Copper-Catalyzed Intramolecular Olefinic C(sp2)-H Amidation for the Synthesis of γ-Alkylidene-γ-lactams.

Herein, we report the copper-catalyzed dehydrogenative C(sp2)-N bond formation of 4-pentenamides via nitrogen-centered radicals. This reaction provides a straightforward and efficient preparation method for γ-alkylidene-γ-lactams. Notably, we could controllably synthesize α,ß-unsaturated- or α,ß-saturated-γ-alkylidene-γ-lactams depending on the reaction conditions.

Polymerization/depolymerization of actin cooperates with the morphology and stability of cell-sized droplets generated in a polymer solution under a depletion effect.

Intercellular fluids in living organisms contain high concentrations of macromolecules such as nucleic acid and protein. Over the past few decades, several studies have examined membraneless organelles in terms of liquid-liquid phase separation. These studies have investigated aggregation/attraction among a rich variety of biomolecules. Here, we studied the association between the polymerization/depolymerization of actin, interconversion between monomeric (G-actin) and filamentous states (F-actin), and water/water phase separation in a binary polymer solution using polyethylene glycol (PEG) and dextran (DEX). We found that actin, which is a representative cytoskeleton, changes its distribution in a PEG/DEX binary solution depending on its polymerization state: monomeric G-actin is distributed homogeneously throughout the solution, whereas polymerized F-actin is localized only within the DEX-rich phase. We extended our study by using fragmin, which is a representative actin-severing and -depolymerizing factor. It took hours to restore a homogeneous actin distribution from localization within the DEX-rich phase, even with the addition of fragmin in an amount that causes complete depolymerization. In contrast, when actin that had been depolymerized by fragmin in advance was added to a solution with microphase-separation, F-actin was found in DEX-rich phase droplets. The micro-droplets tended to deform into a non-spherical morphology under conditions where they contained F-actin. These findings suggest that microphase-separation is associated with the dynamics of polymerization and localization of the actin cytoskeleton. We discuss our observations by taking into consideration the polymer depletion effect.

GTP-dependent formation of straight tubulin oligomers leads to microtubule nucleation.

Nucleation of microtubules (MTs) is essential for cellular activities, but its mechanism is unknown because of the difficulty involved in capturing rare stochastic events in the early stage of polymerization. Here, combining rapid flush negative stain electron microscopy (EM) and kinetic analysis, we demonstrate that the formation of straight oligomers of critical size is essential for nucleation. Both GDP and GTP tubulin form single-stranded oligomers with a broad range of curvatures, but upon nucleation, the curvature distribution of GTP oligomers is shifted to produce a minor population of straight oligomers. With tubulin having the Y222F mutation in the ß subunit, the proportion of straight oligomers increases and nucleation accelerates. Our results support a model in which GTP binding generates a minor population of straight oligomers compatible with lateral association and further growth to MTs. This study suggests that cellular factors involved in nucleation promote it via stabilization of straight oligomers.

Secure Physical Layer Network Coding versus Secure Network Coding.

When a network has relay nodes, there is a risk that a part of the information is leaked to an untrusted relay. Secure network coding (secure NC) is known as a method to resolve this problem, which enables the secrecy of the message when the message is transmitted over a noiseless network and a part of the edges or a part of the intermediate (untrusted) nodes are eavesdropped. If the channels on the network are noisy, the error correction is applied to noisy channels before the application of secure NC on an upper layer. In contrast, secure physical layer network coding (secure PLNC) is a method to securely transmit a message by a combination of coding operation on nodes when the network is composed of set of noisy channels. Since secure NC is a protocol on an upper layer, secure PLNC can be considered as a cross-layer protocol. In this paper, we compare secure PLNC with a simple combination of secure NC and error correction over several typical network models studied in secure NC.

Finite-Length Analyses for Source and Channel Coding on Markov Chains.

We derive finite-length bounds for two problems with Markov chains: source coding with side-information where the source and side-information are a joint Markov chain and channel coding for channels with Markovian conditional additive noise. For this purpose, we point out two important aspects of finite-length analysis that must be argued when finite-length bounds are proposed. The first is the asymptotic tightness, and the other is the efficient computability of the bound. Then, we derive finite-length upper and lower bounds for the coding length in both settings such that their computational complexity is low. We argue the first of the above-mentioned aspects by deriving the large deviation bounds, the moderate deviation bounds, and second-order bounds for these two topics and show that these finite-length bounds achieve the asymptotic optimality in these senses. Several kinds of information measures for transition matrices are introduced for the purpose of this discussion.

Reduction Theorem for Secrecy over Linear Network Code for Active Attacks.

We discuss the effect of sequential error injection on information leakage under a network code. We formulate a network code for the single transmission setting and the multiple transmission setting. Under this formulation, we show that the eavesdropper cannot increase the power of eavesdropping by sequential error injection when the operations in the network are linear operations. We demonstrated the usefulness of this reduction theorem by applying a concrete example of network.

Perfect Discrimination in Approximate Quantum Theory of General Probabilistic Theories.

As a modern approach for the foundation of quantum theory, existing studies of general probabilistic theories gave various models of states and measurements that are quite different from quantum theory. In this Letter, to seek a more realistic situation, we investigate models approximately close to quantum theory. We define larger measurement classes that are smoothly connected with the class of POVMs via a parameter, and investigate the performance of perfect discrimination. As a result, we give a sufficient condition of perfect discrimination, which shows a significant improvement beyond the class of POVMs.

Self-Emergent Protocells Generated in an Aqueous Solution with Binary Macromolecules through Liquid-Liquid Phase Separation.

Recently, liquid-liquid phase separation (LLPS) has attracted considerable attention among researchers in the life sciences as a plausible mechanism for the generation of microstructures inside cells. LLPS occurs through multiple nonspecific interactions and does not always require a lock-and-key interaction with a binary macromolecular solution. The remarkable features of LLPS include the non-uniform localization and concentration of solutes, resulting in the ability to isolate certain chemical systems and thereby parallelize multiple chemical reactions within the limited space of a living cell. We report that, by using the macromolecules, poly(ethylene glycol) (PEG) and dextran, that exhibit LLPS in an aqueous solution, cell-sized liposomes are spontaneously formed therein in the presence of phospholipids. In this system, LLPS is generated through the depletion effect of macromolecules. The results showed that cell-like microdroplets entrapping DNA wrapped by a phospholipid layer emerge in a self-organized manner.

D-Loop Mutation G42A/G46A Decreases Actin Dynamics.

Depolymerization and polymerization of the actin filament are indispensable in eukaryotes. The DNase I binding loop (D-loop), which forms part of the interface between the subunits in the actin filament, is an intrinsically disordered loop with a large degree of conformational freedom. Introduction of the double mutation G42A/G46A to the D-loop of the beta cytoskeletal mammalian actin restricted D-loop conformational freedom, whereas changes to the critical concentration were not large, and no major structural changes were observed. Polymerization and depolymerization rates at both ends of the filament were reduced, and cofilin binding was inhibited by the double mutation. These results indicate that the two glycines at the tip of the D-loop are important for actin dynamics, most likely by contributing to the large degree of conformational freedom.

Application of the Resource Theory of Channels to Communication Scenarios.

We introduce a resource theory of channels relevant to communication via quantum channels, in which the set of constant channels-useless channels for communication tasks-are considered as free resources. We find that our theory with such a simple structure is useful to address central problems in quantum Shannon theory-in particular, we provide a converse bound for the one-shot nonsignaling assisted classical capacity that naturally leads to its strong converse property, as well as obtain the one-shot channel simulation cost with nonsignaling assistance. We clarify an intimate connection between the nonsignaling assistance and our formalism by identifying the nonsignaling assisted channel coding with the channel transformation under the maximal set of resource nongenerating superchannels, providing a physical characterization of the latter. Our results provide new perspectives and concise arguments to those problems, connecting the recently developed fields of resource theories to "classic" settings in quantum information theory and shedding light on the validity of resource theories of channels as effective tools to address practical problems.

Copper-Catalyzed Oxidative Benzylic C(sp3 )-H Cyclization for the Synthesis of ß-Lactams.

ß-Lactams are important structural motifs because of their ubiquity in natural products and pharmaceuticals. We report herein a Cu-catalyzed intramolecular oxidative C(sp3 )-H amidation for the synthesis of ß-lactams using tBuOOtBu. This method is based on Kharasch-Sosnovsky amidation and does not require prefunctionalization of C(sp3 )-H bonds or the installation of a directing group, thereby allowing for the straightforward synthesis of ß-lactams. Our intramolecular functionalization protocol can be extended to diverse benzylic C(sp3 )-H bonds and shows excellent functional-group tolerance.

Quantum computational universality of hypergraph states with Pauli-X and Z basis measurements.

Measurement-based quantum computing is one of the most promising quantum computing models. Although various universal resource states have been proposed so far, it was open whether only two Pauli bases are enough for both of universal measurement-based quantum computing and its verification. In this paper, we construct a universal hypergraph state that only requires X and Z-basis measurements for universal measurement-based quantum computing. We also show that universal measurement-based quantum computing on our hypergraph state can be verified in polynomial time using only X and Z-basis measurements. Furthermore, in order to demonstrate an advantage of our hypergraph state, we construct a verifiable blind quantum computing protocol that requires only X and Z-basis measurements for the client.

Correction to 'Quantum stopwatch: how to store time in a quantum memory'.

[This corrects the article DOI: 10.1098/rspa.2017.0773.][This corrects the article DOI: 10.1098/rspa.2017.0773.].

Efficient Verification of Pure Quantum States in the Adversarial Scenario.

Efficient verification of pure quantum states in the adversarial scenario is crucial to many applications in quantum information processing, such as blind measurement-based quantum computation and quantum networks. However, little is known about this topic so far. Here, we establish a general framework for verifying pure quantum states in the adversarial scenario and clarify the resource cost. Moreover, we propose a simple and general recipe to constructing efficient verification protocols for the adversarial scenario from protocols for the nonadversarial scenario. With this recipe, arbitrary pure states can be verified in the adversarial scenario with almost the same efficiency as in the nonadversarial scenario. Many important quantum states can be verified in the adversarial scenario using local projective measurements with unprecedented high efficiencies.

Quantum stopwatch: how to store time in a quantum memory.

Quantum mechanics imposes a fundamental trade-off between the accuracy of time measurements and the size of the systems used as clocks. When the measurements of different time intervals are combined, the errors due to the finite clock size accumulate, resulting in an overall inaccuracy that grows with the complexity of the set-up. Here, we introduce a method that, in principle, eludes the accumulation of errors by coherently transferring information from a quantum clock to a quantum memory of the smallest possible size. Our method could be used to measure the total duration of a sequence of events with enhanced accuracy, and to reduce the amount of quantum communication needed to stabilize clocks in a quantum network.

Specific Spatial Localization of Actin and DNA in a Water/Water Microdroplet: Self-Emergence of a Cell-Like Structure.

The effect of binary hydrophilic polymers on a pair of representative bio-macromolecules in a living cell has been examined. The results showed that these bio-macromolecules exhibited specific localization in cell-sized droplets that were spontaneously formed through water/water microphase segregation under crowding conditions with coexisting polymers. In these experiments, a simple binary polymer system with poly(ethylene glycol) (PEG) and dextran (DEX) was used. Under the conditions of microphase segregation, DNA was entrapped within cell-sized droplets rich in DEX. Similarly, F-actin, linearly polymerized actin, was entrapped specifically within microdroplets rich in DEX, whereas G-actin, a monomeric actin, was distributed evenly inside and outside these droplets. This study has been extended to a system with both F-actin and DNA, and it was found that DNA molecules were localized separately from aligned F-actin proteins to create microdomains inside microdroplets, reflecting the self-emergence of a cellular morphology similar to a stage of cell division.

Morphological Control of Microtubule-Encapsulating Giant Vesicles by Changing Hydrostatic Pressure.

For the development of artificial cell-like machinery, liposomes encapsulating cytoskeletons have drawn much recent attention. However, there has been no report showing isothermally reversible morphological changes of liposomes containing cytoskeletons. We succeeded in reversibly changing the shape of cell-sized giant vesicles by controlling the polymerization/depolymerization state of cytoskeletal microtubules that were encapsulated in the vesicles using pressure changes. The result indicates that it is possible to manipulate artificial cell models composed of molecules such as lipids and proteins. The findings obtained in this study will be helpful in clarifying the details of cooperation between cytoskeletal dynamics and morphogenesis of biological membranes and in improving the design and construction of further advanced artificial cell-like machinery, such as drug-delivery systems. In addition, the experimental system used in this study can be applied to research to elucidate the adaptive strategy of living organisms to external stimuli and extreme conditions such as osmotic stress and high-pressure environments like the deep sea.

Universally Fisher-Symmetric Informationally Complete Measurements.

A quantum measurement is Fisher symmetric if it provides uniform and maximal information on all parameters that characterize the quantum state of interest. Using (complex projective) 2-designs, we construct measurements on a pair of identically prepared quantum states that are Fisher symmetric for all pure states. Such measurements are optimal in achieving the minimal statistical error without adaptive measurements. We then determine all collective measurements on a pair that are Fisher symmetric for the completely mixed state and for all pure states simultaneously. For a qubit, these measurements are Fisher symmetric for all states. The minimal optimal measurements are tied to the elusive symmetric informationally complete measurements, which reflects a deep connection between local symmetry and global symmetry. In the study, we derive a fundamental constraint on the Fisher information matrix of any collective measurement on a pair, which offers a useful tool for characterizing the tomographic efficiency of collective measurements.

Optimal performance of generalized heat engines with finite-size baths of arbitrary multiple conserved quantities beyond independent-and-identical-distribution scaling.

In quantum thermodynamics, effects of finiteness of the baths have been less considered. In particular, there is no general theory which focuses on finiteness of the baths of multiple conserved quantities. Then, we investigate how the optimal performance of generalized heat engines with multiple conserved quantities alters in response to the size of the baths. In the context of general theories of quantum thermodynamics, the size of the baths has been given in terms of the number of identical copies of a system, which does not cover even such a natural scaling as the volume. In consideration of the asymptotic extensivity, we deal with a generic scaling of the baths to naturally include the volume scaling. Based on it, we derive a bound for the performance of generalized heat engines reflecting finite-size effects of the baths, which we call fine-grained generalized Carnot bound. We also construct a protocol to achieve the optimal performance of the engine given by this bound. Finally, applying the obtained general theory, we deal with simple examples of generalized heat engines. As for an example of non-independent-and-identical-distribution scaling and multiple conserved quantities, we investigate a heat engine with two baths composed of an ideal gas exchanging particles, where the volume scaling is applied. The result implies that the mass of the particle explicitly affects the performance of this engine with finite-size baths.

Discrimination Power of a Quantum Detector.

We investigate the ability of a quantum measurement device to discriminate two states or, generically, two hypotheses. In full generality, the measurement can be performed a number n of times, and arbitrary preprocessing of the states and postprocessing of the obtained data are allowed. There is an intrinsic error associated with the measurement device, which we aim to quantify, that limits its discrimination power. We minimize various error probabilities (averaged or constrained) over all pairs of n-partite input states. These probabilities, or their exponential rates of decrease in the case of large n, give measures of the discrimination power of the device. For the asymptotic rate of the averaged error probability, we obtain a Chernoff-type bound, dual to the standard Chernoff bound for which the state pair is fixed and the optimization is over all measurements. The key point in the derivation is that identical copies of input states become optimal in asymptotic settings. Optimal asymptotic rates are also obtained for constrained error probabilities, dual to Stein's lemma and Hoeffding's bound. We further show that adaptive protocols where the state preparer gets feedback from the measurer do not improve the asymptotic rates. These rates thus quantify the ultimate discrimination power of a measurement device.