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Background: Athletes often experience poor sleep quality due to stress, altitude exposure, travel across different time zones, and pre-competition nervousness. Coaches use daytime naps to counteract the negative effects of fragmented nighttime sleep. Napping before competitions has also been used to enhance performance in athletes without sleep problems, with mixed results in previous studies, particularly for endurance performance. Thus, we investigated the effects of napping after partial sleep deprivation (PSD) on endurance performance and wakefulness in athletes. Methods: We recruited 12 healthy and trained participants (seven female and five male) for a randomized crossover study design. The participants underwent two test sessions: a five-hour night of sleep without a nap (noNap) and a five-hour night of sleep with a 30-min nap opportunity (Nap30). Participants recorded their sleep-wake rhythm one week before and during the study using the Consensus Sleep Diary-Core and the Morningness–Eveningness Questionnaire to examine their circadian rhythm type. We quantified PSD and the nap with pupillography (pupil unrest index, PUI), a subjective level of sleepiness questionnaire (Karolinska Sleepiness Scale, KSS), and polysomnography. After each night, participants performed a maximal cycling ergometry test to determine time to exhaustion (TTE) and maximal oxygen uptake (VO 2max). Results: Participants had an average sleep duration of 7.2 ± 0.7 h and were identified as moderately morning types (n = 5), neither type (n = 5), and moderately evening types (n = 2). There was a significant difference in both sleepiness parameters between the two conditions, with the PUI (p = 0.015) and KSS (p ≤ 0.01) significantly decreased at 5 h and nap compared with only 5 h of sleep. The PUI (p ≤ 0.01) and KSS (p ≤ 0.01) decreased significantly from before to after the nap. However, there was no significant difference in physical exercise test results between the conditions for TTE (p = 0.367) or VO 2max (p = 0.308). Conclusions: Our results suggest that napping after light PSD does not significantly influence endurance performance. We conclude that aerobic performance is a multidimensional construct, and napping after PSD may not enhance it. However, napping is an effective method to increase wakefulness and vigilance, which can be beneficial for sports competitions.

International journal of molecular sciences 22(7), 3691 (2021). doi:10.3390/ijms22073691, Quantitative cellular in vitro nanoparticle uptake measurements are possible with a large number of different techniques, however, all have their respective restrictions. Here, we demonstrate the application of synchrotron-based X-ray fluorescence imaging (XFI) on prostate tumor cells, which have internalized differently functionalized gold nanoparticles. Total nanoparticle uptake on the order of a few hundred picograms could be conveniently observed with microsamples consisting of only a few hundreds of cells. A comparison with mass spectroscopy quantification is provided, experimental results are both supported and sensitivity limits of this XFI approach extrapolated by Monte-Carlo simulations, yielding a minimum detectable nanoparticle mass of just 5 pg. This study demonstrates the high sensitivity level of XFI, allowing non-destructive uptake measurements with very small microsamples within just seconds of irradiation time., Published by Molecular Diversity Preservation International, Basel

Zeitschrift für Kristallographie / Crystalline materials 233(9-10), 695 - 706 (2018). doi:10.1515/zkri-2018-2060, The structure of glutathione, γ-l-Glutamyl-l-cysteinyl-glycine (C$_{10}$H$_{17}$N$_3$O$_6$S), was studied by multi-temperature single-crystal X-ray diffraction. Residual density maps from conventional independent atom model refinement gave indication of anharmonic motion in the molecule. This was further investigated by invariom refinement with anisotropic displacement parameters for all atoms, which described asphericity due to chemical bonding and lone pairs; afterwards only the residual-density signal of anharmonic motion remained. Treating anharmonicity with third-order Gram-Charlier displacement parameters led to regions with unphysical negative electron density. In contrast, a maximum entropy method (MEM) determination of the electron density successfully takes the features into account. Respective difference electron density plots (MEM minus prior and [Invariom+GC] minus invariom) agree well with each other. Challenges in treating and understanding the phenomenon are discussed. A procedure is proposed how unphysical negative electron density can be avoided. It is closely related to the free lunch algorithm., Published by De Gruyter, Berlin

Direct protein crystallization on fixed-target sample holders allows highly efficient serial crystallography experiments and ligand-binding studies., Efficient and reliable sample delivery has remained one of the bottlenecks for serial crystallography experiments. Compared with other methods, fixed-target sample delivery offers the advantage of significantly reduced sample consumption and shorter data collection times owing to higher hit rates. Here, a new method of on-chip crystallization is reported which allows the efficient and reproducible growth of large numbers of protein crystals directly on micro-patterned silicon chips for in-situ serial crystallography experiments. Crystals are grown by sitting-drop vapor diffusion and previously established crystallization conditions can be directly applied. By reducing the number of crystal-handling steps, the method is particularly well suited for sensitive crystal systems. Excessive mother liquor can be efficiently removed from the crystals by blotting, and no sealing of the fixed-target sample holders is required to prevent the crystals from dehydrating. As a consequence, ‘naked’ crystals are obtained on the chip, resulting in very low background scattering levels and making the crystals highly accessible for external manipulation such as the application of ligand solutions. Serial diffraction experiments carried out at cryogenic temperatures at a synchrotron and at room temperature at an X-ray free-electron laser yielded high-quality X-ray structures of the human membrane protein aquaporin 2 and two new ligand-bound structures of thermolysin and the human kinase DRAK2. The results highlight the applicability of the method for future high-throughput on-chip screening of pharmaceutical compounds.

Scientific reports 8(1), 16561 (2018). doi:10.1038/s41598-018-34925-3, Accurate in vivo localisation of minimal amounts of functionalised gold-nanoparticles, enabling e.g. early-tumour diagnostics and pharmacokinetic tracking studies, requires a precision imaging system offering very high sensitivity, temporal and spatial resolution, large depth penetration, and arbitrarily long serial measurements. X-ray fluorescence imaging could offer such capabilities; however, its utilisation for human-sized scales is hampered by a high intrinsic background level. Here we measure and model this anisotropic background and present a spatial filtering scheme for background reduction enabling the localisation of nanoparticle-amounts as reported from small-animal tumour models. As a basic application study towards precision pharmacokinetics, we demonstrate specific localisation to sites of disease by adapting gold-nanoparticles with small targeting ligands in murine spinal cord injury models, at record sensitivity levels using sub-mm resolution. Both studies contribute to the future use of molecularly-targeted gold-nanoparticles as next-generation clinical diagnostic and pharmacokinetic tools., Published by Springer Nature, [London]

SummaryPhotosystem II (PSII) catalyzes a key step in photosynthesis, the oxidation of water to oxygen. Excellent structural models exist for the dimeric PSII core complex of cyanobacteria, but higher order physiological assemblies readily dissociate when solubilized from the native thylakoid membrane with detergent. Here, we describe the crystallization of PSII from Thermosynechococcus elongatus with a postcrystallization treatment involving extraction of the detergent C12E8. This resulted in a transition from Type II to Type I-like membrane protein crystals and improved diffraction to 2.44 Å resolution. The obtained PSII packing in precise rows, interconnected by specific pairs of galactolipids and a loop in the PsbO subunit specific to cyanobacteria, is superimposable with previous electron microscopy images of the thylakoid membrane. The study provides a detailed model of such a superstructure and its organization of light-harvesting pigments with possible implications for the understanding of their efficient use of solar energy.

Acta crystallographica / D 73(7), 581 - 590(2017). doi:10.1107/S2059798317006970, Cadmium ions can be effectively used to promote crystal growth and for experimental phasing. Here, the use of cadmium ions as a suitable anomalous scatterer at the standard wavelength of 1 Å is demonstrated. The structures of three different proteins were determined using cadmium single-wavelength anomalous dispersion (SAD) phasing. Owing to the strong anomalous signal, the structure of lysozyme could be automatically phased and built using a very low anomalous multiplicity (1.1) and low-completeness (77%) data set. Additionally, it is shown that cadmium ions can easily substitute divalent ions in ATP–divalent cation complexes. This property could be generally applied for phasing experiments of a wide range of nucleotide-binding proteins. Improvements in crystal growth and quality, good anomalous signal at standard wavelengths (i.e. no need to change photon energy) and rapid phasing and refinement using a single data set are benefits that should allow cadmium ions to be widely used for experimental phasing., Published by Wiley-Blackwell, Oxford

The room-temperature structure of lysozyme is determined using 40000 individual diffraction patterns from micro-crystals flowing in liquid suspension across a synchrotron microfocus beamline., A new approach for collecting data from many hundreds of thousands of microcrystals using X-ray pulses from a free-electron laser has recently been developed. Referred to as serial crystallography, diffraction patterns are recorded at a constant rate as a suspension of protein crystals flows across the path of an X-ray beam. Events that by chance contain single-crystal diffraction patterns are retained, then indexed and merged to form a three-dimensional set of reflection intensities for structure determination. This approach relies upon several innovations: an intense X-ray beam; a fast detector system; a means to rapidly flow a suspension of crystals across the X-ray beam; and the computational infrastructure to process the large volume of data. Originally conceived for radiation-damage-free measurements with ultrafast X-ray pulses, the same methods can be employed with synchrotron radiation. As in powder diffraction, the averaging of thousands of observations per Bragg peak may improve the ratio of signal to noise of low-dose exposures. Here, it is shown that this paradigm can be implemented for room-temperature data collection using synchrotron radiation and exposure times of less than 3 ms. Using lysozyme microcrystals as a model system, over 40 000 single-crystal diffraction patterns were obtained and merged to produce a structural model that could be refined to 2.1 Å resolution. The resulting electron density is in excellent agreement with that obtained using standard X-ray data collection techniques. With further improvements the method is well suited for even shorter exposures at future and upgraded synchrotron radiation facilities that may deliver beams with 1000 times higher brightness than they currently produce.

The dinuclear phenoxido-bridged nickel(II) complex [{Ni(Hsalhyph)Cl(H2O)}2] with the hydrazone ligand H2salhyph, derived from salicylaldehyde and benzoic acid hydrazide, has been synthesized and structurally characterized. The dinuclear Ni2O2 core unit of the complex facilitates the formation of intramolecular O–H···Cl hydrogen bonds. The chlorido ligand is involved in additional N–H···Cl hydrogen bonding leading to an aggregation of the dinuclear complexes forming one-dimensional staged chains. Within the chains the supramolecular structure is governed by hydrogen bonding and π–π-stacking interactions. In the crystal structure two additional DMF molecules of crystallization are present per dinuclear complex. The DMF molecules are located between the chains and involved in O–H···O=C hydrogen bonding with the aqua ligands of the dinickel core. Magnetic susceptibility measurements show the presence of antiferromagnetic exchange interactions (H = –JS1S2) with J = –14.8 cm–1 between the nickel(II) ions and indicate a zero-field-splitting of D = 12.6 cm–1.

Nicotinic acid mononucleotide adenylyltransferase (NaMNAT) is an indispensable enzyme for the synthesis of NAD and NAD phosphate. It catalyzes the adenylylation of nicotinic acid mononucleotide (NaMN) to yield nicotinic acid adenine dinucleotide (NaAD). Since NAD(H) and NAD phosphate(H) are essentially involved in metabolic and redox regulatory reactions, NaMNAT is an attractive drug target in the fight against bacterial and parasitic infections. Notably, NaMNAT of the malaria parasite Plasmodium falciparum possesses only 20% sequence identity with the homologous human enzyme. Here, we present for the first time the two X-ray structures of P. falciparum NaMNAT (PfNaMNAT)—in the product-bound state with NaAD and complexed with an α,β-non-hydrolizable ATP analog—the structures were determined to a resolution of 2.2 Å and 2.5 Å, respectively. The overall architecture of PfNaMNAT was found to be more similar to its bacterial homologs than its human counterparts although the PPHK motif conserved in bacteria is missing. Furthermore, PfNaMNAT possesses two cysteine residues within the active site that have not been described for any other NaMNATase so far and are likely to be involved in redox regulation of PfNaMNAT activity. Enzymatic studies and surface plasmon resonance data reveal that PfNaMNAT is capable of utilizing NaMN and nicotinamide mononucleotide with a slight preference for NaMN. Surprisingly, a comparison with the active site of Escherichia coli NaMNAT showed very similar architectures, despite different substrate preferences.

The pK(a) values of six amine-linked pseudodisaccharides have been determined by using an NMR-based titration method. The pK(a) varies significantly depending on the linkage position and is inverse ...

Based on the sugar-modified Schiff-base ligand derived from salicylaldehyde and benzyl 2-deoxy-2-amino-α- d -glucopyranoside (H2salagluc) the new mixed-ligand nickel(II) complex [Ni(Hsalagluc)(tptz)]ClO4 has been synthesized (tptz = 2,4,6-tri-(2-pyridyl)-1,3,5-triazine). The X-ray crystal structure reveals a distorted octahedral geometry at the nickel(II) center with the rare 2,3-chelation of the trans-configured donor atoms of the carbohydrate backbone. Intermolecular hydrogen bonding leads to dimeric units of the complex cations. The supramolecular assembly of these units by π-stacking of the tptz coligands affords one-dimensional chains along the two fold screw axis. O–H⋯π(Ar) hydrogen bonding is observed for a methanol molecule of crystallization. Magnetic susceptibility measurements are consistent with a high-spin nickel(II) ion with a zero-field-splitting of D = −11.5 cm−1 (g = 2.311).

Condensation of a derivatized 2-aminoglucose fragment with salicylaldehyde affords the new sugar-based Schiff base ligand benzyl 4,6-O-benzylidene-2-deoxy-2-salicylideneamino-α-D-glucopyranoside (H2L). The reaction of the dibasic ligand H2L with [Cu(CH3COO)2]·H2O leads to the formation of the tetranuclear copper(II) complex [{Cu(L)}4] (3) by a self-assembly process. The X-ray structural analysis of complex 3 which crystallizes together with two molecules of chloroform and one molecule of ethanol in the space group P212121 revealed for all copper atoms a NO3 coordination environment with a square-planar geometry. The tetranuclear molecule 3 consists of four chiral building blocks {Cu(L)} with the rare 2,3-coordination of the trans-configured donor atoms of the sugar backbone. The observed coordination mode of the building blocks exemplifies how chitosan-derived polysaccharide ligands can act as a chiral support for transition-metal complexes. The C-3 alcoholate oxygen atoms of the carbohydrate unit is bridging adjacent {Cu(L)} moieties resulting in an eight-membered Cu4O4 ring with a boat-like conformation. Temperature-dependent magnetic measurements of 3 indicate moderate antiferromagnetic interactions between the four copper(II) ions with a coupling constant of J = –130 cm–1.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

Trifluorinated germanium anions attracted attention of theoretical chemists already in the late 1990s to predict their physical and chemical properties. However these species were not synthesized in the laboratory, although substantial evidence for their existence was obtained from the mass. spectrometry of GeF4. The present study shows that controlled fluorination of LMNMe2 (L = PhC((NBu)-Bu-t)(2), M = Ge, Sn) using HF center dot pyridine in toluene leads to the formation of [LH2](+)[MF3](-) under elimination of HNMe2. The products contain the trifluorinated Ge(II) and Sn(II) anionic species which are stabilized by interionic H center dot center dot center dot F bonds. The new compounds were characterized by single crystal X-ray structural analysis, NMR spectroscopy, and elemental analysis.

The title compound, C28H41NO6, was obtained by reduction of benzyl 2-de­oxy-2-(3,5-di-tert-but­ylsalicylideneamino)-α-d-gluco­pyran­oside. The benzyl substituent is in an axial position, whereas the 3,5-di-tert-butyl­salicylamino substituent and the hydroxyl groups are in equatorial positions. The enantio­merically pure title compound is a potential O,N,O-chelate ligand suitable as a precursor for chiral transition metal complexes. The absolute configuration was determined by NMR experiments.

The title compound, C20H23NO5, crystallizes exclusively as the α-anomer. All substituents are in equatorial positions except the benzyl substituent which occupies an axial position. Owing to its two vicinal donor atoms and its enanti­omeric purity, the title compound is a suitable N,O-bidentate ligand for complexation of transition metals.

The title compound, C21H24O11, crystallizes exclusively as the α-anomer. The 3-formyl­phenyl substituent at C1 is in the axial position, whereas all other groups are in equatorial positions. As a consequence, the re-face of the aldehyde group is somewhat shielded by the C6 acetyl group.

Beamline P11 at PETRA III is dedicated to structural investigations of biological samples. It provides two experimental stations, one for macromolecular crystallography and one for X-ray microscopy. The microscope will provide full field Zernike phase contrast and scanning microscopy both in 2D and in tomographic mode. Full field microscopy with a field of view of 50 x 50 μm2 will allow to generate an overview of the sample and to select regions of interest for later inspection of the element distribution by X-ray fluorescence and diffraction in scanning mode. Central part of the microscope is an inhouse developed flexure based x,y,z scanner on top of a rotation stage. The scanner is operated in closed loop with piezo motors, has a travel range of 4 mm in horizontal and of 3 mm in vertical direction. With laser interferometers for closed loop operation a positioning accuracy of better than 5 nm is achieved in all directions. For precise sample rotation an in-vacuum air-bearing has been developed. An open bore in the center of the air-bearing allows cryogenic sample cooling by a cold He or N2 gas stream. Different optical elements such as beam defining pinholes, a condensor, zone plates, OSA, phase rings, etc. can be centered in the beam path by piezomotor driven x,y flexure elements mounted on a rail system which allows further positioning along the beam path. Different 2D detectors and two fluoresence detectors can be attached to the microscope.

Successful cryogenic X-ray structure determination from a single high-pressure-frozen bovine enterovirus 2 crystal is reported. The presented high-pressure-freezing procedure is based on a commercially available device and allows the cryocooling of macromolecular crystals directly in their mother liquor without the time- and crystal-consuming search for optimal cryoconditions. The method is generally applicable and will allow cryogenic data collection from all types of macromolecular crystals.

High-pressure freezing (HPF) is a method which allows sample vitrification without cryoprotectants. In the present work, protein crystals were cooled to cryogenic temperatures at a pressure of 210 MPa. In contrast to other HPF methods published to date in the field of cryocrystallography, this protocol involves rapid sample cooling using a standard HPF device. The fast cooling rates allow HPF of protein crystals directly in their mother liquor without the need for cryoprotectants or external reagents. HPF was first attempted with hen egg-white lysozyme and cubic insulin crystals, yielding good to excellent diffraction quality. Non-cryoprotected crystals of the membrane protein photosystem II have been successfully cryocooled for the first time. This indicates that the presented HPF method is well suited to the vitrification of challenging systems with large unit cells and weak crystal contacts.

The reaction of benzyl 2-amino-4,6-O-benzylidene-2-deoxy-alpha-D-glucopyranoside (HL) with the metal salts Cu(ClO(4))(2)6 H(2)O and Ni(NO(3))(2)6 H(2)O affords via self-assembly a tetranuclear mu(4)-hydroxido bridged copper(II) complex [(mu(4)-OH)Cu(4)(L)(4)(MeOH)(3)(H(2)O)](ClO(4))(3) (1) and a trinuclear alcoholate bridged nickel(II) complex [Ni(3)(L)(5)(HL)]NO(3) (2), respectively. Both complexes crystallize in the acentric space group P2(1). The X-ray crystal structure reveals the rare (mu(4)-OH)Cu(4)O(4) core for complex 1 which is mu(2)-alcoholate bridged. The copper(II) ions possess a distorted square-pyramidal geometry with an [NO(4)] donor set. The core is stabilized by hydrogen bonding between the coordinating amino group of the glucose backbone and the benzylidene protected oxygen atom O4 of a neighboring {Cu(L)} fragment as hydrogen-bond acceptor. For complex 2 an [N(4)O(2)] donor set is observed at the nickel(II) ions with a distorted octahedral geometry. The trinuclear isosceles Ni(3) core is bridged by mu(3)-alcoholate O3 oxygen atoms of two glucose ligands. The two short edges are capped by mu(2)-alcoholate O3 oxygen atoms of the two ligands coordinated at the nickel(II) ion at the vertex of these two edges. Along the elongated edge of the triangle a strong hydrogen bond (244 pm) between the O3 oxygen atoms of ligands coordinating at the two relevant nickel(II) ions is observed. The coordinating amino groups of the these two glucose ligands are involved in additional hydrogen bonds with O4 oxygen atoms of adjacent ligands further stabilizing the trinuclear core. The carbohydrate backbones in all cases adopt the stable (4)C(1) chair conformation and exhibit the rare chitosan-like trans-2,3-chelation. Temperature dependent magnetic measurements indicate an overall antiferromagnetic behavior for complex 1 with J(1)=-260 and J(2)=-205 cm(-1) (g=2.122). Compound 2 is the first ferromagnetically coupled trinuclear nickel(II) complex with J(A)=16.4 and J(B)=11.0 cm(-1) (g(1,2)=2.183, g(3)=2.247). For the high-spin nickel(II) centers a zero-field splitting of D(1,2)=3.7 cm(-1) and D(3)=1.8 cm(-1) is observed. The S=3 ground state of complex 2 is consistent with magnetization measurements at low temperatures.

The sugar-modified Schiff base ligand benzyl 2-deoxy-2-salicylideneamino-alpha-D-glucopyranoside H 2L, prepared by condensation of salicylaldehyde and the monomeric chitosan analogue benzyl 2-deoxy-2-amino-alpha-D-glucopyranoside, reacts with copper(II) acetate to form a self-assembled, alkoxo-bridged tetranuclear homoleptic copper(II) complex [{Cu(L)}4] (4) with Cu4O4 heterocubane core. The chiral complex 4 crystallizes in the space group P2 12 12 1. The tetranuclear complex 4 is composed of two dinuclear {Cu(L)}2 entities linked by the four mu 3-bridging C-3 alkoxide oxygen atoms of the sugar backbone. The preorganization of the dimeric {Cu(L)}2 entities is enforced by strong hydrogen bonds between the phenolate oxygen atom and the C-4 hydroxy group of the two constituting chiral monomeric building blocks. Therefore the Cu4O4 core can be classified as a type I or 2 + 4 cubane. The chirality of the structure is confirmed by circular dichroism (CD) spectra, which reveal a significant dichroism associated with the copper centered transitions at around 600 nm. Temperature dependent magnetic susceptibility measurements indicate ferromagnetic exchange interactions in complex 4. Fitting of the experimental data with a two J model based on the 2 + 4 topology ( H = - J1(S1S3 + S2S4) - J2(S1 + S3)(S2 + S4)) leads to exchange coupling constants of J1 = 64 and J2 = 4 cm(-1). The observed ferromagnetic coupling can be attributed to the very small Cu-O-Cu bridging angles within the Cu2O2 core of the constituting dimeric entities, which are a result of the conformational requirements introduced by the sugar backbone. 4 is not only the first example of an alkoxo-bridged tetranuclear copper(II) complex with Cu4O4 core representing the 2 + 4 cubane class with ferromagnetic ground state but also a rare example for the class of molecules combining a ferromagnetic ground state with optical activity. The ferromagnetic S = 2 ground state of 4 is confirmed by magnetization measurements and ESR spectroscopy.

Two mononuclear nickel(II) complexes with Schiff-base ligands derived from the epimeric sugars glucosamine and mannosamine have been synthesized. The X-ray crystal structure reveals a distorted octahedral geometry at the nickel(II) ions with an N4O2 donor set and the rare 2,3-chelation of the donor atoms of the carbohydrate backbone. Upon complexation only the glucopyranose ring maintains the 4C1 chair conformation, whereas the mannopyranose ring adopts the OS5 screw-boat conformation. Dimeric units of complex cations are formed by intermolecular hydrogen bonding which are further assembled by π-stacking affording one-dimensional chains with a twofold screw symmetry.

The bio-imaging and diffraction beamline P11 at PETRA III is dedicated to structure determination of periodic (crystalline) and aperiodic biological samples. The beamline features two experimental endstations: an X-ray microscope and a crystallography experiment. Basis of design was to provide an extremely stable and flexible setup ideally suited for micro and nano beam applications. The X-ray optics consist of a HHL double crystal monochromator, followed by two horizontal deflecting and one vertical deflecting X-ray mirrors. All mirrors are dynamically bendable and used to generate an intermediate focus at 65.5 m from the source with a size of 37 × 221 µm2FWHM (v × h). All experiments are installed on an 8 m long granite support which provides a very stable setup for micro beam experiments. The crystallography endstation is located at the end of the granite at 72.9 m from the source. The experiment is equipped with a high precision single axis goniostat with a combined sphere of confusion of less than 100 nm. X-ray energies are tunable between 5.5 and 30 keV. A second focusing bendable KB mirror system can be used for further demagnification of the secondary source. In this way the beam size can be freely adjusted between 4 × 9 µm2and 300 × 300 µm2FWHM (v × h) with 1013ph/s at 12 keV. Smaller beam sizes down to 1 × 1 µm2with more than 2 × 1011ph/s in the focus can be realized by slitting down the secondary source at the cost of flux. The crystallography endstation is equipped with a Pilatus 6M-F detector which allows fast data collection with up to 25 Hz. Due to the very small beam divergence of the X-ray beam P11 is ideally suited to measure large unit cell systems, such as viruses or large molecular complexes. In addition, the beamline is capable of high-throughput crystallography and fast crystal screening. Crystals can be mounted in less than 10 s using an automatic sample changer. The large sample dewar provides space for 368 crystals.

The sugar-modified Schiff-base ligands derived from benzyl 2-deoxy-2-salicylideneamino-α-D-glucopyranoside (H2L(5-Br) and H2L(3-OMe)) were used to prepare the chiral oxidovanadium(V) complexes [VO(L(5-Br))(OMe)] (1) and [VO(L(3-OMe))(OMe)] (2) which can be isolated from a methanol solution as the six-coordinate complexes with an additional methanol ligand [VO(L(5-Br))(OMe)(MeOH)] (1-MeOH) and [VO(L(3-OMe))(OMe) (MeOH)] (2-MeOH). Both complexes crystallize in the orthorhombic space group P2(1)2(1)2(1) together with two solvent molecules of methanol as 1-MeOH·2MeOH and 1-MeOH·2MeOH. In both crystal structures, only diastereomers with A configuration at the chiral vanadium centre (OC-6-24-A) are observed which corresponds to an cis configuration of the oxido group at the vanadium centre and the benzyl group at the anomeric carbon of the sugar backbone. Upon recrystallization of 2-MeOH from chloroform, the five-coordinate complex 2 was obtained which crystallizes in the monoclinic space group P2(1) with one co-crystallized chloroform molecule (2·CHCl3). For the chiral vanadium centre in 2·CHCl3, a C configuration (SPY-5-43-C) is observed which corresponds to an trans structure as far as the orientations of the oxido and benzyl groups are concerned. (1)H and (51)V NMR spectra of 1 and 2 indicate the presence of two diastereomers in solution. Their absolute configurations can be assigned based on the magnetic anisotropy effect of the oxidovanadium group. This effect leads to significant differences for the (1)H NMR chemical shifts of the H-2 (1.1 ppm) and H-3 protons (0.3 ppm) of the glucose backbone of the two diastereomers, with the downfield shift observed for the H-2 proton of the C-configured and the H-3 proton of the A-configured diastereomer at the vanadium centre. For 1 and 2 the difference between the (51)V NMR chemical shifts of the two diastereomers is 30 and 28 ppm, respectively. Also in the (13)C NMR significant chemical shift differences between the two diastereomers are observed for the carbon atoms C2 (2 ppm) and C3 (4 ppm). DFT calculations of the NMR chemical shift parameters have been performed which are in good agreement with the experimental data. Moreover, the isomerization mechanism between the diastereomers is analysed on the basis of DFT calculations which indicate the required presence of methanol molecules as protic donors.