@article{13367, abstract = {Confining molecules can fundamentally change their chemical and physical properties. Confinement effects are considered instrumental at various stages of the origins of life, and life continues to rely on layers of compartmentalization to maintain an out-of-equilibrium state and efficiently synthesize complex biomolecules under mild conditions. As interest in synthetic confined systems grows, we are realizing that the principles governing reactivity under confinement are the same in abiological systems as they are in nature. In this Review, we categorize the ways in which nanoconfinement effects impact chemical reactivity in synthetic systems. Under nanoconfinement, chemical properties can be modulated to increase reaction rates, enhance selectivity and stabilize reactive species. Confinement effects also lead to changes in physical properties. The fluorescence of light emitters, the colours of dyes and electronic communication between electroactive species can all be tuned under confinement. Within each of these categories, we elucidate design principles and strategies that are widely applicable across a range of confined systems, specifically highlighting examples of different nanocompartments that influence reactivity in similar ways.}, author = {Grommet, Angela B. and Feller, Moran 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 = {256--271}, publisher = {Springer Nature}, title = {{Chemical reactivity under nanoconfinement}}, doi = {10.1038/s41565-020-0652-2}, volume = {15}, year = {2020}, } @article{13368, abstract = {Scanning nanoscale superconducting quantum interference devices (nanoSQUIDs) are of growing interest for highly sensitive quantitative imaging of magnetic, spintronic, and transport properties of low-dimensional systems. Utilizing specifically designed grooved quartz capillaries pulled into a sharp pipette, we have fabricated the smallest SQUID-on-tip (SOT) devices with effective diameters down to 39 nm. Integration of a resistive shunt in close proximity to the pipette apex combined with self-aligned deposition of In and Sn, has resulted in SOTs with a flux noise of 42 nΦ0 Hz−1/2, yielding a record low spin noise of 0.29 μB Hz−1/2. In addition, the new SOTs function at sub-Kelvin temperatures and in high magnetic fields of over 2.5 T. Integrating the SOTs into a scanning probe microscope allowed us to image the stray field of a single Fe3O4 nanocube at 300 mK. Our results show that the easy magnetization axis direction undergoes a transition from the 〈111〉 direction at room temperature to an in-plane orientation, which could be attributed to the Verwey phase transition in Fe3O4.}, author = {Anahory, Y. and Naren, H. R. and Lachman, E. O. and Buhbut Sinai, S. and Uri, A. and Embon, L. and Yaakobi, E. and Myasoedov, Y. and Huber, M. E. and Klajn, Rafal and Zeldov, E.}, issn = {2040-3372}, journal = {Nanoscale}, keywords = {General Materials Science}, number = {5}, pages = {3174--3182}, publisher = {Royal Society of Chemistry}, title = {{SQUID-on-tip with single-electron spin sensitivity for high-field and ultra-low temperature nanomagnetic imaging}}, doi = {10.1039/c9nr08578e}, volume = {12}, year = {2020}, } @article{10866, abstract = {Recent discoveries have shown that, when two layers of van der Waals (vdW) materials are superimposed with a relative twist angle between them, the electronic properties of the coupled system can be dramatically altered. Here, we demonstrate that a similar concept can be extended to the optics realm, particularly to propagating phonon polaritons–hybrid light-matter interactions. To do this, we fabricate stacks composed of two twisted slabs of a vdW crystal (α-MoO3) supporting anisotropic phonon polaritons (PhPs), and image the propagation of the latter when launched by localized sources. Our images reveal that, under a critical angle, the PhPs isofrequency curve undergoes a topological transition, in which the propagation of PhPs is strongly guided (canalization regime) along predetermined directions without geometric spreading. These results demonstrate a new degree of freedom (twist angle) for controlling the propagation of polaritons at the nanoscale with potential for nanoimaging, (bio)-sensing, or heat management.}, author = {Duan, Jiahua and Capote-Robayna, Nathaniel and Taboada-Gutiérrez, Javier and Álvarez-Pérez, Gonzalo and Prieto Gonzalez, Ivan and Martín-Sánchez, Javier and Nikitin, Alexey Y. and Alonso-González, Pablo}, issn = {1530-6992}, journal = {Nano Letters}, keywords = {Mechanical Engineering, Condensed Matter Physics, General Materials Science, General Chemistry, Bioengineering}, number = {7}, pages = {5323--5329}, publisher = {American Chemical Society}, title = {{Twisted nano-optics: Manipulating light at the nanoscale with twisted phonon polaritonic slabs}}, doi = {10.1021/acs.nanolett.0c01673}, volume = {20}, year = {2020}, } @article{13366, abstract = {The ability to reversibly assemble nanoparticles using light is both fundamentally interesting and important for applications ranging from reversible data storage to controlled drug delivery. Here, the diverse approaches that have so far been developed to control the self-assembly of nanoparticles using light are reviewed and compared. These approaches include functionalizing nanoparticles with monolayers of photoresponsive molecules, placing them in photoresponsive media capable of reversibly protonating the particles under light, and decorating plasmonic nanoparticles with thermoresponsive polymers, to name just a few. The applicability of these methods to larger, micrometer-sized particles is also discussed. Finally, several perspectives on further developments in the field are offered.}, author = {Bian, Tong and Chu, Zonglin and Klajn, Rafal}, issn = {1521-4095}, journal = {Advanced Materials}, keywords = {Mechanical Engineering, Mechanics of Materials, General Materials Science}, number = {20}, publisher = {Wiley}, title = {{The many ways to assemble nanoparticles using light}}, doi = {10.1002/adma.201905866}, volume = {32}, year = {2019}, } @article{13370, abstract = {Efficient isomerization of photochromic molecules often requires conformational freedom and is typically not available under solvent-free conditions. Here, we report a general methodology allowing for reversible switching of such molecules on the surfaces of solid materials. Our method is based on dispersing photochromic compounds within polysilsesquioxane nanowire networks (PNNs), which can be fabricated as transparent, highly porous, micrometer-thick layers on various substrates. We found that azobenzene switching within the PNNs proceeded unusually fast compared with the same molecules in liquid solvents. Efficient isomerization of another photochromic system, spiropyran, from a colorless to a colored form was used to create reversible images in PNN-coated glass. The coloration reaction could be induced with sunlight and is of interest for developing “smart” windows.}, author = {Chu, Zonglin and Klajn, Rafal}, issn = {1530-6992}, journal = {Nano Letters}, keywords = {Mechanical Engineering, Condensed Matter Physics, General Materials Science, General Chemistry, Bioengineering}, number = {10}, pages = {7106--7111}, publisher = {American Chemical Society}, title = {{Polysilsesquioxane nanowire networks as an “Artificial Solvent” for reversible operation of photochromic molecules}}, doi = {10.1021/acs.nanolett.9b02642}, volume = {19}, year = {2019}, } @article{13371, abstract = {Diamondoid nanoporous crystals represent a synthetically challenging class of materials that typically have been obtained from tetrahedral building blocks. In this issue of Chem, Stoddart and coworkers demonstrate that it is possible to generate diamondoid frameworks from a hexacationic building block lacking a tetrahedral symmetry. These results highlight the great potential of self-assembly for rapidly transforming small molecules into structurally complex functional materials.}, author = {Białek, Michał J. and Klajn, Rafal}, issn = {2451-9294}, journal = {Chem}, keywords = {Materials Chemistry, Biochemistry (medical), General Chemical Engineering, Environmental Chemistry, Biochemistry, General Chemistry}, number = {9}, pages = {2283--2285}, publisher = {Elsevier}, title = {{Diamond grows up}}, doi = {10.1016/j.chempr.2019.08.012}, volume = {5}, year = {2019}, } @article{10622, abstract = {We demonstrate a method for manipulating small ensembles of vortices in multiply connected superconducting structures. A micron-size magnetic particle attached to the tip of a silicon cantilever is used to locally apply magnetic flux through the superconducting structure. By scanning the tip over the surface of the device and by utilizing the dynamical coupling between the vortices and the cantilever, a high-resolution spatial map of the different vortex configurations is obtained. Moving the tip to a particular location in the map stabilizes a distinct multivortex configuration. Thus, the scanning of the tip over a particular trajectory in space permits nontrivial operations to be performed, such as braiding of individual vortices within a larger vortex ensemble—a key capability required by many proposals for topological quantum computing.}, author = {Polshyn, Hryhoriy and Naibert, Tyler and Budakian, Raffi}, issn = {1530-6992}, journal = {Nano Letters}, keywords = {mechanical engineering, condensed matter physics, general materials science, general chemistry, bioengineering}, number = {8}, pages = {5476--5482}, publisher = {American Chemical Society}, title = {{Manipulating multivortex states in superconducting structures}}, doi = {10.1021/acs.nanolett.9b01983}, volume = {19}, year = {2019}, } @article{13255, abstract = {Focused ion beams perfectly suit for patterning two-dimensional (2D) materials, but the optimization of irradiation parameters requires full microscopic understanding of defect production mechanisms. In contrast to freestanding 2D systems, the details of damage creation in supported 2D materials are not fully understood, whereas the majority of experiments have been carried out for 2D targets deposited on substrates. Here, we suggest a universal and computationally efficient scheme to model the irradiation of supported 2D materials, which combines analytical potential molecular dynamics with Monte Carlo simulations and makes it possible to independently assess the contributions to the damage from backscattered ions and atoms sputtered from the substrate. Using the scheme, we study the defect production in graphene and MoS2 sheets, which are the two most important and wide-spread 2D materials, deposited on a SiO2 substrate. For helium and neon ions with a wide range of initial ion energies including those used in a commercial helium ion microscope (HIM), we demonstrate that depending on the ion energy and mass, the defect production in 2D systems can be dominated by backscattered ions and sputtered substrate atoms rather than by the direct ion impacts and that the amount of damage in 2D materials heavily depends on whether a substrate is present or not. We also study the factors which limit the spatial resolution of the patterning process. Our results, which agree well with the available experimental data, provide not only insights into defect production but also quantitative information, which can be used for the minimization of damage during imaging in HIM or optimization of the patterning process.}, author = {Kretschmer, Silvan and Maslov, Mikhail and Ghaderzadeh, Sadegh and Ghorbani-Asl, Mahdi and Hlawacek, Gregor and Krasheninnikov, Arkady V.}, issn = {1944-8244}, journal = {ACS Applied Materials & Interfaces}, keywords = {General Materials Science}, number = {36}, pages = {30827--30836}, publisher = {American Chemical Society}, title = {{Supported two-dimensional materials under ion irradiation: The substrate governs defect production}}, doi = {10.1021/acsami.8b08471}, volume = {10}, year = {2018}, } @article{8443, abstract = {Characterizing the structure of membrane proteins (MPs) generally requires extraction from their native environment, most commonly with detergents. Yet, the physicochemical properties of detergent micelles and lipid bilayers differ markedly and could alter the structural organization of MPs, albeit without general rules. Dodecylphosphocholine (DPC) is the most widely used detergent for MP structure determination by NMR, but the physiological relevance of several prominent structures has been questioned, though indirectly, by other biophysical techniques, e.g., functional/thermostability assay (TSA) and molecular dynamics (MD) simulations. Here, we resolve unambiguously this controversy by probing the functional relevance of three different mitochondrial carriers (MCs) in DPC at the atomic level, using an exhaustive set of solution-NMR experiments, complemented by functional/TSA and MD data. Our results provide atomic-level insight into the structure, substrate interaction and dynamics of the detergent–membrane protein complexes and demonstrates cogently that, while high-resolution NMR signals can be obtained for MCs in DPC, they systematically correspond to nonfunctional states.}, author = {Kurauskas, Vilius and Hessel, Audrey and Ma, Peixiang and Lunetti, Paola and Weinhäupl, Katharina and Imbert, Lionel and Brutscher, Bernhard and King, Martin S. and Sounier, Rémy and Dolce, Vincenza and Kunji, Edmund R. S. and Capobianco, Loredana and Chipot, Christophe and Dehez, François and Bersch, Beate and Schanda, Paul}, issn = {1948-7185}, journal = {The Journal of Physical Chemistry Letters}, keywords = {General Materials Science}, number = {5}, pages = {933--938}, publisher = {American Chemical Society}, title = {{How detergent impacts membrane proteins: Atomic-level views of mitochondrial carriers in dodecylphosphocholine}}, doi = {10.1021/acs.jpclett.8b00269}, volume = {9}, year = {2018}, } @article{9066, abstract = {The novel electronic state of the canted antiferromagnetic (AFM) insulator, strontium iridate (Sr2IrO4) has been well described by the spin-orbit-entangled isospin Jeff = 1/2, but the role of isospin in transport phenomena remains poorly understood. In this study, antiferromagnet-based spintronic functionality is demonstrated by combining unique characteristics of the isospin state in Sr2IrO4. Based on magnetic and transport measurements, large and highly anisotropic magnetoresistance (AMR) is obtained by manipulating the antiferromagnetic isospin domains. First-principles calculations suggest that electrons whose isospin directions are strongly coupled to in-plane net magnetic moment encounter the isospin mismatch when moving across antiferromagnetic domain boundaries, which generates a high resistance state. By rotating a magnetic field that aligns in-plane net moments and removes domain boundaries, the macroscopically-ordered isospins govern dynamic transport through the system, which leads to the extremely angle-sensitive AMR. As with this work that establishes a link between isospins and magnetotransport in strongly spin-orbit-coupled AFM Sr2IrO4, the peculiar AMR effect provides a beneficial foundation for fundamental and applied research on AFM spintronics.}, author = {Lee, Nara and Ko, Eunjung and Choi, Hwan Young and Hong, Yun Jeong and Nauman, Muhammad and Kang, Woun and Choi, Hyoung Joon and Choi, Young Jai and Jo, Younjung}, issn = {0935-9648}, journal = {Advanced Materials}, keywords = {Mechanical Engineering, General Materials Science, Mechanics of Materials}, number = {52}, publisher = {Wiley}, title = {{Antiferromagnet‐based spintronic functionality by controlling isospin domains in a layered perovskite iridate}}, doi = {10.1002/adma.201805564}, volume = {30}, year = {2018}, } @article{13375, abstract = {Dissipative self-assembly leads to structures and materials that exist away from equilibrium by continuously exchanging energy and materials with the external environment. Although this mode of self-assembly is ubiquitous in nature, where it gives rise to functions such as signal processing, motility, self-healing, self-replication, and ultimately life, examples of dissipative self-assembly processes in man-made systems are few and far between. Herein, recent progress in developing diverse synthetic dissipative self-assembly systems is discussed. The systems reported thus far can be categorized into three classes, in which: i) the fuel chemically modifies the building blocks, thus triggering their self-assembly, ii) the fuel acts as a template interacting with the building blocks noncovalently, and iii) transient states are induced by the addition of two mutually exclusive stimuli. These early studies give rise to materials that would be difficult to obtain otherwise, including hydrogels with programmable lifetimes, vesicular nanoreactors, and membranes exhibiting transient conductivity.}, author = {De, Soumen and Klajn, Rafal}, issn = {1521-4095}, journal = {Advanced Materials}, keywords = {Mechanical Engineering, Mechanics of Materials, General Materials Science}, number = {41}, publisher = {Wiley}, title = {{Dissipative self-assembly driven by the consumption of chemical fuels}}, doi = {10.1002/adma.201706750}, volume = {30}, year = {2018}, } @article{13379, author = {Bléger, David and Klajn, Rafal}, issn = {1521-3927}, journal = {Macromolecular Rapid Communications}, keywords = {Materials Chemistry, Polymers and Plastics, Organic Chemistry}, number = {1}, publisher = {Wiley}, title = {{Integrating macromolecules with molecular switches}}, doi = {10.1002/marc.201700827}, volume = {39}, year = {2018}, } @article{10357, abstract = {The misfolding and aggregation of proteins into linear fibrils is widespread in human biology, for example, in connection with amyloid formation and the pathology of neurodegenerative disorders such as Alzheimer’s and Parkinson’s diseases. The oligomeric species that are formed in the early stages of protein aggregation are of great interest, having been linked with the cellular toxicity associated with these conditions. However, these species are not characterized in any detail experimentally, and their properties are not well understood. Many of these species have been found to have approximately spherical morphology and to be held together by hydrophobic interactions. We present here an analytical statistical mechanical model of globular oligomer formation from simple idealized amphiphilic protein monomers and show that this correlates well with Monte Carlo simulations of oligomer formation. We identify the controlling parameters of the model, which are closely related to simple quantities that may be fitted directly from experiment. We predict that globular oligomers are unlikely to form at equilibrium in many polypeptide systems but instead form transiently in the early stages of amyloid formation. We contrast the globular model of oligomer formation to a well-established model of linear oligomer formation, highlighting how the differing ensemble properties of linear and globular oligomers offer a potential strategy for characterizing oligomers from experimental measurements.}, author = {Dear, Alexander J. and Šarić, Anđela and Michaels, Thomas C. T. and Dobson, Christopher M. and Knowles, Tuomas P. J.}, issn = {1520-5207}, journal = {The Journal of Physical Chemistry B}, keywords = {materials chemistry}, number = {49}, pages = {11721--11730}, publisher = {American Chemical Society}, title = {{Statistical mechanics of globular oligomer formation by protein molecules}}, doi = {10.1021/acs.jpcb.8b07805}, volume = {122}, year = {2018}, } @article{8453, abstract = {Transverse relaxation rate measurements in magic-angle spinning solid-state nuclear magnetic resonance provide information about molecular motions occurring on nanosecond-to-millisecond (ns–ms) time scales. The measurement of heteronuclear (13C, 15N) relaxation rate constants in the presence of a spin-lock radiofrequency field (R1ρ relaxation) provides access to such motions, and an increasing number of studies involving R1ρ relaxation in proteins have been reported. However, two factors that influence the observed relaxation rate constants have so far been neglected, namely, (1) the role of CSA/dipolar cross-correlated relaxation (CCR) and (2) the impact of fast proton spin flips (i.e., proton spin diffusion and relaxation). We show that CSA/D CCR in R1ρ experiments is measurable and that the CCR rate constant depends on ns–ms motions; it can thus provide insight into dynamics. We find that proton spin diffusion attenuates this CCR due to its decoupling effect on the doublet components. For measurements of dynamics, the use of R1ρ rate constants has practical advantages over the use of CCR rates, and this article reveals factors that have so far been disregarded and which are important for accurate measurements and interpretation.}, author = {Kurauskas, Vilius and Weber, Emmanuelle and Hessel, Audrey and Ayala, Isabel and Marion, Dominique and Schanda, Paul}, issn = {1520-6106}, journal = {The Journal of Physical Chemistry B}, keywords = {Physical and Theoretical Chemistry, Materials Chemistry, Surfaces, Coatings and Films}, number = {34}, pages = {8905--8913}, publisher = {American Chemical Society}, title = {{Cross-correlated relaxation of dipolar coupling and chemical-shift anisotropy in magic-angle spinning R1ρ NMR measurements: Application to protein backbone dynamics measurements}}, doi = {10.1021/acs.jpcb.6b06129}, volume = {120}, year = {2016}, } @article{8455, abstract = {Solid-state NMR spectroscopy allows the characterization of the structure, interactions and dynamics of insoluble and/or very large proteins. Sensitivity and resolution are often major challenges for obtaining atomic-resolution information, in particular for very large protein complexes. Here we show that the use of deuterated, specifically CH3-labelled proteins result in significant sensitivity gains compared to previously employed CHD2 labelling, while line widths increase only marginally. We apply this labelling strategy to a 468 kDa-large dodecameric aminopeptidase, TET2, and the 1.6 MDa-large 50S ribosome subunit of Thermus thermophilus.}, author = {Kurauskas, Vilius and Crublet, Elodie and Macek, Pavel and Kerfah, Rime and Gauto, Diego F. and Boisbouvier, Jérôme and Schanda, Paul}, issn = {1359-7345}, journal = {Chemical Communications}, keywords = {Materials Chemistry, Electronic, Optical and Magnetic Materials, General Chemistry, Surfaces, Coatings and Films, Metals and Alloys, Ceramics and Composites, Catalysis}, number = {61}, pages = {9558--9561}, publisher = {Royal Society of Chemistry}, title = {{Sensitive proton-detected solid-state NMR spectroscopy of large proteins with selective CH3labelling: Application to the 50S ribosome subunit}}, doi = {10.1039/c6cc04484k}, volume = {52}, year = {2016}, } @article{13385, abstract = {Novel light-responsive nanoparticles were synthesized by decorating the surfaces of gold and silver nanoparticles with a nitrospiropyran molecular photoswitch. Upon exposure to UV light in nonpolar solvents, these nanoparticles self-assembled to afford spherical aggregates, which disassembled rapidly when the UV stimulus was turned off. The sizes of these aggregates depended on the nanoparticle concentration, and their lifetimes could be controlled by adjusting the surface concentration of nitrospiropyran on the nanoparticles. The conformational flexibility of nitrospiropyran, which was altered by modifying the structure of the background ligand, had a profound impact on the self-assembly process. By coating the nanoparticles with a spiropyran lacking the nitro group, a conceptually different self-assembly system, relying on a reversible proton transfer, was realized. The resulting particles spontaneously (in the dark) assembled into aggregates that could be readily disassembled upon exposure to blue light.}, author = {Kundu, Pintu K. and Das, Sanjib and Ahrens, Johannes and Klajn, Rafal}, issn = {2040-3372}, journal = {Nanoscale}, keywords = {General Materials Science}, number = {46}, pages = {19280--19286}, publisher = {Royal Society of Chemistry}, title = {{Controlling the lifetimes of dynamic nanoparticle aggregates by spiropyran functionalization}}, doi = {10.1039/c6nr05959g}, volume = {8}, year = {2016}, } @article{13386, abstract = {Azobenzenealkanethiols in self-assembled monolayers (SAMs) on Au(111) exhibit reversible trans–cis photoisomerization when diluted with alkanethiol spacers. Using these mixed SAMs, we show switching of the linear optical and second-harmonic response. The effective switching of these surface optical properties relies on a reasonably large cross section and a high photoisomerization yield as well as a long lifetime of the metastable cis isomer. We quantified the switching process by X-ray absorption spectroscopy. The cross sections for the trans–cis and cis–trans photoisomerization with 365 and 455 nm light, respectively, are 1 order of magnitude smaller than in solution. In vacuum, the 365 nm photostationary state comprises 50–74% of the molecules in the cis form, limited by their rapid thermal isomerization back to the trans state. In contrast, the 455 nm photostationary state contains nearly 100% trans-azobenzene. We determined time constants for the thermal cis–trans isomerization of only a few minutes in vacuum and in a dry nitrogen atmosphere but of more than 1 day in ambient air. Our results suggest that adventitious water adsorbed on the surface of the SAM stabilizes the polar cis configuration of azobenzene under ambient conditions. The back reaction rate constants differing by 2 orders of magnitude underline the huge influence of the environment and, accordingly, its importance when comparing various experiments.}, author = {Moldt, Thomas and Przyrembel, Daniel and Schulze, Michael and Bronsch, Wibke and Boie, Larissa and Brete, Daniel and Gahl, Cornelius and Klajn, Rafal and Tegeder, Petra and Weinelt, Martin}, issn = {1520-5827}, journal = {Langmuir}, keywords = {Electrochemistry, Spectroscopy, Surfaces and Interfaces, Condensed Matter Physics, General Materials Science}, number = {42}, pages = {10795--10801}, publisher = {American Chemical Society}, title = {{Differing isomerization kinetics of azobenzene-functionalized self-assembled monolayers in ambient air and in vacuum}}, doi = {10.1021/acs.langmuir.6b01690}, volume = {32}, year = {2016}, } @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}, } @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}, }