Mucus concentration-dependent biophysical abnormalities unify submucosal gland and superficial airway dysfunction in cystic fibrosis.

Cystic fibrosis (CF) is characterized by abnormal transepithelial ion transport. However, a description of CF lung disease pathophysiology unifying superficial epithelial and submucosal gland (SMG) dysfunctions has remained elusive. We hypothesized that biophysical abnormalities associated with CF mucus hyperconcentration provide a unifying mechanism.

High Level Electronic Structure Calculation of Molecular Solid-State NMR Shielding Constants.

In this work, we present a quantum mechanics/molecular mechanics (QM/MM) approach for the computation of solid-state nuclear magnetic resonance (SS-NMR) shielding constants (SCs) for molecular crystals. Besides applying standard-DFT functionals like GGAs (PBE), meta-GGAs (TPSS), and hybrids (B3LYP), we apply a double-hybrid (DSD-PBEP86) functional as well as MP2, using the domain-based local pair natural orbital (DLPNO) formalism, to calculate the NMR SCs of six amino acid crystals. All the electronic structure methods used exhibit good correlation of the NMR shieldings with respect to experimental chemical shifts for both H and C.

DLPNO-MP2 second derivatives for the computation of polarizabilities and NMR shieldings.

We present a derivation and efficient implementation of the formally complete analytic second derivatives for the domain-based local pair natural orbital second order Møller-Plesset perturbation theory (MP2) method, applicable to electric or magnetic field-response properties but not yet to harmonic frequencies. We also discuss the occurrence and avoidance of numerical instability issues related to singular linear equation systems and near linear dependences in the projected atomic orbital domains. A series of benchmark calculations on medium-sized systems is performed to assess the effect of the local approximation on calculated nuclear magnetic resonance shieldings and the static dipole polarizabilities.

Molecular Characterization of Polymer Networks.

Polymer networks are complex systems consisting of molecular components. Whereas the properties of the individual components are typically well understood by most chemists, translating that chemical insight into polymer networks themselves is limited by the statistical and poorly defined nature of network structures. As a result, it is challenging, if not currently impossible, to extrapolate from the molecular behavior of components to the full range of performance and properties of the entire polymer network.

Computation of NMR Shielding Constants for Solids Using an Embedded Cluster Approach with DFT, Double-Hybrid DFT, and MP2.

In this work, we explore the accuracy of post-Hartree-Fock (HF) methods and double-hybrid density functional theory (DFT) for the computation of solid-state NMR chemical shifts. We apply an embedded cluster approach and investigate the convergence with cluster size and embedding for a series of inorganic solids with long-range electrostatic interactions. In a systematic study, we discuss the cluster design, the embedding procedure, and basis set convergence using gauge-including atomic orbital (GIAO) NMR calculations at the DFT and MP2 levels of theory.

Efficient and Accurate Prediction of Nuclear Magnetic Resonance Shielding Tensors with Double-Hybrid Density Functional Theory.

Analytic calculation of nuclear magnetic resonance chemical shielding tensors, based on gauge-including atomic orbitals, is implemented for double-hybrid density functional theory (DHDFT), using the resolution of the identity (RI) approximation for its second order Møller-Plesset perturbation theory (MP2) correlation contributions. A benchmark set of 15 small molecules, containing H, C, N, O, F, and P nuclei, is used to assess the accuracy of the results in comparison to coupled cluster and empirical equilibrium reference data, as well as to calculations with MP2, Hartree-Fock, and commonly used pure and hybrid density functionals. Investigated are also errors due to basis set incompleteness, the frozen core approximation, different auxiliary basis sets for the RI approximation, and grids used for the chain-of-spheres exchange integral evaluation.

Self-Consistent Field Calculation of Nuclear Magnetic Resonance Chemical Shielding Constants Using Gauge-Including Atomic Orbitals and Approximate Two-Electron Integrals.

The chain-of-spheres method (COS) for approximating two-electron integrals is applied to Hartree-Fock and density functional theory calculations of nuclear magnetic resonance chemical shielding tensors, based on gauge-including atomic orbitals. The accuracy of the approximation is compared to that of the resolution of the identity (RI) approach, using a benchmark test set of 15 small molecules. Reasonable auxiliary basis sets and grid sizes are selected on the basis of a careful investigation of how approximating each of the two-electron terms in the self-consistent field (SCF) and coupled perturbed SCF equations affects the calculated shielding constants.

4D Biofabrication Using Shape-Morphing Hydrogels.

Despite the tremendous potential of bioprinting techniques toward the fabrication of highly complex biological structures and the flourishing progress in 3D bioprinting, the most critical challenge of the current approaches is the printing of hollow tubular structures. In this work, an advanced 4D biofabrication approach, based on printing of shape-morphing biopolymer hydrogels, is developed for the fabrication of hollow self-folding tubes with unprecedented control over their diameters and architectures at high resolution. The versatility of the approach is demonstrated by employing two different biopolymers (alginate and hyaluronic acid) and mouse bone marrow stromal cells.

Porous Stimuli-Responsive Self-Folding Electrospun Mats for 4D Biofabrication.

We report fabrication and characterization of electrospun, porous multi-layer scaffolds based-on thermo-responsive polymers polycaprolactone (PCL) and poly(N-isopropylacrylamide). We found that the electrospun mats fold into various 3D structures in an aqueous environment at different temperatures. We could determine the mechanism behind different folding behaviors under different conditions by consideration of the properties of the individual polymers.

4D Origami by Smart Embroidery.

There exist many methods for processing of materials: extrusion, injection molding, fibers spinning, 3D printing, to name a few. In most cases, materials with a static, fixed shape are produced. However, numerous advanced applications require customized elements with reconfigurable shape.

Automatic Generation of Auxiliary Basis Sets.

A procedure was developed to automatically generate auxiliary basis sets (ABSs) for use with the resolution of the identity (RI) approximation, starting from a given orbital basis set (OBS). The goal is to provide an accurate and universal solution for cases where no optimized ABSs are available. In this context, "universal" is understood as the ability of the ABS to be used for Coulomb, exchange, and correlation energy fitting.

Reversibly Actuating Solid Janus Polymeric Fibers.

It is commonly assumed that the substantial element of reversibly actuating soft polymeric materials is chemical cross-linking, which is needed to provide elasticity required for the reversible actuation. On the example of melt spun and three-dimensional printed Janus fibers, we demonstrate here for the first time that cross-linking is not an obligatory prerequisite for reversible actuation of solid entangled polymers, since the entanglement network itself can build elasticity during crystallization. Indeed, we show that not-cross-linked polymers, which typically demonstrate plastic deformation in melt, possess enough elastic behavior to actuate reversibly.

Controlled Retention and Release of Biomolecular Transport Systems Using Shape-Changing Polymer Bilayers.

Biomolecular transport systems based on cytoskeletal filaments and motor proteins have become promising tools for a wide range of nanotechnological applications. In this paper, we report control of such transport systems using substrates with switchable shape. We demonstrate this approach on the example of microtubules gliding on surfaces of self-folding polymer bilayers with adsorbed kinesin motors.

Actuating Fibers: Design and Applications.

Actuators are devices capable of moving or controlling objects and systems by applying mechanical force on them. Among all kinds of actuators with different shapes, fibrous ones deserve particular attention. In spite of their apparent simplicity, actuating fibers allow for very complex actuation behavior.

Programmed assembly of oppositely charged homogeneously decorated and Janus particles.

The exploitation of colloidal building blocks with morphological and functional anisotropy facilitates the generation of complex structures with unique properties, which are not exhibited by isotropic particle assemblies. Herein, we demonstrate an easy and scalable bottom-up approach for the programmed assembly of hairy oppositely charged homogeneously decorated and Janus particles based on electrostatic interactions mediated by polyelectrolytes grafted onto their surface. Two different assembly routes are proposed depending on the target structures: raspberry-like/half-raspberry-like or dumbbell-like micro-clusters.

Coil-like Enzymatic Biohybrid Structures Fabricated by Rational Design: Controlling Size and Enzyme Activity over Sequential Nanoparticle Bioconjugation and Filtration Steps.

Well-defined enzymatic biohybrid structures (BHS) composed of avidin, biotinylated poly(propyleneimine) glycodendrimers, and biotinylated horseradish peroxidase were fabricated by a sequential polyassociation reaction to adopt directed enzyme prodrug therapy to protein-glycopolymer BHS for potential biomedical applications. To tailor and gain fundamental insight into pivotal properties such as size and molar mass of these BHS, the dependence on the fabrication sequence was probed and thoroughly investigated by several complementary methods (e.g.

Electron beam-induced formation of crystalline nanoparticle chains from amorphous cadmium hydroxide nanofibers.

Quantum dots (QDs) and especially quantum dot arrays have been attracting tremendous attention due to their potential applications in various high-tech devices, including QD lasers, solar cells, single photon emitters, QD memories, etc. Here, a dendrimer-based approach for the controlled synthesis of ultra-thin amorphous cadmium hydroxide nanofibers was developed. The fragmentation of the obtained nanofibers in crystalline nanoparticle chains under the irradiation with electron beam was observed in both ambient and cryo-conditions.

Hybrid Hairy Janus Particles Decorated with Metallic Nanoparticles for Catalytic Applications.

We report for the first time on the design of an advanced hairy hybrid Janus-type catalyst, which is comprised of an inorganic silica core covered with two distinct polymeric shells (hydrophilic and hydrophobic) on its opposite sides, while the catalytic species (in our case silver or gold nanoparticles) are immobilized directly into the hydrophilic stimuli-responsive polymer shell. The primary 200 nm large Janus particles with poly(acrylic acid) serving as the hydrophilic and polystyrene as the hydrophobic polymer were synthesized through a Pickering emulsion and a combination of "grafting from"/"grafting to" approaches. The incorporation of silver and gold nanoparticles within the hydrophilic polymer shell was achieved by infiltrating the respective metal ions into the polymer matrix, and nanoparticles were formed upon the addition of a reducing agent (triethylamine).

Self-assembly behavior of hairy colloidal particles with different architectures: mixed versus janus.

In this paper, we investigated the aggregation and assembly behavior of hairy core-shell particles with different architectures consisting of a hard silica core and soft polymer brush shells. We varied the nature of the polymers which form the shell: we used different hydrophilic positively (poly(2-(dimethylamino)ethyl methacrylate), PDMAEMA) and negatively (poly(acrylic acid), PAA) charged polymers, uncharged hydrophilic (polyethylene glycol, PEG) polymers, and hydrophobic (poly(lauryl methacrylate), PLMA; polystyrene, PS) polymers. We synthesized particles covered by polymer of one sort (homogeneously coated particles) as well as Janus particles (two polymers are grafted to the opposite sides of the core) and investigated/compared the aggregation behavior of different fully covered particles, their mixtures, and Janus particles.

Platelet Janus particles with hairy polymer shells for multifunctional materials.

A novel approach is developed for the large-scale synthesis of Janus particles with platelet geometry and dense polymer shells by employing simultaneous "grafting from" of hydrophilic and hydrophobic polymers using surface-induced ATRP in emulsion. The method is based on the fabrication of an emulsion consisting of a water solution of a hydrophilic monomer and a solution of a hydrophobic monomer in an organic solvent, which is stabilized by initiator-modified kaolinite particles. Two polymers are grafted simultaneously on the opposite faces of the kaolinite particle during polymerization.

Stimuli-responsive microjets with reconfigurable shape.

Flexible thermoresponsive polymeric microjets are formed by the self-folding of polymeric layers containing a thin Pt film used as catalyst for self-propulsion in solutions containing hydrogen peroxide. The flexible microjets can reversibly fold and unfold in an accurate manner by applying changes in temperature to the solution in which they are immersed. This effect allows microjets to rapidly start and stop multiple times by controlling the radius of curvature of the microjet.

Highly efficient phase boundary biocatalysis with enzymogel nanoparticles.

The enzymogel nanoparticle made of a magnetic core and polymer brush shell demonstrates a novel type of remote controlled phase-boundary biocatalysis that involves remotely directed binding to and engulfing insoluble substrates, high mobility, and stability of the catalytic centers. The mobile enzymes reside in the polymer brush scaffold and shuttle between the enzymogel interior and surface of the engulfed substrate in the bioconversion process. Biocatalytic activity of the mobile enzymes is preserved in the enzymogel while the brush-like architecture favors the efficient interfacial interaction when the enzymogel spreads over the substrate and extends substantially the reaction area as compared with rigid particles.

Stimuli-responsive hierarchically self-assembled 3D porous polymer-based structures with aligned pores.

We have developed a novel approach for the fabrication of self-assembled porous materials with uniaxial tubular pores. The approach is based on the use of microtubes formed by stimuli-induced rolling of polymer bilayers consisting of hydrophobic and stimuli-responsive hydrophilic polymers. Different objects, for example yeast cells, can be encapsulated inside the tubes during their rolling.

Shape-programmed folding of stimuli-responsive polymer bilayers.

We investigated the folding of rectangular stimuli-responsive hydrogel-based polymer bilayers with different aspect ratios and relative thicknesses placed on a substrate. It was found that long-side rolling dominates at high aspect ratios (ratio of length to width) when the width is comparable to the circumference of the formed tubes, which corresponds to a small actuation strain. Rolling from all sides occurs for higher actuation, namely when the width and length considerably exceed the deformed circumference.