Spatially Separating the Conformers of a Dipeptide.

Atomic-resolution-imaging approaches for single molecules, such as coherent X-ray diffraction at free-electron lasers, require the delivery of high-density beams of identical molecules. However, even very cold beams of biomolecules typically have multiple conformational states populated. We demonstrate the production of very cold (Trot ≈2.3 K) molecular beams of intact dipeptide molecules, which were then spatially separated into the individual populated conformational states. This is achieved using the combination of supersonic expansion laser-desorption vaporization with electrostatic deflection in strong inhomogeneous fields. This represents the first demonstration of a conformer-separated and rotationally cold molecular beam of a peptide, which enables the investigation of conformer-specific chemistry using inherently non-conformer-specific techniques. It furthermore represents a milestone toward the direct structural imaging of individual biological molecules with atomic resolution by ultrafast diffractive-imaging methods.

Characterizing and optimizing a laser-desorption molecular beam source.

The design and characterization of a new laser-desorption molecular beam source, tailored for use in x-ray free-electron laser and ultrashort-pulse laser imaging experiments, is presented. It consists of a single mechanical unit containing all source components, including the molecular-beam valve, the sample, and the fiber-coupled desorption laser, which is movable in five axes, as required for experiments at central facilities. Utilizing strong-field ionization, we characterize the produced molecular beam and evaluate the influence of desorption laser pulse energy, relative timing of valve opening and desorption laser, sample bar height, and which part of the molecular packet is probed on the sample properties. Strong-field ionization acts as a universal probe and allows detecting all species present in the molecular beam, and hence enables us to analyze the purity of the produced molecular beam, including molecular fragments. We present optimized experimental parameters for the production of the purest molecular beam, containing the highest yield of intact parent ions, which we find to be very sensitive to the placement of the desorbed-molecule plumes within the supersonic expansion.

Methylthioureas and their morpholine and dioxane adducts; hydrogen-bonding patterns.

We have redetermined the known structures of (i) methylthiourea (MTU) and (ii) 1,1-dimethylthiourea (1,1-DMTU), and investigated the structure of 1,3-dimethylthiourea (1,3-DMTU), which was however severely disordered. We report the structures of crystalline adducts of (iii) MTU with morpholine (1:1), (iv) 1,1-DMTU with 1,4-dioxane (2:1) and (v) 1,3-DMTU with 1,4-dioxane (2:1). Finally, (vi) we determined the structure of tetramethylthiourea (TetMTU). (i) In both independent molecules of MTU, the methyl group is trans to the C=S group across the C-N bond. The two molecules are connected to form an R2(2)(8) dimer by mutual N-H...S=C interactions. The packing involves six N-H...S=C interactions and is three-dimensional. (ii) The packing of the MTU-morpholine adduct is a layer structure, within which both molecules form linear aggregates parallel to the b axis. (iii) The packing of 1,1-DMTU involves N-H...S=C hydrogen bonds forming a corrugated layer structure. (iv) In the 2:1 adduct between 1,1-DMTU and 1,4-dioxane, the DMTU molecule occupies a general position whereas the dioxane molecule lies across an inversion centre. The crystal packing involves chains of alternating 1,1-DMTU R2(2)(8) dimers and dioxanes, both across inversion centres. (v) In the 2:1 adduct between 1,3-DMTU and dioxane, the 1,3-DMTU molecule occupies a general position, while the dioxane molecule lies across an inversion centre. One methyl group of the DMTU is trans and one cis to the sulfur across the corresponding C-N bond. The molecules form chains of alternating 1,3-DMTU R2(2)(8) dimers and dioxanes, both across inversion centres. Crystals of the 2:1 adduct between 1,3-DMTU and morpholine were also obtained, and were isotypic with the dioxane adduct. The morpholine molecule is disordered across the inversion centre. (vi) The molecule of TetMTU displays crystallographic twofold symmetry. Significant distortions reflect the steric pressure between methyl groups trans to sulfur. The packing of TetMTU involves only a weak hydrogen bond, C-Hmethyl...S, which connects the molecules to form layers.