@article{8446, abstract = {Solid‐state NMR spectroscopy can provide insight into protein structure and dynamics at the atomic level without inherent protein size limitations. However, a major hurdle to studying large proteins by solid‐state NMR spectroscopy is related to spectral complexity and resonance overlap, which increase with molecular weight and severely hamper the assignment process. Here the use of two sets of experiments is shown to expand the tool kit of 1H‐detected assignment approaches, which correlate a given amide pair either to the two adjacent CO–CA pairs (4D hCOCANH/hCOCAcoNH), or to the amide 1H of the neighboring residue (3D HcocaNH/HcacoNH, which can be extended to 5D). The experiments are based on efficient coherence transfers between backbone atoms using INEPT transfers between carbons and cross‐polarization for heteronuclear transfers. The utility of these experiments is exemplified with application to assemblies of deuterated, fully amide‐protonated proteins from approximately 20 to 60 kDa monomer, at magic‐angle spinning (MAS) frequencies from approximately 40 to 55 kHz. These experiments will also be applicable to protonated proteins at higher MAS frequencies. The resonance assignment of a domain within the 50.4 kDa bacteriophage T5 tube protein pb6 is reported, and this is compared to NMR assignments of the isolated domain in solution. This comparison reveals contacts of this domain to the core of the polymeric tail tube assembly.}, author = {Fraga, Hugo and Arnaud, Charles‐Adrien and Gauto, Diego F. and Audin, Maxime and Kurauskas, Vilius and Macek, Pavel and Krichel, Carsten and Guan, Jia‐Ying and Boisbouvier, Jerome and Sprangers, Remco and Breyton, Cécile and Schanda, Paul}, issn = {1439-4235}, journal = {ChemPhysChem}, keywords = {Physical and Theoretical Chemistry, Atomic and Molecular Physics, and Optics}, number = {19}, pages = {2697--2703}, publisher = {Wiley}, title = {{Solid‐state NMR H–N–(C)–H and H–N–C–C 3D/4D correlation experiments for resonance assignment of large proteins}}, doi = {10.1002/cphc.201700572}, volume = {18}, year = {2017}, } @article{13387, abstract = {Come on in, the water's fine! Non-photoresponsive nanoparticles can be reversibly assembled using light by placing them in an aqueous solution of a photo­acid. Upon exposure to visible light, the photoacid reduces the pH of the solution, which induces attractive interactions between the nanoparticles. In the dark, the resulting nanoparticle aggregates spontaneously disassemble. The process can be repeated many times.}, author = {Samanta, Dipak and Klajn, Rafal}, issn = {2195-1071}, journal = {Advanced Optical Materials}, keywords = {Atomic and Molecular Physics, and Optics, Electronic, Optical and Magnetic Materials}, number = {9}, pages = {1373--1377}, publisher = {Wiley}, title = {{Aqueous light-controlled self-assembly of nanoparticles}}, doi = {10.1002/adom.201600364}, volume = {4}, year = {2016}, } @misc{13388, abstract = {The Inside Cover picture illustrates the fluorescent properties of a gold nanocluster functionalized with several copies of a red-emitting merocyanine (image by Ella Marushchenko). The red fluorescence can be turned on and off reversibly by using an external stimulus.}, author = {Udayabhaskararao, T. and Kundu, Pintu K. and Ahrens, Johannes and Klajn, Rafal}, booktitle = {ChemPhysChem}, issn = {1439-7641}, keywords = {Physical and Theoretical Chemistry, Atomic and Molecular Physics, and Optics}, number = {12}, pages = {1711--1711}, publisher = {Wiley}, title = {{Inside cover: Reversible photoisomerization of spiropyran on the surfaces of Au25 nanoclusters (ChemPhysChem 12/2016)}}, doi = {10.1002/cphc.201600480}, volume = {17}, year = {2016}, } @article{13389, abstract = {Au25 nanoclusters functionalized with a spiropyran molecular switch are synthesized via a ligand-exchange reaction at low temperature. The resulting nanoclusters are characterized by optical and NMR spectroscopies as well as by mass spectrometry. Spiropyran bound to nanoclusters isomerizes in a reversible fashion when exposed to UV and visible light, and its properties are similar to those of free spiropyran molecules in solution. The reversible photoisomerization entails the modulation of fluorescence as well as the light-controlled self-assembly of nanoclusters.}, author = {Udayabhaskararao, T. and Kundu, Pintu K. and Ahrens, Johannes and Klajn, Rafal}, issn = {1439-7641}, journal = {ChemPhysChem}, keywords = {Physical and Theoretical Chemistry, Atomic and Molecular Physics, and Optics}, number = {12}, pages = {1805--1809}, publisher = {Wiley}, title = {{Reversible photoisomerization of spiropyran on the surfaces of Au25 nanoclusters}}, doi = {10.1002/cphc.201500897}, volume = {17}, year = {2016}, } @article{14012, abstract = {Monochromatization of high-harmonic sources has opened fascinating perspectives regarding time-resolved photoemission from all phases of matter. Such studies have invariably involved the use of spectral filters or spectrally dispersive optical components that are inherently lossy and technically complex. Here we present a new technique for the spectral selection of near-threshold harmonics and their spatial separation from the driving beams without any optical elements. We discover the existence of a narrow phase-matching gate resulting from the combination of the non-collinear generation geometry in an extended medium, atomic resonances and absorption. Our technique offers a filter contrast of up to 104 for the selected harmonics against the adjacent ones and offers multiple temporally synchronized beamlets in a single unified scheme. We demonstrate the selective generation of 133, 80 or 56 nm femtosecond pulses from a 400-nm driver, which is specific to the target gas. These results open new pathways towards phase-sensitive multi-pulse spectroscopy in the vacuum- and extreme-ultraviolet, and frequency-selective output coupling from enhancement cavities.}, author = {Rajeev, Rajendran and Hellwagner, Johannes and Schumacher, Anne and Jordan, Inga and Huppert, Martin and Tehlar, Andres and Niraghatam, Bhargava Ram and Baykusheva, Denitsa Rangelova and Lin, Nan and von Conta, Aaron and Wörner, Hans Jakob}, issn = {2047-7538}, journal = {Light: Science & Applications}, keywords = {Atomic and Molecular Physics, and Optics, Electronic, Optical and Magnetic Materials}, number = {11}, pages = {e16170--e16170}, publisher = {Springer Nature}, title = {{In situ frequency gating and beam splitting of vacuum- and extreme-ultraviolet pulses}}, doi = {10.1038/lsa.2016.170}, volume = {5}, year = {2016}, } @article{13392, abstract = {The chemical behaviour of molecules can be significantly modified by confinement to volumes comparable to the dimensions of the molecules. Although such confined spaces can be found in various nanostructured materials, such as zeolites, nanoporous organic frameworks and colloidal nanocrystal assemblies, the slow diffusion of molecules in and out of these materials has greatly hampered studying the effect of confinement on their physicochemical properties. Here, we show that this diffusion limitation can be overcome by reversibly creating and destroying confined environments by means of ultraviolet and visible light irradiation. We use colloidal nanocrystals functionalized with light-responsive ligands that readily self-assemble and trap various molecules from the surrounding bulk solution. Once trapped, these molecules can undergo chemical reactions with increased rates and with stereoselectivities significantly different from those in bulk solution. Illumination with visible light disassembles these nanoflasks, releasing the product in solution and thereby establishes a catalytic cycle. These dynamic nanoflasks can be useful for studying chemical reactivities in confined environments and for synthesizing molecules that are otherwise hard to achieve in bulk solution.}, author = {Zhao, Hui and Sen, Soumyo and Udayabhaskararao, T. and Sawczyk, Michał and Kučanda, Kristina and Manna, Debasish and Kundu, Pintu K. and Lee, Ji-Woong and Král, Petr and Klajn, Rafal}, issn = {1748-3395}, journal = {Nature Nanotechnology}, keywords = {Electrical and Electronic Engineering, Condensed Matter Physics, General Materials Science, Biomedical Engineering, Atomic and Molecular Physics, and Optics, Bioengineering}, pages = {82--88}, publisher = {Springer Nature}, title = {{Reversible trapping and reaction acceleration within dynamically self-assembling nanoflasks}}, doi = {10.1038/nnano.2015.256}, volume = {11}, year = {2015}, } @article{14017, abstract = {The detection of electron motion and electronic wave-packet dynamics is one of the core goals of attosecond science. Recently, choosing the nitric oxide molecule as an example, we have introduced and demonstrated an experimental approach to measure coupled valence electronic and rotational wave packets using high-order-harmonic-generation (HHG) spectroscopy [Kraus et al., Phys. Rev. Lett. 111, 243005 (2013)]. A short outline of the theory to describe the combination of the pump and HHG probe process was published together with an extensive discussion of experimental results [Baykusheva et al., Faraday Discuss. 171, 113 (2014)]. The comparison of theory and experiment showed good agreement on a quantitative level. Here, we present the theory in detail, which is based on a generalized density-matrix approach that describes the pump process and the subsequent probing of the wave packets by a semiclassical quantitative rescattering approach. An in-depth analysis of the different Raman scattering contributions to the creation of the coupled rotational and electronic spin-orbit wave packets is made. We present results for parallel and perpendicular linear polarizations of the pump and probe laser pulses. Furthermore, an analysis of the combined rotational-electronic density matrix in terms of irreducible components is presented that facilitates interpretation of the results.}, author = {Zhang, Song Bin and Baykusheva, Denitsa Rangelova and Kraus, Peter M. and Wörner, Hans Jakob and Rohringer, Nina}, issn = {1094-1622}, journal = {Physical Review A}, keywords = {Atomic and Molecular Physics, and Optics}, number = {2}, publisher = {American Physical Society}, title = {{Theoretical study of molecular electronic and rotational coherences by high-order-harmonic generation}}, doi = {10.1103/physreva.91.023421}, volume = {91}, year = {2015}, } @article{14021, abstract = {We present the detailed analysis of a new two-pulse orientation scheme that achieves macroscopic field-free orientation at the high particle densities required for attosecond and high-harmonic spectroscopies (Kraus et al 2013 arXiv:1311.3923). Carbon monoxide molecules are oriented by combining one-colour and delayed two-colour non-resonant femtosecond laser pulses. High-harmonic generation is used to probe the oriented wave-packet dynamics and reveals that a very high degree of orientation (Nup/Ntotal = 0.73–0.82) is achieved. We further extend this approach to orienting carbonyl sulphide molecules. We show that the present two-pulse scheme selectively enhances orientation created by the hyperpolarizability interaction whereas the ionization-depletion mechanism plays no role. We further control and optimize orientation through the delay between the one- and two-colour pump pulses. Finally, we demonstrate a complementary encoding of electronic-structure features, such as shape resonances, in the even- and odd-harmonic spectrum. The achieved progress makes two-pulse field-free orientation an attractive tool for a broad class of time-resolved measurements.}, author = {Kraus, P M and Baykusheva, Denitsa Rangelova and Wörner, H J}, issn = {1361-6455}, journal = {Journal of Physics B: Atomic, Molecular and Optical Physics}, keywords = {Condensed Matter Physics, Atomic and Molecular Physics, and Optics}, number = {12}, publisher = {IOP Publishing}, title = {{Two-pulse orientation dynamics and high-harmonic spectroscopy of strongly-oriented molecules}}, doi = {10.1088/0953-4075/47/12/124030}, volume = {47}, year = {2014}, } @article{8470, abstract = {Adding a new dimension: 4D or 3D proton‐detected spectra of perdeuterated protein samples with 1H labelled amides and methyl groups permit collecting unambiguous distance restraints with high sensitivity and determining protein structure by solid‐state NMR (see picture).}, author = {Huber, Matthias and Hiller, Sebastian and Schanda, Paul and Ernst, Matthias and Böckmann, Anja and Verel, René and Meier, Beat H.}, issn = {1439-4235}, journal = {ChemPhysChem}, keywords = {Physical and Theoretical Chemistry, Atomic and Molecular Physics, and Optics}, number = {5}, pages = {915--918}, publisher = {Wiley}, title = {{A proton-detected 4D solid-state NMR experiment for protein structure determination}}, doi = {10.1002/cphc.201100062}, volume = {12}, year = {2011}, }