A Review of Laser-Induced Crystallization from Solution.

Crystallization abounds in nature and industrial practice. A plethora of indispensable products ranging from agrochemicals and pharmaceuticals to battery materials are produced in crystalline form in industrial practice. Yet, our control over the crystallization process across scales, from molecular to macroscopic, is far from complete. This bottleneck not only hinders our ability to engineer the properties of crystalline products essential for maintaining our quality of life but also hampers progress toward a sustainable circular economy in resource recovery. In recent years, approaches leveraging light fields have emerged as promising alternatives to manipulate crystallization. In this review article, we classify laser-induced crystallization approaches where light-material interactions are utilized to influence crystallization phenomena according to proposed underlying mechanisms and experimental setups. We discuss nonphotochemical laser-induced nucleation, high-intensity laser-induced nucleation, laser trapping-induced crystallization, and indirect methods in detail. Throughout the review, we highlight connections among these separately evolving subfields to encourage the interdisciplinary exchange of ideas.

Quantum Circuits with Classically Simulable Operator Scrambling.

We introduce a new family of quantum circuits for which the scrambling of a subspace of nonlocal operators is classically simulable. We call these circuits "super-Clifford circuits" since the Heisenberg time evolution of these operators corresponds to Clifford evolution in operator space. Thus we are able to classically simulate the time evolution of certain single Pauli strings into operators with operator entanglement that grows linearly with the number of qubits. These circuits provide a new technique for studying scrambling in systems with a large number of qubits, and are an explicit counter example to the intuition that classical simulability implies the absence of scrambling.

Structure and Efficiency in Bacterial Photosynthetic Light Harvesting.

Photosynthetic organisms use networks of chromophores to absorb and deliver solar energy to reaction centers. We present a detailed model of the light-harvesting complexes in purple bacteria, including explicit interaction with sunlight, radiative and nonradiative energy loss, and dephasing and thermalizing effects of coupling to a vibrational bath. We capture the effect of slow vibrations by introducing time-dependent disorder. Our model describes the experimentally observed high efficiency of light harvesting, despite the absence of long-range quantum coherence. The one-exciton part of the quantum state fluctuates continuously but remains highly mixed at all times. These results suggest a relatively minor role for structure in determining efficiency. We build hypothetical models with randomly arranged chromophores but still observe high efficiency when nearest-neighbor distances are comparable to those in nature. This helps explain the high transport efficiency in organisms with widely differing antenna structures and suggests new design criteria for artificial light-harvesting devices.

Robustness of Measurement, Discrimination Games, and Accessible Information.

We introduce a resource theory of measurement informativeness. This allows us to define an associated quantifier, which we call the robustness of measurement. It describes how much "noise" must be added to a measurement before it becomes completely uninformative. We show that this geometric quantifier has operational significance in terms of the advantage the measurement provides over guessing at random in a suitably chosen state discrimination game and that it is the single-shot generalization of the accessible information of a certain quantum-to-classical channel. Using this insight, we further show that the recently introduced robustness of asymmetry or coherence is the single-shot generalization of the accessible information of an ensemble. Finally, we discuss more generally the connection between robustness-based measures, discrimination problems, and information-theoretic quantities.

The dynamical interplay between a megadalton peptide nanocage and solutes probed by microsecond atomistic MD; implications for design.

Understanding the assembly and dynamics of protein-based supramolecular capsids and cages is of fundamental importance and could lead to applications in synthetic biology and biotechnology. Here we present long and large atomistic molecular dynamics simulations of de novo designed self-assembling protein nanocages (SAGEs) in aqueous media. Microsecond simulations, comprised of ≈42 million atoms for three pre-formed SAGEs of different charges, in the presence of solutes and solvent have been completed. Here, the dynamics, stability and porosity of the peptide networks are explored along with their interactions with ions, small molecules and macromolecular solutes. All assemblies are stable over the µs timescale, and the solutes show a mixture of transport behaviour across or adherence to the fabric of the SAGE particles. Solute proteins largely retained native-like conformation on contact with SAGE. Certain residues of the SAGE peptides are identified as "repeat offenders" for contacting many different solutes, which suggest modifications to reduce non-specific binding. These studies highlight how molecular dynamics can aid the design process of SAGE and similar assemblies for potential applications as diverse as platforms for drug and vaccine delivery and nanoreactors to encapsulate enzyme pathways.

Optimal Verification of Entangled States with Local Measurements.

Consider the task of verifying that a given quantum device, designed to produce a particular entangled state, does indeed produce that state. One natural approach would be to characterize the output state by quantum state tomography, or alternatively, to perform some kind of Bell test, tailored to the state of interest. We show here that neither approach is optimal among local verification strategies for 2-qubit states. We find the optimal strategy in this case and show that quadratically fewer total measurements are needed to verify to within a given fidelity than in published results for quantum state tomography, Bell test, or fidelity estimation protocols. We also give efficient verification protocols for any stabilizer state. Additionally, we show that requiring that the strategy be constructed from local, nonadaptive, and noncollective measurements only incurs a constant-factor penalty over a strategy without these restrictions.

Bioinspired Silicification Reveals Structural Detail in Self-Assembled Peptide Cages.

Understanding how molecules in self-assembled soft-matter nanostructures are organized is essential for improving the design of next-generation nanomaterials. Imaging these assemblies can be challenging and usually requires processing, e.g., staining or embedding, which can damage or obscure features. An alternative is to use bioinspired mineralization, mimicking how certain organisms use biomolecules to template mineral formation. Previously, we have reported the design and characterization of Self-Assembled peptide caGEs (SAGEs) formed from de novo peptide building blocks. In SAGEs, two complementary, 3-fold symmetric, peptide hubs combine to form a hexagonal lattice, which curves and closes to form SAGE nanoparticles. As hexagons alone cannot tile onto spheres, the network must also incorporate nonhexagonal shapes. While the hexagonal ultrastructure of the SAGEs has been imaged, these defects have not been observed. Here, we show that positively charged SAGEs biotemplate a thin, protective silica coating. Electron microscopy shows that these SiO2-SAGEs do not collapse, but maintain their 3D shape when dried. Atomic force microscopy reveals a network of hexagonal and irregular features on the SiO2-SAGE surface. The dimensions of these (7.2 nm ± 1.4 nm across, internal angles 119.8° ± 26.1°) are in accord with the designed SAGE network and with coarse-grained modeling of the SAGE assembly. The SiO2-SAGEs are permeable to small molecules (<2 nm), but not to larger biomolecules (>6 nm). Thus, bioinspired silicification offers a mild technique that preserves soft-matter nanoparticles for imaging, revealing structural details <10 nm in size, while also maintaining desirable properties, such as permeability to small molecules.

Beyond icosahedral symmetry in packings of proteins in spherical shells.

The formation of quasi-spherical cages from protein building blocks is a remarkable self-assembly process in many natural systems, where a small number of elementary building blocks are assembled to build a highly symmetric icosahedral cage. In turn, this has inspired synthetic biologists to design de novo protein cages. We use simple models, on multiple scales, to investigate the self-assembly of a spherical cage, focusing on the regularity of the packing of protein-like objects on the surface. Using building blocks, which are able to pack with icosahedral symmetry, we examine how stable these highly symmetric structures are to perturbations that may arise from the interplay between flexibility of the interacting blocks and entropic effects. We find that, in the presence of those perturbations, icosahedral packing is not the most stable arrangement for a wide range of parameters; rather disordered structures are found to be the most stable. Our results suggest that (i) many designed, or even natural, protein cages may not be regular in the presence of those perturbations and (ii) optimizing those flexibilities can be a possible design strategy to obtain regular synthetic cages with full control over their surface properties.

How Markovian is exciton dynamics in purple bacteria?

We investigate the extent to which the dynamics of excitons in the light-harvesting complex LH2 of purple bacteria can be described using a Markovian approximation. To analyse the degree of non-Markovianity in these systems, we introduce a measure based on fitting Lindblad dynamics, as well as employing a recently introduced trace-distance measure. We apply these measures to a chromophore-dimer model of exciton dynamics and use the hierarchical equation-of-motion method to take into account the broad, low-frequency phonon bath. With a smooth phonon bath, small amounts of non-Markovianity are present according to the trace-distance measure, but the dynamics is poorly described by a Lindblad master equation unless the excitonic dimer coupling strength is modified. Inclusion of underdamped, high-frequency modes leads to significant deviations from Markovian evolution in both measures. In particular, we find that modes that are nearly resonant with gaps in the excitonic spectrum produce dynamics that deviate most strongly from the Lindblad approximation, despite the trace distance measuring larger amounts of non-Markovianity for higher frequency modes. Overall we find that the detailed structure in the high-frequency region of the spectral density has a significant impact on the nature of the dynamics of excitons.

How Static Disorder Mimics Decoherence in Anisotropy Pump-Probe Experiments on Purple-Bacteria Light Harvesting Complexes.

Anisotropy pump-probe experiments have provided insights into the character of excitons formed in photosynthetic complexes. Rapid decay in the observed anisotropy is cited as evidence of the strength of coupling of the excitonic degrees of freedom to their environment. Here we show that ensemble averaging over realistic model Hamiltonians leads to a rapid decay of anisotropy to a value close to the observed asymptote, and at a rate comparable to observed decay rates, even in the absence of coupling to the environment. While coupling to the environment will clearly play a role in the dynamics of such systems, our calculations suggest that caution is needed in deducing the strength of this coupling from anisotropy experiments. We also set out to clarify the nature of the quantum states and processes involved in the dynamics of such systems and the associated terminology.

Local and macroscopic electrostatic interactions in single α-helices.

The noncovalent forces that stabilize protein structures are not fully understood. One way to address this is to study equilibria between unfolded states and α-helices in peptides. Electrostatic forces-which include interactions between side chains, the backbone and side chains, and side chains and the helix macrodipole-are believed to contribute to these equilibria. Here we probe these interactions experimentally using designed peptides. We find that both terminal backbone-side chain and certain side chain-side chain interactions (which include both local effects between proximal charges and interatomic contacts) contribute much more to helix stability than side chain-helix macrodipole electrostatics, which are believed to operate at larger distances. This has implications for current descriptions of helix stability, the understanding of protein folding and the refinement of force fields for biomolecular modeling and simulations. In addition, this study sheds light on the stability of rod-like structures formed by single α-helices, which are common in natural proteins such as non-muscle myosins.

Rapid spatial equilibration of a particle in a box.

We study the equilibration behavior of a quantum particle in a one-dimensional box, with respect to a coarse-grained position measurement (whether it lies in a certain spatial window or not). We show that equilibration in this context indeed takes place and does so very rapidly, in a time comparable to the time for the initial wave packet to reach the edges of the box. We also show that, for this situation, the equilibration behavior is relatively insensitive to the precise choice of position measurements or initial condition.

Quantum systems equilibrate rapidly for most observables.

Considering any Hamiltonian, any initial state, and measurements with a small number of possible outcomes compared to the dimension, we show that most measurements are already equilibrated. To investigate nontrivial equilibration, we therefore consider a restricted set of measurements. When the initial state is spread over many energy levels, and we consider the set of observables for which this state is an eigenstate, most observables are initially out of equilibrium yet equilibrate rapidly. Moreover, all two-outcome measurements, where one of the projectors is of low rank, equilibrate rapidly.

Entanglement enhances cooling in microscopic quantum refrigerators.

Small self-contained quantum thermal machines function without external source of work or control but using only incoherent interactions with thermal baths. Here we investigate the role of entanglement in a small self-contained quantum refrigerator. We first show that entanglement is detrimental as far as efficiency is concerned-fridges operating at efficiencies close to the Carnot limit do not feature any entanglement. Moving away from the Carnot regime, we show that entanglement can enhance cooling and energy transport. Hence, a truly quantum refrigerator can outperform a classical one. Furthermore, the amount of entanglement alone quantifies the enhancement in cooling.

Rapid resolution of psychotic symptoms in a patient with schizophrenia using allopurinol as an adjuvant: a case report.

CONTEXT: Despite multiple trials of different adjuvant therapies to an antipsychotic regimen, there have been few promising results. Allopurinol may be one promising adjunctive therapy based on three randomized controlled trials. OBJECTIVE: To determine whether adjuvant allopurinol would be beneficial to a patient already on multiple trials of antipsychotics with no improvement. RESULTS: Allopurinol was started with this particular patient who was on the inpatient unit for over three months with no prior improvement. Within two weeks of allopurinol adjuvant therapy, the patient showed significant improvement with regards to his positive and negative symptoms of schizophrenia (PANSS scores went from a score of 88 to a score of 41 two weeks later). CONCLUSIONS: Despite some limitations of this particular case report, it is possible that allopurinol can play an effective role as an adjuvant to antipsychotic regimens in reducing the symptoms of schizophrenia.

Connection between Bell nonlocality and Bayesian game theory.

In 1964, Bell discovered that quantum mechanics is a nonlocal theory. Three years later, in a seemingly unconnected development, Harsanyi introduced the concept of Bayesian games. Here we show that, in fact, there is a deep connection between Bell nonlocality and Bayesian games, and that the same concepts appear in both fields. This link offers interesting possibilities for Bayesian games, namely of allowing the players to receive advice in the form of nonlocal correlations, for instance using entangled quantum particles or more general no-signalling boxes. This will lead to novel joint strategies, impossible to achieve classically. We characterize games for which nonlocal resources offer a genuine advantage over classical ones. Moreover, some of these strategies represent equilibrium points, leading to the notion of quantum/no-signalling Nash equilibrium. Finally, we describe new types of question in the study of nonlocality, namely the consideration of nonlocal advantage given a set of Bell expressions.

Self-assembling cages from coiled-coil peptide modules.

An ability to mimic the boundaries of biological compartments would improve our understanding of self-assembly and provide routes to new materials for the delivery of drugs and biologicals and the development of protocells. We show that short designed peptides can be combined to form unilamellar spheres approximately 100 nanometers in diameter. The design comprises two, noncovalent, heterodimeric and homotrimeric coiled-coil bundles. These are joined back to back to render two complementary hubs, which when mixed form hexagonal networks that close to form cages. This design strategy offers control over chemistry, self-assembly, reversibility, and size of such particles.

Virtual qubits, virtual temperatures, and the foundations of thermodynamics.

We argue that thermal machines can be understood from the perspective of "virtual qubits" at "virtual temperatures": The relevant way to view the two heat baths which drive a thermal machine is as a composite system. Virtual qubits are two-level subsystems of this composite, and their virtual temperatures can take on any value, positive or negative. Thermal machines act upon an external system by placing it in thermal contact with a well-selected range of virtual qubits and temperatures. We demonstrate these claims by studying the smallest thermal machines. We show further that this perspective provides a powerful way to view thermodynamics, by analyzing a number of phenomena. This includes approaching Carnot efficiency (where we find that all machines do so essentially by becoming equivalent to the smallest thermal machines), entropy production in irreversible machines, and a way to view work in terms of negative temperature and population inversion. Moreover we introduce the idea of "genuine" thermal machines and are led to considering the concept of "strength" of work.

A de novo peptide hexamer with a mutable channel.

The design of new proteins that expand the repertoire of natural protein structures represents a formidable challenge. Success in this area would increase understanding of protein structure and present new scaffolds that could be exploited in biotechnology and synthetic biology. Here we describe the design, characterization and X-ray crystal structure of a new coiled-coil protein. The de novo sequence forms a stand-alone, parallel, six-helix bundle with a channel running through it. Although lined exclusively by hydrophobic leucine and isoleucine side chains, the 6-Å channel is permeable to water. One layer of leucine residues within the channel is mutable, accepting polar aspartic acid and histidine side chains, which leads to subdivision and organization of solvent within the lumen. Moreover, these mutants can be combined to form a stable and unique (Asp-His)(3) heterohexamer. These new structures provide a basis for engineering de novo proteins with new functions.