Laser-induced acoustic desorption of natural and functionalized biochromophores.

Laser-induced acoustic desorption (LIAD) has recently been established as a tool for analytical chemistry. It is capable of launching intact, neutral, or low charged molecules into a high vacuum environment. This makes it ideally suited to mass spectrometry. LIAD can be used with fragile biomolecules and very massive compounds alike. Here, we apply LIAD time-of-flight mass spectrometry (TOF-MS) to the natural biochromophores chlorophyll, hemin, bilirubin, and biliverdin and to high mass fluoroalkyl-functionalized porphyrins. We characterize the variation in the molecular fragmentation patterns as a function of the desorption and the VUV postionization laser intensity. We find that LIAD can produce molecular beams an order of magnitude slower than matrix-assisted laser desorption (MALD), although this depends on the substrate material. Using titanium foils we observe a most probable velocity of 20 m/s for functionalized molecules with a mass m = 10,000 Da.

Matter-wave interference of particles selected from a molecular library with masses exceeding 10,000 amu.

The quantum superposition principle, a key distinction between quantum physics and classical mechanics, is often perceived as a philosophical challenge to our concepts of reality, locality or space-time since it contrasts with our intuitive expectations with experimental observations on isolated quantum systems. While we are used to associating the notion of localization with massive bodies, quantum physics teaches us that every individual object is associated with a wave function that may eventually delocalize by far more than the body's own extension. Numerous experiments have verified this concept at the microscopic scale but intuition wavers when it comes to delocalization experiments with complex objects. While quantum science is the uncontested ideal of a physical theory, one may ask if the superposition principle can persist on all complexity scales. This motivates matter-wave diffraction and interference studies with large compounds in a three-grating interferometer configuration which also necessitates the preparation of high-mass nanoparticle beams at low velocities. Here we demonstrate how synthetic chemistry allows us to prepare libraries of fluorous porphyrins which can be tailored to exhibit high mass, good thermal stability and relatively low polarizability, which allows us to form slow thermal beams of these high-mass compounds, which can be detected using electron ionization mass spectrometry. We present successful superposition experiments with selected species from these molecular libraries in a quantum interferometer, which utilizes the diffraction of matter-waves at an optical phase grating. We observe high-contrast quantum fringe patterns of molecules exceeding a mass of 10,000 amu and having 810 atoms in a single particle.

Single-photon ionization of organic molecules beyond 10 kDa.

The volatilization and soft ionization of complex neutral macromolecules at low energies has remained an outstanding challenge for several decades. Most volatilization techniques in mass spectrometry produce ions already in the source and most of them lead to particle velocities in excess of several hundred meters per second. For many macromolecules, post-ionization is inefficient since electronic or optical excitations can be followed by competing non-ionizing internal conversion, electron recapture, or fragmentation processes. Here, we explore the laser-assisted volatilization of neutral perfluoroalkyl-functionalized tetraphenylporphyrins as well as their single-photon ionization using vacuum ultraviolet (VUV) light at 157 nm. A systematic investigation of the ionization curves allows us to determine the molecular velocity distribution and ionization cross sections. We demonstrate the detection of single photon ionized intact organic molecules in excess of 10 kDa from a slow molecular beam.

Real-time single-molecule imaging of quantum interference.

The observation of interference patterns in double-slit experiments with massive particles is generally regarded as the ultimate demonstration of the quantum nature of these objects. Such matter-wave interference has been observed for electrons, neutrons, atoms and molecules and, in contrast to classical physics, quantum interference can be observed when single particles arrive at the detector one by one. The build-up of such patterns in experiments with electrons has been described as the "most beautiful experiment in physics". Here, we show how a combination of nanofabrication and nano-imaging allows us to record the full two-dimensional build-up of quantum interference patterns in real time for phthalocyanine molecules and for derivatives of phthalocyanine molecules, which have masses of 514 AMU and 1,298 AMU respectively. A laser-controlled micro-evaporation source was used to produce a beam of molecules with the required intensity and coherence, and the gratings were machined in 10-nm-thick silicon nitride membranes to reduce the effect of van der Waals forces. Wide-field fluorescence microscopy detected the position of each molecule with an accuracy of 10 nm and revealed the build-up of a deterministic ensemble interference pattern from single molecules that arrived stochastically at the detector. In addition to providing this particularly clear demonstration of wave-particle duality, our approach could also be used to study larger molecules and explore the boundary between quantum and classical physics.

Quantum interference of large organic molecules.

The wave nature of matter is a key ingredient of quantum physics and yet it defies our classical intuition. First proposed by Louis de Broglie a century ago, it has since been confirmed with a variety of particles from electrons up to molecules. Here we demonstrate new high-contrast quantum experiments with large and massive tailor-made organic molecules in a near-field interferometer. Our experiments prove the quantum wave nature and delocalization of compounds composed of up to 430 atoms, with a maximal size of up to 60 Å, masses up to m=6,910 AMU and de Broglie wavelengths down to λ(dB)=h/mv≃1 pm. We show that even complex systems, with more than 1,000 internal degrees of freedom, can be prepared in quantum states that are sufficiently well isolated from their environment to avoid decoherence and to show almost perfect coherence.

Quantum interference distinguishes between constitutional isomers.

Matter waves, as introduced by de Broglie in 1923 (L. de Broglie, Nature, 1923, 112, 540), are a fundamental quantum phenomenon, describing the delocalized center of mass motion of massive bodies and we show here their sensitivity to the molecular structure of constitutional isomers.

Amphiphilic diblock copolymers for molecular recognition: metal-nitrilotriacetic acid functionalized vesicles.

Here we describe the design, synthesis, and characterization of new, metal-functionalized, amphiphilic diblock copolymers for molecular recognition. Polybutadiene-block-polyethylenoxide copolymers were synthesized by living anionic polymerization and end group functionalized with nitrilotriacetic acid and tris(nitrilotriacetic acid). After complexation with nickel and copper, these groups are known to selectively bind to oligohistidine residues of proteins. The polymers were characterized by 1H NMR spectroscopy, size exclusion chromatography, electron paramagnetic resonance, and UV-vis spectroscopy. Mixtures of these polymers with the respective nonfunctionalized block copolymers self-assemble in aqueous solution into vesicular structures with a controlled density of the metal complex end-groups on their surface. The accessibility of these binding sites was tested using maltose binding protein carrying a terminal decahistidine moiety and His-tagged enhanced green fluorescent protein as model systems. Fluorescence correlation spectroscopy clearly showed a significant and selective binding of these proteins to the vesicle surface.