Highly sensitive single-molecule detection of macromolecule ion beams.

The analysis of proteins in the gas phase benefits from detectors that exhibit high efficiency and precise spatial resolution. Although modern secondary electron multipliers already address numerous analytical requirements, additional methods are desired for macromolecules at energies lower than currently used in post-acceleration detection. Previous studies have proven the sensitivity of superconducting detectors to high-energy particles in time-of-flight mass spectrometry. Here, we demonstrate that superconducting nanowire detectors are exceptionally well suited for quadrupole mass spectrometry and exhibit an outstanding quantum yield at low-impact energies. At energies as low as 100 eV, the sensitivity of these detectors surpasses conventional ion detectors by three orders of magnitude, and they offer the possibility to discriminate molecules by their impact energy and charge. We demonstrate three developments with these compact and sensitive devices, the recording of 2D ion beam profiles, photochemistry experiments in the gas phase, and advanced cryogenic electronics to pave the way toward highly integrated detectors.

Giving the Green Light to Photochemical Uncaging of Large Biomolecules in High Vacuum.

The isolation of biomolecules in a high vacuum enables experiments on fragile species in the absence of a perturbing environment. Since many molecular properties are influenced by local electric fields, here we seek to gain control over the number of charges on a biopolymer by photochemical uncaging. We present the design, modeling, and synthesis of photoactive molecular tags, their labeling to peptides and proteins as well as their photochemical validation in solution and in the gas phase. The tailored tags can be selectively cleaved off at a well-defined time and without the need for any external charge-transferring agents. The energy of a single or two green photons can already trigger the process, and it is soft enough to ensure the integrity of the released biomolecular cargo. We exploit differences in the cleavage pathways in solution and in vacuum and observe a surprising robustness in upscaling the approach from a model system to genuine proteins. The interaction wavelength of 532 nm is compatible with various biomolecular entities, such as oligonucleotides or oligosaccharides.

Nanoscale Magnetism Probed in a Matter-Wave Interferometer.

We explore a wide range of fundamental magnetic phenomena by measuring the dephasing of matter-wave interference fringes upon application of a variable magnetic gradient. The versatility of our interferometric Stern-Gerlach technique enables us to study the magnetic properties of alkali atoms, organic radicals, and fullerenes in the same device, with magnetic moments ranging from a Bohr magneton to less than a nuclear magneton. We find evidence for magnetization of a supersonic beam of organic radicals and, most notably, observe a strong magnetic response of a thermal C_{60} beam consistent with high-temperature atomlike deflection of rotational magnetic moments.

Kapitza-Dirac Blockade: A Universal Tool for the Deterministic Preparation of Non-Gaussian Oscillator States.

Harmonic oscillators count among the most fundamental quantum systems with important applications in molecular physics, nanoparticle trapping, and quantum information processing. Their equidistant energy level spacing is often a desired feature, but at the same time a challenge if the goal is to deterministically populate specific eigenstates. Here, we show how interference in the transition amplitudes in a bichromatic laser field can suppress the sequential climbing of harmonic oscillator states (Kapitza-Dirac blockade) and achieve selective excitation of energy eigenstates, cat states, and other non-Gaussian states. This technique can transform the harmonic oscillator into a coherent two-level system or be used to build a large-momentum-transfer beam splitter for matter waves. To illustrate the universality of the concept, we discuss feasible experiments that cover many orders of magnitude in mass, from single electrons over large molecules to dielectric nanoparticles.

Relative Abundances of Species or Sequence Variants Can Be Misleading: Soil Fungal Communities as an Example.

Plant production systems that are more sustainable than conventional monoculture croplands are the vision of future agriculture. With numerous environmental benefits, agroforestry is among the most promising alternatives. Although soil fungi are key drivers of plant productivity and ecosystem processes, investigations of these microorganisms in temperate agroforestry systems are scarce, leaving our understanding of agricultural systems under agroforestry practice incomplete. Here, we assessed the composition and diversity of the soil fungal community as well as the frequency (relative abundance) of fungal groups in three paired temperate poplar-based alley cropping (agroforestry) and monoculture cropland systems by amplicon sequencing. Analysis of microbiomes using relative abundances of species or sequence variants obtained from amplicon sequencing ignores microbial population size, which results in several problems. For example, species stimulated by environmental parameters may appear unaffected or suppressed in amplicon counts. Therefore, we determined absolute abundances of selected fungal groups as well as total fungal population size by real-time polymerase chain reaction (PCR). Tree rows strongly affected the community composition and increased the population size and species richness of soil fungi. Furthermore, ectomycorrhiza were strongly promoted by the tree rows. We speculate that mycorrhiza improved the nutrient acquisition in unfertilized tree rows, thereby contributing to the total productivity of the system. Comparison of relative and absolute abundances revealed dramatic discrepancies, highlighting that amplicon sequencing alone cannot adequately assess population size and dynamics. The results of our study highlight the necessity of combining frequency data based on amplicon sequencing with absolute quantification.

Bragg Diffraction of Large Organic Molecules.

We demonstrate Bragg diffraction of the antibiotic ciprofloxacin and the dye molecule phthalocyanine at a thick optical grating. The observed patterns show a single dominant diffraction order with the expected dependence on the incidence angle as well as oscillating population transfer between the undiffracted and diffracted beams. We achieve an equal-amplitude splitting of 14ℏk (photon momenta) and maximum momentum transfer of 18ℏk. This paves the way for efficient, large-momentum beam splitters and mirrors for hot and complex molecules.

Quantum-assisted diamagnetic deflection of molecules.

We measure the diamagnetic deflection of anthracene and adamantane in a long-baseline matter-wave interferometer. From the nanometer-level deflection we extract the magnetic susceptibilities of the molecules which we compare with calculations and previous results. Adamantane yields an isotropic average mass susceptibility of -8.0 ± 1.1 m3 kg-1, consistent with expectations, while anthracene yields a higher-than-anticipated value of -13.6 ± 1.3 m3 kg-1. We attribute the high anthracene value to the planar aromatic molecule's magnetic anisotropy and partial alignment in the molecular beam, and estimate the magnitude of the effect on the observed deflection.

Matter-wave interference and deflection of tripeptides decorated with fluorinated alkyl chains.

Studies of neutral biomolecules in the gas phase allow for the study of molecular properties in the absence of solvent and charge effects, thus complementing spectroscopic and analytical methods in solution or in ion traps. Some properties, such as the static electronic susceptibility, are best accessed in experiments that act on the motion of the neutral molecules in an electric field. Here, we screen seven peptides for their thermal stability and electron impact ionizability. We identify two tripeptides as sufficiently volatile and thermostable to be evaporated and interfered in the long-baseline universal matter-wave interferometer. Monitoring the deflection of the interferometric molecular nanopattern in a tailored external electric field allows us to measure the static molecular susceptibility of Ala-Trp-Ala and Ala-Ala-Trp bearing fluorinated alkyl chains at C- and N-termini. The respective values are 4 π ε 0 × 330 ± 150 Å 3 and 4 π ε 0 × 270 ± 80 Å 3 .

A fiber-based beam profiler for high-power laser beams in confined spaces and ultra-high vacuum.

Laser beam profilometry is an important scientific task with well-established solutions for beams propagating in air. It has, however, remained an open challenge to measure beam profiles of high-power lasers in ultra-high vacuum and in tightly confined spaces. Here we present a novel scheme that uses a single multi-mode fiber to scatter light and guide it to a detector. The method competes well with commercial systems in position resolution, can reach through apertures smaller than 500×500 µm2 and is compatible with ultra-high vacuum conditions. The scheme is simple, compact, reliable and can withstand laser intensities beyond 2 MW/cm2.

Neutralization of insulin by photocleavage under high vacuum.

Charge reduction and neutralization of electro-sprayed peptides are realized by selective gas-phase photocleavage of tailored covalent tags. The concept is demonstrated with four model peptides in positive and negative ion modes and tagged insulin as the largest construct.

Silicon microcavity arrays with open access and a finesse of half a million.

Optical resonators are essential for fundamental science, applications in sensing and metrology, particle cooling, and quantum information processing. Cavities can significantly enhance interactions between light and matter. For many applications they perform this task best if the mode confinement is tight and the photon lifetime is long. Free access to the mode center is important in the design to admit atoms, molecules, nanoparticles, or solids into the light field. Here, we demonstrate how to machine microcavity arrays of extremely high quality in pristine silicon. Etched to an almost perfect parabolic shape with a surface roughness on the level of 2 Å and coated to a finesse exceeding F = 500,000, these new devices can have lengths below 17 µm, confining the photons to 5 µm waists in a mode volume of 88λ3. Extending the cavity length to 150 µm, on the order of the radius of curvature, in a symmetric mirror configuration yields a waist smaller than 7 µm, with photon lifetimes exceeding 64 ns. Parallelized cleanroom fabrication delivers an entire microcavity array in a single process. Photolithographic precision furthermore yields alignment structures that result in mechanically robust, pre-aligned, symmetric microcavity arrays, representing a light-matter interface with unprecedented performance.

Conformer Selection by Matter-Wave Interference.

We establish that matter-wave diffraction at near-resonant ultraviolet optical gratings can be used to spatially separate individual conformers of complex molecules. Our calculations show that the conformational purity of the prepared beam can be close to 100% and that all molecules remain in their electronic ground state. The proposed technique is independent of the dipole moment and the spin of the molecule and thus paves the way for structure-sensitive experiments with hydrocarbons and biomolecules, such as neurotransmitters and hormones, which have evaded conformer-pure isolation so far.

A Quantum Ruler for Magnetic Deflectometry.

Matter-wave near-field interference can imprint a nano-scale fringe pattern onto a molecular beam, which allows observing its shifts in the presence of even very small external forces. Here we demonstrate quantum interference of the pre-vitamin 7-dehydrocholesterol and discuss the conceptual challenges of magnetic deflectometry in a near-field interferometer as a tool to explore photochemical processes within molecules whose center of mass is quantum delocalized.

Optically driven ultra-stable nanomechanical rotor.

Nanomechanical devices have attracted the interest of a growing interdisciplinary research community, since they can be used as highly sensitive transducers for various physical quantities. Exquisite control over these systems facilitates experiments on the foundations of physics. Here, we demonstrate that an optically trapped silicon nanorod, set into rotation at MHz frequencies, can be locked to an external clock, transducing the properties of the time standard to the rod's motion with a remarkable frequency stability f r/Δf r of 7.7 × 1011. While the dynamics of this periodically driven rotor generally can be chaotic, we derive and verify that stable limit cycles exist over a surprisingly wide parameter range. This robustness should enable, in principle, measurements of external torques with sensitivities better than 0.25 zNm, even at room temperature. We show that in a dilute gas, real-time phase measurements on the locked nanorod transduce pressure values with a sensitivity of 0.3%.

In search of multipath interference using large molecules.

The superposition principle is fundamental to the quantum description of both light and matter. Recently, a number of experiments have sought to directly test this principle using coherent light, single photons, and nuclear spin states. We extend these experiments to massive particles for the first time. We compare the interference patterns arising from a beam of large dye molecules diffracting at single, double, and triple slit material masks to place limits on any high-order, or multipath, contributions. We observe an upper bound of less than one particle in a hundred deviating from the expectations of quantum mechanics over a broad range of transverse momenta and de Broglie wavelength.

Quantum-Assisted Metrology of Neutral Vitamins in the Gas Phase.

It has recently been shown that matter-wave interferometry can be used to imprint a periodic nanostructure onto a molecular beam, which provides a highly sensitive tool for beam displacement measurements. Herein, we used this feature to measure electronic properties of provitamin A, vitamin E, and vitamin K1 in the gas phase for the first time. The shift of the matter-wave fringes in a static electric field encodes the molecular susceptibility and the time-averaged dynamic electric dipole moment. The dependence of the fringe pattern on the intensity of the central light-wave diffraction grating was used to determine the molecular optical polarizability. Comparison of our experimental findings with molecular dynamics simulations and density functional theory provides a rich picture of the electronic structures and dynamics of these biomolecules in the gas phase with ß-carotene as a particularly interesting example.

Selective photodissociation of tailored molecular tags as a tool for quantum optics.

Recent progress in synthetic chemistry and molecular quantum optics has enabled demonstrations of the quantum mechanical wave-particle duality for complex particles, with masses exceeding 10 kDa. Future experiments with even larger objects will require new optical preparation and manipulation methods that shall profit from the possibility to cleave a well-defined molecular tag from a larger parent molecule. Here we present the design and synthesis of two model compounds as well as evidence for the photoinduced beam depletion in high vacuum in one case.

New avenues for matter-wave-enhanced spectroscopy.

We present matter-wave interferometry as a tool to advance spectroscopy for a wide class of nanoparticles, clusters and molecules. The high sensitivity of de Broglie interference fringes to external perturbations enables measurements in the limit of an individual particle absorbing only a single photon on average, or even no photon at all. The method allows one to extract structural and electronic information from the loss of the interference contrast. It is minimally invasive and works even for dilute ensembles.

Simulated Interactive Research Experiments as Educational Tools for Advanced Science.

Experimental research has become complex and thus a challenge to science education. Only very few students can typically be trained on advanced scientific equipment. It is therefore important to find new tools that allow all students to acquire laboratory skills individually and independent of where they are located. In a design-based research process we have investigated the feasibility of using a virtual laboratory as a photo-realistic and scientifically valid representation of advanced scientific infrastructure to teach modern experimental science, here, molecular quantum optics. We found a concept based on three educational principles that allows undergraduate students to become acquainted with procedures and concepts of a modern research field. We find a significant increase in student understanding using our Simulated Interactive Research Experiment (SiReX), by evaluating the learning outcomes with semi-structured interviews in a pre/post design. This suggests that this concept of an educational tool can be generalized to disseminate findings in other fields.