@inproceedings{2190, abstract = {We present a new algorithm to construct a (generalized) deterministic Rabin automaton for an LTL formula φ. The automaton is the product of a master automaton and an array of slave automata, one for each G-subformula of φ. The slave automaton for G ψ is in charge of recognizing whether FG ψ holds. As opposed to standard determinization procedures, the states of all our automata have a clear logical structure, which allows for various optimizations. Our construction subsumes former algorithms for fragments of LTL. Experimental results show improvement in the sizes of the resulting automata compared to existing methods.}, author = {Esparza, Javier and Kretinsky, Jan}, pages = {192 -- 208}, publisher = {Springer}, title = {{From LTL to deterministic automata: A safraless compositional approach}}, doi = {10.1007/978-3-319-08867-9_13}, volume = {8559}, year = {2014}, } @article{13399, abstract = {Nature has long inspired scientists with its seemingly unlimited ability to harness solar energy and to utilize it to drive various physiological processes. With the help of man-made molecular photoswitches, we now have the potential to outperform natural systems in many ways, with the ultimate goal of fabricating multifunctional materials that operate at different light wavelengths. An important challenge in developing light-controlled artificial molecular machines lies in attaining a detailed understanding of the photoisomerization-coupled conformational changes that occur in macromolecules and molecular assemblies. In this issue of ACS Nano, Bléger, Rabe, and co-workers use force microscopy to provide interesting insights into the behavior of individual photoresponsive molecules and to identify contraction, extension, and crawling events accompanying light-induced isomerization.}, author = {Kundu, Pintu K. and Klajn, Rafal}, issn = {1936-086X}, journal = {ACS Nano}, keywords = {General Physics and Astronomy, General Engineering, General Materials Science}, number = {12}, pages = {11913--11916}, publisher = {American Chemical Society}, title = {{Watching single molecules move in response to light}}, doi = {10.1021/nn506656r}, volume = {8}, year = {2014}, } @article{13400, abstract = {Organizing inorganic nanocrystals into complex architectures is challenging and typically relies on preexisting templates, such as properly folded DNA or polypeptide chains. We found that under carefully controlled conditions, cubic nanocrystals of magnetite self-assemble into arrays of helical superstructures in a template-free manner with >99% yield. Computer simulations revealed that the formation of helices is determined by the interplay of van der Waals and magnetic dipole-dipole interactions, Zeeman coupling, and entropic forces and can be attributed to spontaneous formation of chiral nanocube clusters. Neighboring helices within their densely packed ensembles tended to adopt the same handedness in order to maximize packing, thus revealing a novel mechanism of symmetry breaking and chirality amplification.}, author = {Singh, Gurvinder and Chan, Henry and Baskin, Artem and Gelman, Elijah and Repnin, Nikita and Král, Petr and Klajn, Rafal}, issn = {1095-9203}, journal = {Science}, keywords = {Multidisciplinary}, number = {6201}, pages = {1149--1153}, publisher = {American Association for the Advancement of Science}, title = {{Self-assembly of magnetite nanocubes into helical superstructures}}, doi = {10.1126/science.1254132}, volume = {345}, year = {2014}, } @article{13401, abstract = {A compound combining the features of a molecular rotor and a photoswitch was synthesized and was shown to exist as three diastereomers, which interconvert via a reversible cyclic reaction scheme. Each of the three diastereomers was isolated, and by following the equilibration kinetics, activation barriers for all reactions were calculated. The results indicate that the properties of molecular switches depend heavily on their immediate chemical environment. The conclusions are important in the context of designing new switchable molecules and materials.}, author = {Kundu, Pintu K. and Lerner, Avishai and Kučanda, Kristina and Leitus, Gregory and Klajn, Rafal}, issn = {1520-5126}, journal = {Journal of the American Chemical Society}, keywords = {Colloid and Surface Chemistry, Biochemistry, General Chemistry, Catalysis}, number = {32}, pages = {11276--11279}, publisher = {American Chemical Society}, title = {{Cyclic kinetics during thermal equilibration of an axially chiral bis-spiropyran}}, doi = {10.1021/ja505948q}, volume = {136}, year = {2014}, } @article{13402, abstract = {Nanoporous frameworks are polymeric materials built from rigid molecules, which give rise to their nanoporous structures with applications in gas sorption and storage, catalysis and others. Conceptually new applications could emerge, should these beneficial properties be manipulated by external stimuli in a reversible manner. One approach to render nanoporous frameworks responsive to external signals would be to immobilize molecular switches within their nanopores. Although the majority of molecular switches require conformational freedom to isomerize, and switching in the solid state is prohibited, the nanopores may provide enough room for the switches to efficiently isomerize. Here we describe two families of nanoporous materials incorporating the spiropyran molecular switch. These materials exhibit a variety of interesting properties, including reversible photochromism and acidochromism under solvent-free conditions, light-controlled capture and release of metal ions, as well reversible chromism induced by solvation/desolvation.}, author = {Kundu, Pintu K. and Olsen, Gregory L. and Kiss, Vladimir and Klajn, Rafal}, issn = {2041-1723}, journal = {Nature Communications}, keywords = {General Physics and Astronomy, General Biochemistry, Genetics and Molecular Biology, General Chemistry, Multidisciplinary}, publisher = {Springer Nature}, title = {{Nanoporous frameworks exhibiting multiple stimuli responsiveness}}, doi = {10.1038/ncomms4588}, volume = {5}, year = {2014}, } @article{13403, abstract = {We show that bimolecular reactions between species confined to the surfaces of nanoparticles can be manipulated by the nature of the linker, as well as by the curvature of the underlying particles.}, author = {Zdobinsky, Tino and Sankar Maiti, Pradipta and Klajn, Rafal}, issn = {1520-5126}, journal = {Journal of the American Chemical Society}, keywords = {Colloid and Surface Chemistry, Biochemistry, General Chemistry, Catalysis}, number = {7}, pages = {2711--2714}, publisher = {American Chemical Society}, title = {{Support curvature and conformational freedom control chemical reactivity of immobilized species}}, doi = {10.1021/ja411573a}, volume = {136}, year = {2014}, } @article{13404, abstract = {In the past few years, spiropyran has emerged as the molecule-of-choice for the construction of novel dynamic materials. This unique molecular switch undergoes structural isomerisation in response to a variety of orthogonal stimuli, e.g. light, temperature, metal ions, redox potential, and mechanical stress. Incorporation of this switch onto macromolecular supports or inorganic scaffolds allows for the creation of robust dynamic materials. This review discusses the synthesis, switching conditions, and use of dynamic materials in which spiropyran has been attached to the surfaces of polymers, biomacromolecules, inorganic nanoparticles, as well as solid surfaces. The resulting materials show fascinating properties whereby the state of the switch intimately affects a multitude of useful properties of the support. The utility of the spiropyran switch will undoubtedly endow these materials with far-reaching applications in the near future.}, author = {Klajn, Rafal}, issn = {1460-4744}, journal = {Chemical Society Reviews}, keywords = {General Chemistry}, number = {1}, pages = {148--184}, publisher = {Royal Society of Chemistry}, title = {{Spiropyran-based dynamic materials}}, doi = {10.1039/c3cs60181a}, volume = {43}, year = {2014}, } @article{1375, abstract = {We consider directed graphs where each edge is labeled with an integer weight and study the fundamental algorithmic question of computing the value of a cycle with minimum mean weight. Our contributions are twofold: (1) First we show that the algorithmic question is reducible to the problem of a logarithmic number of min-plus matrix multiplications of n×n-matrices, where n is the number of vertices of the graph. (2) Second, when the weights are nonnegative, we present the first (1+ε)-approximation algorithm for the problem and the running time of our algorithm is Õ(nωlog3(nW/ε)/ε),1 where O(nω) is the time required for the classic n×n-matrix multiplication and W is the maximum value of the weights. With an additional O(log(nW/ε)) factor in space a cycle with approximately optimal weight can be computed within the same time bound.}, author = {Chatterjee, Krishnendu and Henzinger, Monika H and Krinninger, Sebastian and Loitzenbauer, Veronika and Raskin, Michael}, journal = {Theoretical Computer Science}, number = {C}, pages = {104 -- 116}, publisher = {Elsevier}, title = {{Approximating the minimum cycle mean}}, doi = {10.1016/j.tcs.2014.06.031}, volume = {547}, year = {2014}, } @inproceedings{1392, abstract = {Fault-tolerant distributed algorithms play an important role in ensuring the reliability of many software applications. In this paper we consider distributed algorithms whose computations are organized in rounds. To verify the correctness of such algorithms, we reason about (i) properties (such as invariants) of the state, (ii) the transitions controlled by the algorithm, and (iii) the communication graph. We introduce a logic that addresses these points, and contains set comprehensions with cardinality constraints, function symbols to describe the local states of each process, and a limited form of quantifier alternation to express the verification conditions. We show its use in automating the verification of consensus algorithms. In particular, we give a semi-decision procedure for the unsatisfiability problem of the logic and identify a decidable fragment. We successfully applied our framework to verify the correctness of a variety of consensus algorithms tolerant to both benign faults (message loss, process crashes) and value faults (message corruption).}, author = {Dragoi, Cezara and Henzinger, Thomas A and Veith, Helmut and Widder, Josef and Zufferey, Damien}, location = {San Diego, USA}, pages = {161 -- 181}, publisher = {Springer}, title = {{A logic-based framework for verifying consensus algorithms}}, doi = {10.1007/978-3-642-54013-4_10}, volume = {8318}, year = {2014}, } @inproceedings{1393, abstract = {Probabilistic programs are usual functional or imperative programs with two added constructs: (1) the ability to draw values at random from distributions, and (2) the ability to condition values of variables in a program via observations. Models from diverse application areas such as computer vision, coding theory, cryptographic protocols, biology and reliability analysis can be written as probabilistic programs. Probabilistic inference is the problem of computing an explicit representation of the probability distribution implicitly specified by a probabilistic program. Depending on the application, the desired output from inference may vary-we may want to estimate the expected value of some function f with respect to the distribution, or the mode of the distribution, or simply a set of samples drawn from the distribution. In this paper, we describe connections this research area called \Probabilistic Programming" has with programming languages and software engineering, and this includes language design, and the static and dynamic analysis of programs. We survey current state of the art and speculate on promising directions for future research.}, author = {Gordon, Andrew and Henzinger, Thomas A and Nori, Aditya and Rajamani, Sriram}, booktitle = {Proceedings of the on Future of Software Engineering}, location = {Hyderabad, India}, pages = {167 -- 181}, publisher = {ACM}, title = {{Probabilistic programming}}, doi = {10.1145/2593882.2593900}, year = {2014}, } @article{14018, abstract = {The sensitivities of high-harmonic generation (HHG) and strong-field ionization (SFI) to coupled electronic and nuclear dynamics are studied, using the nitric oxide (NO) molecule as an example. A coherent superposition of electronic and rotational states of NO is prepared by impulsive stimulated Raman scattering and probed by simultaneous detection of HHG and SFI yields. We observe a fourfold higher sensitivity of high-harmonic generation to electronic dynamics and attribute it to the presence of inelastic quantum paths connecting coherently related electronic states [Kraus et al., Phys. Rev. Lett.111, 243005 (2013)]. Whereas different harmonic orders display very different sensitivities to rotational or electronic dynamics, strong-field ionization is found to be most sensitive to electronic motion. We introduce a general theoretical formalism for high-harmonic generation from coupled nuclear-electronic wave packets. We show that the unequal sensitivities of different harmonic orders to electronic or rotational dynamics result from the angle dependence of the photorecombination matrix elements which encode several autoionizing and shape resonances in the photoionization continuum of NO. We further study the dependence of rotational and electronic coherences on the intensity of the excitation pulse and support the observations with calculations.}, author = {Baykusheva, Denitsa Rangelova and Kraus, Peter M. and Zhang, Song Bin and Rohringer, Nina and Wörner, Hans Jakob}, issn = {1364-5498}, journal = {Faraday Discussions}, keywords = {Physical and Theoretical Chemistry}, pages = {113--132}, publisher = {Royal Society of Chemistry}, title = {{The sensitivities of high-harmonic generation and strong-field ionization to coupled electronic and nuclear dynamics}}, doi = {10.1039/c4fd00018h}, volume = {171}, year = {2014}, } @article{14019, abstract = {The cyclopropene radical cation (c-C3H₄⁺) is an important but poorly characterized three-membered-ring hydrocarbon. We report on a measurement of the high-resolution photoelectron and photoionization spectra of cyclopropene and several deuterated isotopomers, from which we have determined the rovibrational energy level structure of the X⁺ (2)B2 ground electronic state of c-C3H₄⁺ at low energies for the first time. The synthesis of the partially deuterated isotopomers always resulted in mixtures of several isotopomers, differing in their number of D atoms and in the location of these atoms, so that the photoelectron spectra of deuterated samples are superpositions of the spectra of several isotopomers. The rotationally resolved spectra indicate a C(2v)-symmetric R0 structure for the ground electronic state of c-C3H₄⁺. Two vibrational modes of c-C3H₄⁺ are found to have vibrational wave numbers below 300 cm(-1), which is surprising for such a small cyclic hydrocarbon. The analysis of the isotopic shifts of the vibrational levels enabled the assignment of the lowest-frequency mode (fundamental wave number of ≈110 cm(-1) in c-C3H₄⁺) to the CH2 torsional mode (ν₈⁺, A2 symmetry) and of the second-lowest-frequency mode (≈210 cm(-1) in c-C3H₄⁺) to a mode combining a CH out-of-plane with a CH2 rocking motion (ν₁₅⁺, B2 symmetry). The potential energy along the CH2 torsional coordinate is flat near the equilibrium structure and leads to a pronounced anharmonicity.}, author = {Vasilatou, K. and Michaud, J. M. and Baykusheva, Denitsa Rangelova and Grassi, G. and Merkt, F.}, issn = {1089-7690}, journal = {The Journal of Chemical Physics}, keywords = {Physical and Theoretical Chemistry, General Physics and Astronomy}, number = {6}, publisher = {AIP Publishing}, title = {{The cyclopropene radical cation: Rovibrational level structure at low energies from high-resolution photoelectron spectra}}, doi = {10.1063/1.4890744}, volume = {141}, year = {2014}, } @article{14020, abstract = {We report the observation of macroscopic field-free orientation, i.e., more than 73% of CO molecules pointing in the same direction. This is achieved through an all-optical scheme operating at high particle densities (>10(17)  cm(-3)) that combines one-color (ω) and two-color (ω+2ω) nonresonant femtosecond laser pulses. We show that the achieved orientation solely relies on the hyperpolarizability interaction as opposed to an ionization-depletion mechanism, thus, opening a wide range of applications. The achieved strong orientation enables us to reveal the molecular-frame anisotropies of the photorecombination amplitudes and phases caused by a shape resonance. The resonance appears as a local maximum in the even-harmonic emission around 28 eV. In contrast, the odd-harmonic emission is suppressed in this spectral region through the combined effects of an asymmetric photorecombination phase and a subcycle Stark effect, generic for polar molecules, that we experimentally identify.}, author = {Kraus, P. M. and Baykusheva, Denitsa Rangelova and Wörner, H. J.}, issn = {1079-7114}, journal = {Physical Review Letters}, keywords = {General Physics and Astronomy}, number = {2}, publisher = {American Physical Society}, title = {{Two-pulse field-free orientation reveals anisotropy of molecular shape resonance}}, doi = {10.1103/physrevlett.113.023001}, volume = {113}, year = {2014}, } @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{14301, abstract = {DNA has become a prime material for assembling complex three-dimensional objects that promise utility in various areas of application. However, achieving user-defined goals with DNA objects has been hampered by the difficulty to prepare them at arbitrary concentrations and in user-defined solution conditions. Here, we describe a method that solves this problem. The method is based on poly(ethylene glycol)-induced depletion of species with high molecular weight. We demonstrate that our method is applicable to a wide spectrum of DNA shapes and that it achieves excellent recovery yields of target objects up to 97 %, while providing efficient separation from non-integrated DNA strands. DNA objects may be prepared at concentrations up to the limit of solubility, including the possibility for bringing DNA objects into a solid phase. Due to the fidelity and simplicity of our method we anticipate that it will help to catalyze the development of new types of applications that use self-assembled DNA objects.}, author = {Stahl, Evi and Martin, Thomas and Praetorius, Florian M and Dietz, Hendrik}, issn = {1521-3773}, journal = {Angewandte Chemie International Edition}, number = {47}, pages = {12949--12954}, publisher = {Wiley}, title = {{Facile and scalable preparation of pure and dense DNA origami solutions}}, doi = {10.1002/ange.201405991}, volume = {126}, year = {2014}, } @inproceedings{1507, abstract = {The Wigner-Dyson-Gaudin-Mehta conjecture asserts that the local eigenvalue statistics of large real and complex Hermitian matrices with independent, identically distributed entries are universal in a sense that they depend only on the symmetry class of the matrix and otherwise are independent of the details of the distribution. We present the recent solution to this half-century old conjecture. We explain how stochastic tools, such as the Dyson Brownian motion, and PDE ideas, such as De Giorgi-Nash-Moser regularity theory, were combined in the solution. We also show related results for log-gases that represent a universal model for strongly correlated systems. Finally, in the spirit of Wigner’s original vision, we discuss the extensions of these universality results to more realistic physical systems such as random band matrices.}, author = {Erdös, László}, booktitle = {Proceedings of the International Congress of Mathematicians}, location = {Seoul, Korea}, pages = {214 -- 236}, publisher = {International Congress of Mathematicians}, title = {{Random matrices, log-gases and Hölder regularity}}, volume = {3}, year = {2014}, } @inproceedings{1516, abstract = {We present a rigorous derivation of the BCS gap equation for superfluid fermionic gases with point interactions. Our starting point is the BCS energy functional, whose minimizer we investigate in the limit when the range of the interaction potential goes to zero. }, author = {Bräunlich, Gerhard and Hainzl, Christian and Seiringer, Robert}, booktitle = {Proceedings of the QMath12 Conference}, location = {Berlin, Germany}, pages = {127 -- 137}, publisher = {World Scientific Publishing}, title = {{On the BCS gap equation for superfluid fermionic gases}}, doi = {10.1142/9789814618144_0007}, year = {2014}, } @article{15161, abstract = {The copper-catalyzed diboration of ketones followed by an acid-catalyzed elimination leads to the formation of 1,1-disubstituted and trisubstituted vinyl boronate esters with moderate to good yields and selectivity. Addition of tosic acid to the crude diboration products provides the corresponding vinyl boronate esters upon elimination. The trisubstituted vinyl boronate esters are formed as the (Z)-olefin isomer, which was established by subjecting the products to a Suzuki–Miyaura coupling reaction to obtain alkenes of known geometry.}, author = {Guan, Weiye and Michael, Alicia Kathleen and McIntosh, Melissa L. and Koren-Selfridge, Liza and Scott, John P. and Clark, Timothy B.}, issn = {1520-6904}, journal = {The Journal of Organic Chemistry}, keywords = {Organic Chemistry}, number = {15}, pages = {7199--7204}, publisher = {American Chemical Society}, title = {{Stereoselective formation of trisubstituted vinyl boronate esters by the acid-mediated elimination of α-hydroxyboronate esters}}, doi = {10.1021/jo500773t}, volume = {79}, year = {2014}, } @article{1629, abstract = {We propose a method for propagating edit operations in 2D vector graphics, based on geometric relationship functions. These functions quantify the geometric relationship of a point to a polygon, such as the distance to the boundary or the direction to the closest corner vertex. The level sets of the relationship functions describe points with the same relationship to a polygon. For a given query point, we first determine a set of relationships to local features, construct all level sets for these relationships, and accumulate them. The maxima of the resulting distribution are points with similar geometric relationships. We show extensions to handle mirror symmetries, and discuss the use of relationship functions as local coordinate systems. Our method can be applied, for example, to interactive floorplan editing, and it is especially useful for large layouts, where individual edits would be cumbersome. We demonstrate populating 2D layouts with tens to hundreds of objects by propagating relatively few edit operations.}, author = {Guerrero, Paul and Jeschke, Stefan and Wimmer, Michael and Wonka, Peter}, journal = {ACM Transactions on Graphics}, number = {2}, publisher = {ACM}, title = {{Edit propagation using geometric relationship functions}}, doi = {10.1145/2591010}, volume = {33}, year = {2014}, } @inproceedings{1643, abstract = {We extend the notion of verifiable random functions (VRF) to constrained VRFs, which generalize the concept of constrained pseudorandom functions, put forward by Boneh and Waters (Asiacrypt’13), and independently by Kiayias et al. (CCS’13) and Boyle et al. (PKC’14), who call them delegatable PRFs and functional PRFs, respectively. In a standard VRF the secret key sk allows one to evaluate a pseudorandom function at any point of its domain; in addition, it enables computation of a non-interactive proof that the function value was computed correctly. In a constrained VRF from the key sk one can derive constrained keys skS for subsets S of the domain, which allow computation of function values and proofs only at points in S. After formally defining constrained VRFs, we derive instantiations from the multilinear-maps-based constrained PRFs by Boneh and Waters, yielding a VRF with constrained keys for any set that can be decided by a polynomial-size circuit. Our VRFs have the same function values as the Boneh-Waters PRFs and are proved secure under the same hardness assumption, showing that verifiability comes at no cost. Constrained (functional) VRFs were stated as an open problem by Boyle et al.}, author = {Fuchsbauer, Georg}, booktitle = {SCN 2014}, editor = {Abdalla, Michel and De Prisco, Roberto}, location = {Amalfi, Italy}, pages = {95 -- 114}, publisher = {Springer}, title = {{Constrained Verifiable Random Functions }}, doi = {10.1007/978-3-319-10879-7_7}, volume = {8642}, year = {2014}, }