen a dramatic increase in activity over the past decade due to their promise to enable label-free optical imaging with high molecular specificity 1. The sensitivity of these techniques, however, is many orders of magnitude weaker than fluorescence, requiring milli-molar molecular concentrations 1,2. Here, we describe a technique that can enable the detection of weak or low concentrations of Raman-active molecules by amplifying their signal with that obtained from strong or abundant Raman scatterers. The interaction of short pulsed lasers in a biological sample generates a variety of coherent Raman scattering signals, each of which carry unique chemical information about the sample. Typically, only one of these signals, e.g. Coherent Anti-stokes Raman scattering (CARS), is used to generate an image while the others are discarded. However, when these other signals, including 3-color CARS and four-wave mixing (FWM), are collected and compared to the CARS signal, otherwise difficult to detect information can be extracted 3. For example, doubly-resonant CARS (DR-CARS) is the result of the constructive interference between two resonant signals 4. We demonstrate how tuning of the three lasers required to produce DR-CARS signals to the 2845 cm-1 CH stretch vibration in lipids and the 2120 cm-1 CD stretching vibration of a deuterated molecule (e.g. deuterated sugars, fatty acids, etc.) can be utilized to probe both Raman resonances simultaneously. Under these conditions, in addition to CARS signals from each resonance, a combined DR-CARS signal probing both is also generated. We demonstrate how detecting the difference between the DR-CARS signal and the amplifying signal from an abundant molecule's vibration can be used to enhance the sensitivity for the weaker signal. We further demonstrate that this approach even extends to applications where both signals are generated from different molecules, such that e.g. using the strong Raman signal of a solvent can enhance the weak Raman signal of a dilute solute.

Differential Imaging of Biological Structures with Doubly-resonant Coherent Anti-stokes Raman Scattering CARS

A combination of three single wavelength short-pulsed lasers is used to generate coherent anti-Stokes Raman scattering (CARS) and doubly-resonant CARS (DR-CARS). The difference between these signals provides enhanced sensitivity for otherwise difficult to detect coherent Raman signals, enabling imaging of weak Raman scatterers.

Differential Imaging biologischer Strukturen mit doppelt-resonanten kohärente Anti-Stokes Raman-Streuung (CARS)

Coherent Raman imaging techniques have seen a dramatic increase in activity over the past decade due to their promise to enable label-free optical imaging ...

Biologie

Verwendung eines VSFG-Mikroskops für die multimodale, schnelle, hyperspektrale chemische Analyse

Multimodal Nonlinear Hyperspectral Chemical Imaging Using Line-Scanning Vibrational Sum-Frequency Generation Microscopy

Vibrational sum-frequency generation (VSFG), a second-order nonlinear optical signal, has traditionally been used to study molecules at interfaces as a spectroscopy technique with a spatial resolution of ~100 &#181;m. However, the spectroscopy is not sensitive to the heterogeneity of a sample. To study mesoscopically heterogeneous samples, we, along with others, pushed the resolution limit of VSFG spectroscopy down to ~1 &#181;m level and constructed the VSFG microscope. This imaging technique not only can resolve sample morphologies through imaging, but also record a broadband VSFG spectrum at every pixel of the images. Being a second-order nonlinear optical technique, its selection rule enables the visualization of non-centrosymmetric or chiral self-assembled structures commonly found in biology, materials science, and bioengineering, among others. In this article, the audience will be guided through an inverted transmission design that allows for imaging unfixed samples. This work also showcases that VSFG microscopy can resolve chemical-specific geometric information of individual self-assembled sheets by combining it with a neural network function solver. Lastly, the images obtained under brightfield, SHG, and VSFG configurations of various samples briefly discuss the unique information revealed by VSFG imaging.

Autor im Rampenlicht: Enthüllung des Potenzials der VSFG-Mikroskopie bei der Untersuchung mesoskopisch heterogener selbstorganisierter Strukturen 

A multimodal, rapid hyperspectral imaging framework was developed to obtain broadband vibrational sum-frequency generation (VSFG) images, along with brightfield, second harmonic generation (SHG) imaging modalities. Due to the infrared frequency being resonant with molecular vibrations, microscopic structural and mesoscopic morphology knowledge is revealed of symmetry-allowed samples.

Multimodale nichtlineare hyperspektrale chemische Bildgebung mit Line-Scanning-Schwingungssummen-Frequenz-Generierungsmikroskopie

Vibrational sum-frequency generation (VSFG), a second-order nonlinear optical signal, has traditionally been used to study molecules at interfaces as a ...

Stereoisomers

On the basis of mirror symmetry, stereoisomers of an organic molecule can be further classified into diastereomers and enantiomers. Diastereomers are stereoisomers that are not mirror images of each other. Substituted alkenes, such as the cis and trans isomers of 2-butene, are diastereomers, as these molecules exhibit different spatial orientations of their constituent atoms, are not mirror images of each other,&#160;and do not interconvert. Here, the interconversion is suppressed due to restricted rotation around the &#960; bond. Another class of diastereomers &#8212; those without &#960; bonds &#8212; are molecules that have non-superposable spatial orientations and exhibit different configurations of their substituent groups at some, but not all, stereocenters. For example, cis-1,2-dimethylcyclohexane and trans-1,2-dimethylcyclohexane are diastereomers, as these molecules are not superposable and have a different configuration of the methyl and hydrogen groups at only one out of their two stereocenters.
Enantiomers are stereoisomers that are mirror images of each other. As only chiral molecules can have non-superposable mirror images, enantiomers are chiral molecules. For example, the chiral molecule 2-butanol and its mirror image are enantiomers, as these molecules exhibit non-superposable spatial orientations of their constituent atoms and are mirror images of each other. A chiral molecule and its mirror image are collectively referred to as an enantiomeric pair, or a pair of enantiomers. The enantiomer of a chiral molecule can be drawn by taking its mirror image from any position or&#160;exchanging the positions of two of the substituents at each stereocenter of the molecule.

Stereoisomers: Diastereomers and Enantiomers

Stereoisomere

On the basis of mirror symmetry, stereoisomers of an organic molecule can be further classified into diastereomers and enantiomers. Diastereomers are ...

Coulomb Explosion Imaging als Instrument zur Unterscheidung zwischen Stereoisomere

Zusammenfassung

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Direkter Vergleich der hyperspektralen stimulierten Raman-Streuung und der kohärenten Anti-Stokes-Raman-Streumikroskopie für die chemische Bildgebung

Differential Imaging biologischer Strukturen mit doppelt-resonanten kohärente Anti-Stokes Raman-Streuung (CARS)

Multimodale nichtlineare hyperspektrale chemische Bildgebung mit Line-Scanning-Schwingungssummen-Frequenz-Generierungsmikroskopie

Multimodale nichtlineare hyperspektrale chemische Bildgebung mit Line-Scanning-Schwingungssummen-Frequenz-Generierungsmikroskopie

Multimodale nichtlineare hyperspektrale chemische Bildgebung mit Line-Scanning-Schwingungssummen-Frequenz-Generierungsmikroskopie

Stereoisomere