Swelling and Orientation Behavior of End-Grafted Polymer Chains by In Situ Attenuated Total Reflection Fourier Transform Infrared Spectroscopy Complementing In Situ Ellipsometry.

The literature lacks established concrete parameters for assigning grafted chain regimes. In this context, dichroic in situ attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy and in situ ellipsometry were used complementarily, offering new opportunities for conformational analysis of end-grafted polymer chains. Especially polymer chain orientation was studied as a new parameter, among others, for proper chain regime assignment in this report. Alkyne-functionalized poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) with a molecular weight of 49.8 kg/mol and a contour length of around 80 nm was grafted to self-assembled monolayers bearing triazole end groups as reported. Different chain regimes were generated by using three different grafting densities. ATR-FTIR spectroscopy based on the ν(C═O) stretching vibration at around 1728 cm-1 provided a new direct approach to determine the GD of polymer chains. Significant shifts in the position of the ν(C═O) band comparing dry and wet states were observed, caused by increased hydrogen bonding interactions between PDMAEMA and water. Finally, the averaged orientation of PDMAEMA chains along the z-axis was determined using dichroic ATR-FTIR spectroscopy based on the dichroic ratios of the ν(C═O) band and molecular order parameters SZ,MOL calculated thereof. High SZ,MOL values were found for the wet state compared to the dry state, confirming that all GD PDMAEMA samples are in the brush regime in the swollen state.

Polarity and functionality tailored conjugated microporous polymer coatings on silica microspheres for enhanced pollutant adsorption.

Many sources of pollution that are generated by modern society are not addressable by conventional methods. Especially organic compounds, like pharmaceutics, are particularly hard to remove from waterbodies. Herein, a new approach is presented using conjugated microporous polymers (CMPs) to coat silica microparticles yielding specifically tailored adsorbents. The CMPs are generated with three different monomers: 2,6-dibromonaphthalene (DBN), 2,5-dibromoaniline (DBA) and 2,5-dibromopyridine (DBPN) respectively coupled to 1,3,5-triethynylbenzene (TEB) via Sonogashira coupling. By optimizing the polarity of the silica surface, all three CMPs were converted into microparticle coatings. The resulting hybrid materials feature the advantages of being adjustable in polarity and functionality, as well as morphology. Sedimentation allows facile removal of the coated microparticles after the adsorption. Further, the expansion of the CMP to a thin coating increases the accessible surface area compared to the bulk material. These effects were demonstrated by the adsorption of the model drug diclofenac. Thereby, the aniline-based CMP proved to be most advantageous due to a secondary crosslinking mechanism of amino and alkyne functionalities. An outstanding adsorption capacity of 228 mg diclofenac per gram of the aniline CMP within the hybrid material was achieved. This represents a five-fold increase compared to the value obtained by the pure CMP material underlining the advantages of the hybrid material.

STM-induced ring closure of vinylheptafulvene molecular dipole switches on Au(111).

Dihydroazulene/vinylheptafulvene pairs are known as molecular dipole switches that undergo a ring-opening/-closure reaction by UV irradiation or thermal excitation. Herein, we show that the ring-closure reaction of a single vinylheptafulvene adsorbed on the Au(111) surface can be induced by voltage pulses from the tip of a scanning tunneling microscope. This cyclization is accompanied by the elimination of HCN, as confirmed by simulations. When inducing lateral movements by applying voltage pulses with the STM tip, we observe that the response of the single molecules changes with the ring closing reaction. This behaviour is discussed by comparing the dipole moment and the charge distribution of the open and closed forms on the surface.

Spiropyran/Merocyanine Amphiphile in Various Solvents: A Joint Experimental-Theoretical Approach to Photophysical Properties and Self-Assembly.

This joint experimental-theoretical work focuses on molecular and photophysical properties of the spiropyran-containing amphiphilic molecule in organic and aqueous solutions. Being dissolved in tested organic solvents, the system demonstrates positive photochromism, i.e., upon UV stimulus the colorless spiropyran form is transformed into colorful merocyanine isomer. However, the aqueous solution of the amphiphile possesses a negative photochromism: the orange-red merocyanine form becomes thermodynamically more stable in water, and both UV and vis stimuli lead to the partial or complete photobleaching of the solution. The explanation of this phenomenon is given on the basis of density functional theory calculations and classical modeling including thermodynamic integration. The simulations reveal that stabilization of merocyanine in water proceeds with the energy of ca. 70 kJ mol-1, and that the Helmholtz free energy of hydration of merocyanine form is 100 kJ mol-1 lower as compared to the behavior of SP isomer in water. The explanation of such a difference lies in the molecular properties of the merocyanine: after ring-opening reaction this molecule transforms into a zwitterionic form, as evidenced by the electrostatic potential plotted around the opened form. The presence of three charged groups on the periphery of a flat conjugated backbone stimulates the self-assembly of merocyanine molecules in water, ending up with the formation of elongated associates with stack-like building blocks, as shown in molecular dynamics simulations of the aqueous solution with the concentration above critical micelle concentration. Our quantitative evaluation of the hydrophilicity switching in spiropyran/merocyanine containing surfactants may prompt the search for new systems, including colloidal and polymeric ones, aiming at remote tuning of their morphology, which could give new promising shapes and patterns for the needs of modern nanotechnology.

Charge-Compensated N-Doped π-Conjugated Polymers: Toward both Thermodynamic Stability of N-Doped States in Water and High Electron Conductivity.

The understanding and applications of electron-conducting π-conjugated polymers with naphtalene diimide (NDI) blocks show remarkable progress in recent years. Such polymers demonstrate a facilitated n-doping due to the strong electron deficiency of the main polymer chain and the presence of the positively charged side groups stabilizing a negative charge of the n-doped backbone. Here, the n-type conducting NDI polymer with enhanced stability of its n-doped states for prospective "in-water" applications is developed. A combined experimental-theoretical approach is used to identify critical features and parameters that control the doping and electron transport process. The facilitated polymer reduction ability and the thermodynamic stability in water are confirmed by electrochemical measurements and doping studies. This material also demonstrates a high conductivity of 10-2  S cm-1  under ambient conditions and 10-1  S cm-1  in vacuum. The modeling explains the stabilizing effects  for various dopants. The simulations show a significant doping-induced "collapse" of the positively charged side chains on the core bearing a partial negative charge. This explains a decrease in the lamellar spacing observed in experiments. This study fundamentally enables a novel pathway for achieving both thermodynamic stability of the n-doped states in water and the high electron conductivity of polymers.

Association between anxiety and mortality in patients with congestive heart failure after implantation of cardiac electronic devices.

OBJECTIVE: Several studies suggest that psychological factors including anxiety are associated with negative outcomes and in particular higher mortality rates among heart failure (HF) patients. However, the impact of anxiety on mortality in patients with implanted cardiac devices has not been fully appreciated. The aim of this study was to assess the association between state (SA) and trait (TA) anxiety and all-cause mortality in patients with HF after cardiac electronic devices implantation. METHODS: The monocentric prospective study enrolled 265 patients (215 men and 50 women) aged 23 to 84 years (mean age 57.1 ± 10.0), who received cardiac resynchronization therapy or cardioverter-defibrillator implantation. Mean duration of prospective follow-up was 62.3 ± 36.6 months. State-Trait Anxiety Inventory (STAI) was used to measure anxiety symptoms. Cox proportional hazards multivariate regression model was used to calculate hazard ratio (HR) of all-cause mortality with 95% confidence interval (95% CI). RESULTS: During the prospective follow-up period, 45 (17.0%) patients died due to all causes. According to quantitative analysis, HR for death used for SA scale was 1.04 (95% CI 1.00-1.07, p = 0.07) and for the TA scale 1.02 (95% CI 0.99-1.05, p = 0.21). Analysis of categorical indicators found statistically significant higher HR of mortality in patients with severe SA (2.35, 95% CI 1.17-4.71, p = 0.02), and TA (2.02, 95% CI 1.04-3.94, p = 0.04). CONCLUSION: High levels of SA and TA was significantly and independently associated with a high risk of all-cause mortality in patients, who underwent implantation of cardiac electronic devices.

Columnar Aggregates of Azobenzene Stars: Exploring Intermolecular Interactions, Structure, and Stability in Atomistic Simulations.

We present a simulation study of supramolecular aggregates formed by three-arm azobenzene (Azo) stars with a benzene-1,3,5-tricarboxamide (BTA) core in water. Previous experimental works by other research groups demonstrate that such Azo stars assemble into needle-like structures with light-responsive properties. Disregarding the response to light, we intend to characterize the equilibrium state of this system on the molecular scale. In particular, we aim to develop a thorough understanding of the binding mechanism between the molecules and analyze the structural properties of columnar stacks of Azo stars. Our study employs fully atomistic molecular dynamics (MD) simulations to model pre-assembled aggregates with various sizes and arrangements in water. In our detailed approach, we decompose the binding energies of the aggregates into the contributions due to the different types of non-covalent interactions and the contributions of the functional groups in the Azo stars. Initially, we investigate the origin and strength of the non-covalent interactions within a stacked dimer. Based on these findings, three arrangements of longer columnar stacks are prepared and equilibrated. We confirm that the binding energies of the stacks are mainly composed of π-π interactions between the conjugated parts of the molecules and hydrogen bonds formed between the stacked BTA cores. Our study quantifies the strength of these interactions and shows that the π-π interactions, especially between the Azo moieties, dominate the binding energies. We clarify that hydrogen bonds, which are predominant in BTA stacks, have only secondary energetic contributions in stacks of Azo stars but remain necessary stabilizers. Both types of interactions, π-π stacking and H-bonds, are required to maintain the columnar arrangement of the aggregates.

Cyclic Photoisomerization of Azobenzene in Atomistic Simulations: Modeling the Effect of Light on Columnar Aggregates of Azo Stars.

This computational study investigates the influence of light on supramolecular aggregates of three-arm azobenzene stars. Every star contains three azobenzene (azo) moieties, each able to undergo reversible photoisomerization. In solution, the azo stars build column-shaped supramolecular aggregates. Previous experimental works report severe morphological changes of these aggregates under UV-Vis light. However, the underlying molecular mechanisms are still debated. Here we aim to elucidate how light affects the structure and stability of the columnar stacks on the molecular scale. The system is investigated using fully atomistic molecular dynamics (MD) simulations. To implement the effects of light, we first developed a stochastic model of the cyclic photoisomerization of azobenzene. This model reproduces the collective photoisomerization kinetics of the azo stars in good agreement with theory and previous experiments. We then apply light of various intensities and wavelengths on an equilibrated columnar stack of azo stars in water. The simulations indicate that the aggregate does not break into separate fragments upon light irradiation. Instead, the stack develops defects in the form of molecular shifts and reorientations and, as a result, it eventually loses its columnar shape. The mechanism and driving forces behind this order-disorder structural transition are clarified based on the simulations. In the end, we provide a new interpretation of the experimentally observed morphological changes.

Searching for Aquamelt Behavior among Silklike Biomimetics during Fibrillation under Flow.

In this paper, we elucidate a generic mechanism behind strain-induced phase transition in aqueous solutions of silk-inspired biomimetics by atomistic molecular dynamics simulations. We show the results of modeling of homopeptides polyglycine Gly30 and polyalanine Ala30 and a heteropeptide (Gly-Ala-Gly-Ala-Gly-Ser)5, i.e., the simplest and yet relevant sequences that could mimic the behavior of natural silk under stress conditions. First, we analyze hydrophobicities of the sequences by calculating the Gibbs free energy of hydration and inspecting the interchain hydrogen bonding and hydration by water. Second, the force-extension profiles are scanned and compared with the results for poly(ethylene oxide), the synthetic polymer for which the aquamelt behavior has been proved recently. Additionally, the conformational transitions of oligopeptides from coiled to extended states are characterized by a generalized order parameter and by the dependence of the solvent-accessible surface area of the chains on applied stretching. Fibrillation itself is surveyed using both the two-dimensional interchain pair correlation function and the SAXS/WAXS patterns for the aggregates formed under stress. These are compared with experimental data found in the literature on fibril structure of silk composite materials doped with oligoalanine peptides. Our results show that tensile stress introduced into aqueous oligopeptide solutions facilitates interchain interactions. The oligopeptides display both a greater resistance to extension as compared to poly(ethylene oxide) and a reduced ability for hydrogen bonding of the stretched chains between oligomers and with water. Fiber formation is proved for all simulated objects, but the most structured one is made of a heteropeptide (Gly-Ala-Gly-Ala-Gly-Ser)5: For this sequence, we obtain the highest degree of the secondary structure motifs in the fiber. We conclude that this is the most promising candidate among considered sequences to find the aquamelt behavior in further experimental studies.

Flow-Induced Formation of Thin PEO Fibers in Water and Their Stability After the Strain Release.

Recently, we have shown that a tensile stress applied to chains of poly(ethylene oxide) (PEO) in water reduces the solubility and leads to phase separation of PEO chains from water with the formation of a two-phase region. In this work, we further elucidate the generic mechanism behind strain-induced phase transitions in aqueous PEO solutions with concentrations of 50-60 wt % by performing all-atom molecular dynamics simulations. In particular, we study the stability of oriented PEO fibers after removing stretching forces. We found that the size of the PEO bundle increased with time, which is associated with the dissolution of PEO chains on the fiber surface due to the reformation of hydrogen bonds between the outer PEO molecules and water. For precise characterization of the fibers, the scattering patterns (small- and wide-angle X-ray spectra) for configurations taken at different relaxation times are calculated. The tendency of the oligomer chains to be peeled off from the surface of the bundle eventually might lead to a complete dissolution of the PEO fiber. We conclude that either entanglement constraints or a quick drying process are necessary to conserve the fiber structure in a quiescent state. The scattering results show that external strain induced a liquid-liquid phase separation first. On long time scales, this can be a precursor for crystallization of the fiber.

Stacks of Azobenzene Stars: Self-Assembly Scenario and Stabilising Forces Quantified in Computer Modelling.

In this paper, the columnar supramolecular aggregates of photosensitive star-shaped azobenzenes with benzene-1,3,5-tricarboxamide core and azobenzene arms are analyzed theoretically by applying a combination of computer simulation techniques. Without a light stimulus, the azobenzene arms adopt the trans-state and build one-dimensional columns of stacked molecules during the first stage of the noncovalent association. These columnar aggregates represent the structural elements of more complex experimentally observed morphologies-fibers, spheres, gels, and others. Here, we determine the most favorable mutual orientations of the trans-stars in the stack in terms of (i) the π - π distance between the cores lengthwise the aggregate, (ii) the lateral displacements due to slippage and (iii) the rotation promoting the helical twist and chirality of the aggregate. To this end, we calculate the binding energy diagrams using density functional theory. The model predictions are further compared with available experimental data. The intermolecular forces responsible for the stability of the stacks in crystals are quantified using Hirshfeld surface analysis. Finally, to characterize the self-assembly mechanism of the stars in solution, we calculate the hydrogen bond lengths, the normalized dipole moments and the binding energies as functions of the columnar length. For this, molecular dynamics trajectories are analyzed. Finally, we conclude about the cooperative nature of the self-assembly of star-shaped azobenzenes with benzene-1,3,5-tricarboxamide core in aqueous solution.

Do Columns of Azobenzene Stars Disassemble under Light Illumination?

The clustering properties of star-shaped molecules comprising three photochromic azobenzene-containing arms are investigated with specific focus on the influence of light on these structures. Previous experimental works report self-assembly of azobenzene stars in aqueous solution into long columnar clusters that are detectable using optical microscopy. These clusters appear to vanish under UV irradiation, which is known to induce trans-to-cis photoisomerization of the azobenzene groups. We have performed MD simulations, density functional theory, and density functional tight binding calculations to determine conformational properties and binding energies of these clusters. Our simulation data suggest that the binding strength of the clusters is large enough to prevent a breaking along their main axis. We conclude that very likely other mechanisms lead to the apparent disappearance of the clusters.

A comparative analysis of symmetric diketopyrrolopyrrole-cored small conjugated molecules with aromatic flanks: From geometry to charge transport.

Diketopyrrolopyrrole (DPP) derivatives are promising compounds for application in organic electronics. Here, we investigate several symmetrical N-unsubstituted and N-methyl substituted DPPs which differ in the heteroatom in the aromatic flanks. The conformational, electronic, and optical properties are characterized for single molecules in vacuum or a solvent. The intermolecular interactions are evaluated for interacting dimers. Here, a number of stacking geometries is tested, and dimers with mutual orientation of the molecules corresponding to the minimal binding energies are determined. The predicted charge carrier mobilities for stacks having minimal binding energies corroborate experimentally measured values. We conclude that DFT prediction of such stacks is a promising and computationally inexpensive approach to a rough estimation of transport properties. Additionally, the super-cell of the experimentally resolved crystal structure is used to study the dynamics and to compute the charge transport along the hopping pathways. We discuss obtained high mobilities and relate them to the symmetry of DPP core. © 2018 Wiley Periodicals, Inc.

Bioinspired thermoresponsive nanoscaled coatings: Tailor-made polymer brushes with bioconjugated arginine-glycine-aspartic acid-peptides.

The development of bioengineered surface coatings with stimuli-responsive properties is beneficial for a number of biomedical applications. Environmentally responsive and switchable polymer brush systems have a great potential to create such smart biointerfaces. This study focuses on the bioconjugation of cell-instructive peptides, containing the arginine-glycine-aspartic acid tripeptide sequence (RGD motif), onto well-defined polymer brush films. Herein, the highly tailored end-grafted homo polymer brushes are either composed of the polyelectrolyte poly(acrylic) acid (PAA), providing the reactive carboxyl functionalities, or of the temperature-responsive poly(N-isopropylacrylamide) (PNIPAAm). Of particular interest is the preparation of grafted-to binary brushes using both polymers and their subsequent conversion to RGD-biofunctionalized PNIPAAm-PAA binary brushes by a carbodiimide conjugation method. The bioconjugation process of two linear RGD-peptides Gly-Arg-Gly-Asp-Ser and Gly-Arg-Gly-Asp-Ser-Pro-Lys and one cyclic RGD-peptide cyclo(Arg-Gly-Asp-D-Tyr-Lys) is comparatively investigated by complementary analysis methods. Both techniques, in situ attenuated total reflectance Fourier transform infrared spectroscopy measurements and the in situ spectroscopic ellipsometric analysis, describe changes of the brush surface properties due to biofunctionalization. Besides, the bound RGD-peptide amount is quantitatively evaluated by ellipsometry in comparison to high performance liquid chromatography analysis data. Additionally, molecular dynamic simulations of the RGD-peptides themselves allow a better understanding of the bioconjugation process depending on the peptide properties. The significant influence on the bioconjugation result can be derived, on the one hand, of the polymer brush composition, especially from the PNIPAAm content, and, on the other hand, of the peptide dimension and its reactivity.

Light-Induced Deformation of Azobenzene-Containing Colloidal Spheres: Calculation and Measurement of Opto-Mechanical Stresses.

We report on light-induced deformation of colloidal spheres consisting of azobenzene-containing polymers. The colloids of the size between 60 nm and 2 µm in diameter were drop casted on a glass surface and irradiated with linearly polarized light. It was found that colloidal particles can be deformed up to ca. 6 times of their initial diameter. The maximum degree of deformation depends on the irradiation wavelength and intensity, as well as on colloidal particles size. On the basis of recently proposed theory by Toshchevikov et al. [ J. Phys. Chem. Lett. 2017 , 8 , 1094 ], we calculated the opto-mechanical stresses (ca. 100 MPa) needed for such giant deformations and compared them with the experimental results.

Photosensitive Cationic Azobenzene Surfactants: Thermodynamics of Hydration and the Complex Formation with Poly(methacrylic acid).

In this computational work, we investigate the photosensitive cationic surfactants with the trimethylammonium or polyamine hydrophilic head and the azobenzene-containing hydrophobic tail. The azobenzene-based molecules are known to undergo a reversible trans-cis-trans isomerization reaction when subjected to UV-visible light irradiation. Combining the density functional theory and the all-atom molecular dynamics simulations, the structural and the hydration properties of the trans- and the cis-isomers and their interaction with the oppositely charged poly(methacrylic acid) in aqueous solution are investigated. We establish and quantify the correlations of the molecular structure and the isomerization state of the surfactants and their hydrophilicity/hydrophobicity and the self-assembling altered by light. For this reason, we compare the hydration free energies of the trans- and the cis-isomers. Moreover, the investigations of the interaction strength between the azobenzene molecules and the polyanion provide additional elucidations of the recent experimental and theoretical studies on the light triggered reversible deformation behavior of the microgels and the polymer brushes loaded with azobenzene surfactants.

Photoisomers of Azobenzene Star with a Flat Core: Theoretical Insights into Multiple States from DFT and MD Perspective.

This study focuses on comparing physical properties of photoisomers of an azobenzene star with benzene-1,3,5-tricarboxamide core. Three azobenzene arms of the molecule undergo a reversible trans-cis isomerization upon UV-vis light illumination giving rise to multiple states from the planar all-trans one, via two mixed states to the kinked all-cis isomer. Employing density functional theory, we characterize the structural and photophysical properties of each state indicating a role the planar core plays in the coupling between azobenzene chromophores. To characterize the light-triggered switching of solvophilicity/solvophobicity of the star, the difference in solvation free energy is calculated for the transfer of an azobenzene star from its gas phase to implicit or explicit solvents. For the latter case, classical all-atom molecular dynamics simulations of aqueous solutions of azobenzene star are performed employing the polymer consistent force field to shed light on the thermodynamics of explicit hydration as a function of the isomerization state and on the structuring of water around the star. From the analysis of two contributions to the free energy of hydration, the nonpolar van der Waals and the electrostatic terms, it is concluded that isomerization specificity largely determines the polarity of the molecule and the solute-solvent electrostatic interactions. This convertible hydrophilicity/hydrophobicity together with readjustable occupied volume and the surface area accessible to water, affects the self-assembly/disassembly of the azobenzene star with a flat core triggered by light.

Charge carrier mobility in one-dimensional aligned π-stacks of conjugated small molecules with a benzothiadiazole central unit.

A theoretical study is applied to gain insight into the microscopic electron and hole transport in benzothiadiazole-cored molecular semiconductors either with furan or thiophene flanks arranged in π-stacks. For the characterization of the energetics of the reduction and oxidation processes and their impact on the molecular geometry, the internal reorganization energy is defined for isolated molecules in the gas phase. The outer-shell reorganization energy is evaluated within the frequency-resolved cavity model and as an electrostatic contribution within the polarizable continuum model. The intermolecular electronic coupling interaction for the Marcus charge hopping is calculated using the energy splitting in dimer method, the generalized Mulliken-Hush approach and the fragment charge difference scheme. In order to probe the relation between the charge hopping rate/charge carrier mobility and the molecular organization within the π-stacks, different stacking modes are investigated: (i) dimers with a perfect registry, i.e. segregated stacking motif, when molecules are placed face-to-face, and (ii) dimers forming slipped cofacial orientations with longitudinal and transverse shifts, i.e. mixed stacking motif. Besides, the effects of molecular planarity and rigidity, influencing internal molecular relaxation upon charging, the effects of non-covalent interactions within stacks and the heteroatom replacement on the charge carrier mobility are studied. The results obtained in the simulations of one-dimensional aligned π-stacks of molecular semiconductors are compared with available experimental data for small conjugated benzothiadiazole-cored molecules with thiophene flanks and benzothiadiazole-quaterthiophene-based copolymers.

Tunneling spectroscopy measurements on hydrogen-bonded supramolecular polymers.

We studied the formation of hydrogen-bonded supramolecular polymers of Ethyl Hexyl Urea Toluene (EHUT) on a gold (111) surface by low temperature scanning tunneling microscopy. Tunneling spectroscopy performed along an individual molecule embedded in a self-assembled layer revealed strong changes in the value of the HOMO-LUMO gap. A variation of the LUMO state is attributed to the effect of space charge accumulation resulting from anisotropic adhesion of the molecule. In addition, for specific tunneling conditions, changes induced through the formation of hydrogen bonds became visible in the differential conductance (dI/dV) maps; isolated molecules, hydrogen bonded dimers and supramolecular polymers of EHUT were distinguishable through their electronic properties.