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The protein corona, which forms on the nanoparticle's surface in most biological media, determines the nanoparticle's physicochemical characteristics. The formation of the protein corona has a significant impact on the biodistribution and clearance of nanoparticles in vivo. Therefore, the ability to influence the formation of the protein corona is essential to most biomedical applications, including drug delivery and imaging. In this study, we investigate the protein adsorption on nanoparticles with a hydrodynamic radius of 30 nm and a coating of thermoresponsive poly(2-isopropyl-2-oxazoline) in serum. Using multiangle dynamic light scattering (DLS) we demonstrate that heating of the nanoparticles above their phase separation temperature induces the formation of agglomerates, with a hydrodynamic radius of 1 mu m. In serum, noticeably stronger agglomeration occurs at lower temperatures compared to serum-free conditions. Cryogenic transmission electron microscopy (cryo-TEM) revealed a high packing density of agglomerates when serum was not present. In contrast, in the presence of serum, agglomerated nanoparticles were loosely packed, indicating that proteins are intercalated between them. Moreover, an increase in protein content is observed upon heating, confirming that protein adsorption is induced by the alteration of the surface during phase separation. After cooling and switching the surface back, most of the agglomerates were dissolved and the main fraction returned to the original size of approximately 30 nm as shown by asymmetrical flow-field flow fractionation (AF-FFF) and DLS. Furthermore, the amounts of adsorbed proteins are similar before and after heating the nanoparticles to above their phase-separation temperature. Overall, our results demonstrate that the thermoresponsivity of the polymer coating enables turning the corona formation on nanoparticles on and off in situ. As the local heating of body areas can be easily done in vivo, the thermoresponsive coating could potentially be used to induce the agglomeration of nanopartides and proteins and the accumulation of nanoparticles in a targeted body region.
By dropping a NaH2PO4 center dot H2O precursor solution to a CaCl2 solution at 90 degrees C under continuous stirring in presence of two biopolymers, i.e. gelatin (G) and chitosan (C), supramolecular calcium phosphate (CP) card house structures are formed. Light microscopic investigations in combination with scanning electron microscopy show that the GC-based flower-like structure is constructed from very thin CP platelets. Titration experiments indicate that H-bonding between both biopolymers is responsible for the synergistic effect in presence of both polymers. Gelatin chitosan water complexes play an important role with regard to supramolecular ordering. FTIR spectra in combination with powder X-ray diffraction show that after burning off all organic components (heating up >600 degrees C) dicalcium and tricalcium phosphate crystallites are formed. From high resolution transmission electron microscopy (HR-TEM) it is obvious to conclude, that individual crystal platelets are dicalcium phosphates, which build up ball-like supramolecular structures. The results reveal that the GC guided crystal growth leads to nano-porous supramolecular structures, potentially attractive candidates for bone repair. (c) 2015 Elsevier B.V. All rights reserved.
The distinction of enantiomers is a key aspect of chemical analysis. In mass spectrometry the distinction of enantiomers has been achieved by ionizing the sample with circularly polarized laser pulses and comparing the ion yields for light of opposite handedness. While resonant excitation conditions are expected to be most efficient, they are not required for the detection of a circular dichroism (CD) in the ion yield. However, the prediction of the size and sign of the circular dichroism becomes challenging if non-resonant multiphoton excitations are used to ionize the sample. Employing femtosecond laser pulses to drive electron wavepacket dynamics based on ab initio calculations, we attempt to reveal underlying mechanisms that determine the CD under non-resonant excitation conditions. Simulations were done for (R)-1,2-propylene oxide, using time-dependent configuration interaction singles with perturbative doubles (TD-CIS(D)) and the aug-cc-pVTZ basis set. Interactions between the electric field and the electric dipole and quadrupole as well as between the magnetic field and the magnetic dipole were explicitly accounted for. The ion yield was determined by treating states above the ionization potential as either stationary or non-stationary with energy-dependent lifetimes based on an approved heuristic approach. The observed population dynamics do not allow for a simple interpretation, because of highly non-linear interactions. Still, the various transition pathways are governed by resonant enantiospecific n-photon excitation, with preferably high transition dipole moments, which eventually dominate the CD in the ionized population.
The distinction of enantiomers is a key aspect of chemical analysis. In mass spectrometry the distinction of enantiomers has been achieved by ionizing the sample with circularly polarized laser pulses and comparing the ion yields for light of opposite handedness. While resonant excitation conditions are expected to be most efficient, they are not required for the detection of a circular dichroism (CD) in the ion yield. However, the prediction of the size and sign of the circular dichroism becomes challenging if non-resonant multiphoton excitations are used to ionize the sample. Employing femtosecond laser pulses to drive electron wavepacket dynamics based on ab initio calculations, we attempt to reveal underlying mechanisms that determine the CD under non-resonant excitation conditions. Simulations were done for (R)-1,2-propylene oxide, using time-dependent configuration interaction singles with perturbative doubles (TD-CIS(D)) and the aug-cc-pVTZ basis set. Interactions between the electric field and the electric dipole and quadrupole as well as between the magnetic field and the magnetic dipole were explicitly accounted for. The ion yield was determined by treating states above the ionization potential as either stationary or non-stationary with energy-dependent lifetimes based on an approved heuristic approach. The observed population dynamics do not allow for a simple interpretation, because of highly non-linear interactions. Still, the various transition pathways are governed by resonant enantiospecific n-photon excitation, with preferably high transition dipole moments, which eventually dominate the CD in the ionized population.
In mass spectrometry enantiomers can be distinguished by multiphoton ionization employing circular polarized laser pulses. The circular dichroism (CD) is detected from the normalized difference in the ion yield after excitation with light of opposite handedness. While there are cases in which fragment and parent ions exhibit the same sign of the CD in the ion yield, several experiments show that they might also differ in sign and magnitude. Supported by experimental observations it has been proposed that the parent ion, once it has been formed, is further excited by the laser, which may result in a change of the CD in the ion yield of the formed fragments compared to the parent ion. To gain a deeper insight in possible excitation pathways we calculated and compared the electronic CD absorption spectra of neutral and cationic (R)-3-methylcyclopentanone, applying density functional theory. In addition, electron wavepacket dynamics were used to compare the CD of one- and two-photon transitions. Our results support the proposed subsequent excitation of the parent ion as a possible origin of the difference of the CD in the ion yield between parent ion and fragments.
Hybrid materials are at the forefront of modern research and technology; hence a large number of publications on hybrid materials has already appeared in the scientific literature. This essay focuses on the specifics and peculiarities of hybrid materials based on two-dimensional (2D) building blocks and confinements, for two reasons: (1) 2D materials have a very broad field of application, but they also illustrate many of the scientific challenges the community faces, both on a fundamental and an application level; (2) all authors of this essay are involved in research on 2D materials, but their perspective and vision of how the field will develop in the future and how it is possible to benefit from these new developments are rooted in very different scientific subfields. The current article will thus present a personal, yet quite broad, account of how hybrid materials, specifically 2D hybrid materials, will provide means to aid modern societies in fields as different as healthcare and energy.
It is demonstrated that the orientation of striped patterns can be reversibly switched between two perpendicular in-plane orientations upon exposure to electric fields. The results on thin films of symmetric polystyrene-block-poly(2-vinyl pyridine) polymer in the intermediate segregation regime disclose two types of reorientation mechanisms from perpendicular to parallel relative to the electric field orientation. Domains orient via grain rotation and via formation of defects such as stretched undulations and temporal phase transitions. The contribution of additional fields to the structural evolution is also addressed to elucidate the generality of the observed phenomena. In particular solvent effects are considered. This study reveals the stabilization of the meta-stable in-plane oriented lamella due to sequential swelling and quenching of the film. Further, the reorientation behavior of lamella domains blended with selective nanoparticles is addressed, which affect the interfacial tensions of the blocks and hence introduce another internal field to the studied system. Switching the orientation of aligned block copolymer patterns between two orthogonal directions may open new applications of nanomaterials as switchable electric nanowires or optical gratings.
Exposure to organic mercury compounds promotes primarily neurological effects. Although methylmercury is recognized as a potent neurotoxicant, its transfer into the central nervous system (CNS) is not fully evaluated. While methylmercury and thiomersal pass the blood–brain barrier, limited data are available regarding the second brain regulating interface, the blood–cerebrospinal fluid (CSF) barrier. This novel study was designed to investigate the effects of organic as well as inorganic mercury compounds on, and their transfer across, a porcine in vitro model of the blood–CSF barrier for the first time. The barrier system is significantly more sensitive towards organic Hg compounds as compared to inorganic compounds regarding the endpoints cytotoxicity and barrier integrity. Whereas there are low transfer rates from the blood side to the CSF side, our results strongly indicate an active transfer of the organic mercury compounds out of the CSF. These results are the first to demonstrate an efflux of organic mercury compounds regarding the CNS and provide a completely new approach in the understanding of mercury compounds specific transport.
System-bath problems in physics and chemistry are often described by Markovian master equations. However, the Markov approximation, i.e., neglect of bath memory effects is not always justified, and different measures of non-Markovianity have been suggested in the literature to judge the validity of this approximation. Here we calculate several computable measures of non-Markovianity for the non-trivial problem of a harmonic oscillator coupled to a large number of bath oscillators. The Multi Configurational Time Dependent Hart ree nietliod is used to provide a numerically converged solution of the system-bath Schrodinger equation, from which the appropriate quantities can be calculated. In particular, we consider measures based on trace-distances and quantum discord for a variety of initial states. These quantities have proven useful in the case of two-level and other small model systems Tpically encountered in quantum optics; but are less straightforward to interpret for the more complex model systems that are relevant for chemical physics.
The present article is among the first reports on the effects of poly(ampholyte)s and poly(betaine) s on the biomimetic formation of calcium phosphate. We have synthesized a series of di- and triblock copolymers based on a non-ionic poly(ethylene oxide) block and several charged methacrylate monomers, 2-(trimethylammonium) ethyl methacrylate chloride, 2-((3-cyanopropyl)-dimethylammonium)ethyl methacrylate chloride, 3-sulfopropyl methacrylate potassium salt, and [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl) ammonium hydroxide. The resulting copolymers are either positively charged, ampholytic, or betaine block copolymers. All the polymers have very high molecular weights of over 10(6) g mol(-1). All polymers are water-soluble and show a strong effect on the precipitation and dissolution of calcium phosphate. The strongest effects are observed with triblock copolymers based on a large poly(ethylene oxide) middle block (nominal M-n = 100 000 g mol(-1)). Surprisingly, the data show that there is a need for positive charges in the polymers to exert tight control over mineralization and dissolution, but that the exact position of the charge in the polymer is of minor importance for both calcium phosphate precipitation and dissolution.
The present article is among the first reports on the effects of poly(ampholyte)s and poly(betaine)s on the biomimetic formation of calcium phosphate. We have synthesized a series of di- and triblock copolymers based on a non-ionic poly(ethylene oxide) block and several charged methacrylate monomers, 2-(trimethylammonium)ethyl methacrylate chloride, 2-((3-cyanopropyl)-dimethylammonium)ethyl methacrylate chloride, 3-sulfopropyl methacrylate potassium salt, and [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide. The resulting copolymers are either positively charged, ampholytic, or betaine block copolymers. All the polymers have very high molecular weights of over 106 g mol−1. All polymers are water-soluble and show a strong effect on the precipitation and dissolution of calcium phosphate. The strongest effects are observed with triblock copolymers based on a large poly(ethylene oxide) middle block (nominal Mn = 100 000 g mol−1). Surprisingly, the data show that there is a need for positive charges in the polymers to exert tight control over mineralization and dissolution, but that the exact position of the charge in the polymer is of minor importance for both calcium phosphate precipitation and dissolution.
We investigate the ergodic properties of a random walker performing (anomalous) diffusion on a random fractal geometry. Extensive Monte Carlo simulations of the motion of tracer particles on an ensemble of realisations of percolation clusters are performed for a wide range of percolation densities. Single trajectories of the tracer motion are analysed to quantify the time averaged mean squared displacement (MSD) and to compare this with the ensemble averaged MSD of the particle motion. Other complementary physical observables associated with ergodicity are studied, as well. It turns out that the time averaged MSD of individual realisations exhibits non-vanishing fluctuations even in the limit of very long observation times as the percolation density approaches the critical value. This apparent non-ergodic behaviour concurs with the ergodic behaviour on the ensemble averaged level. We demonstrate how the non-vanishing fluctuations in single particle trajectories are analytically expressed in terms of the fractal dimension and the cluster size distribution of the random geometry, thus being of
purely geometrical origin. Moreover, we reveal that the convergence scaling law to ergodicity, which is known to be inversely proportional to the observation time T for ergodic diffusion processes, follows a power-law BTh with h o 1 due to the fractal structure of the accessible space. These results provide useful measures for differentiating the subdiffusion on random fractals from an otherwise closely related process, namely, fractional Brownian motion. Implications of our results on the analysis of single particle tracking experiments are provided.
Femtosecond-laser pulse driven non-adiabatic spectroscopy and dynamics in molecular and condensed phase systems continue to be a challenge for theoretical modelling. One of the main obstacles is the "curse of dimensionality" encountered in non-adiabatic, exact wavepacket propagation. A possible route towards treating complex molecular systems is via semiclassical surface-hopping schemes, in particular if they account not only for non-adiabatic post-excitation dynamics but also for the initial optical excitation. One such approach, based on initial condition filtering, will be put forward in what follows. As a simple test case which can be compared with exact wavepacket dynamics, we investigate the influence of the different parameters determining the shape of a laser pulse (e.g., its finite width and a possible chirp) on the predissociation dynamics of a NaI molecule, upon photoexcitation of the A(0(+)) state. The finite-pulse effects are mapped into the initial conditions for semiclassical surface-hopping simulations. The simulated surface-hopping diabatic populations are in qualitative agreement with the quantum mechanical results, especially concerning the subpicosend photoinduced dynamics, the main deviations being the relative delay of the non-adiabatic transitions in the semiclassical picture. Likewise, these differences in the time-dependent electronic populations calculated via the semiclassical and the quantum methods are found to have a mild influence on the overall probability density distribution. As a result, the branching ratios between the bound and the dissociative reaction channels and the time-evolution of the molecular wavepacket predicted by the semiclassical method agree with those computed using quantum wavepacket propagation. Implications for more challenging molecular systems are given. (C) 2015 AIP Publishing LLC.
A multi-reference study of the byproduct formation for a ring-closed dithienylethene photoswitch
(2015)
Photodriven molecular switches are sometimes hindered in their performance by forming byproducts which act as dead ends in sequences of switching cycles, leading to rapid fatigue effects. Understanding the reaction pathways to unwanted byproducts is a prerequisite for preventing them. This article presents a study of the photochemical reaction pathways for byproduct formation in the photochromic switch 1,2-bis-(3-thienyl)-ethene. Specifically, using single-and multi-reference methods the post-deexcitation reaction towards the byproduct in the electronic ground state S-0 when starting from the S-1-S-0 conical intersection (CoIn), is considered in detail. We find an unusual low-energy pathway, which offers the possibility for the formation of a dyotropic byproduct. Several high-energy pathways can be excluded with high probability.
A multi-reference study of the byproduct formation for a ring-closed dithienylethene photoswitch
(2015)
Photodriven molecular switches are sometimes hindered in their performance by forming byproducts which act as dead ends in sequences of switching cycles, leading to rapid fatigue effects. Understanding the reaction pathways to unwanted byproducts is a prerequisite for preventing them. This article presents a study of the photochemical reaction pathways for byproduct formation in the photochromic switch 1,2-bis-(3-thienyl)-ethene. Specifically, using single- and multi-reference methods the post-deexcitation reaction towards the byproduct in the electronic ground state S0 when starting from the S1–S0 conical intersection (CoIn), is considered in detail. We find an unusual low-energy pathway, which offers the possibility for the formation of a dyotropic byproduct. Several high-energy pathways can be excluded with high probability.
The computation of dispersive site energy shifts due to van der Waals interaction (London dispersion forces) was combined with mixed quantum-classical methodology to calculate the linear optical absorption spectra of large pheophorbide a (Pheo) dendrimers. The computed spectra agreed very well with the measurements considering three characteristic optical features occurring with increasing aggregate size: a strong line broadening, a redshift, and a low-energy shoulder. The improved mixed quantum-classical methodology is considered a powerful tool in investigating molecular aggregates.
We propose a new approach for calculating the change of the absorption spectrum of a molecule when moved from the gas phase to a crystalline morphology. The so-called gas-to-crystal shift Delta epsilon(m) is mainly caused by dispersion effects and depends sensitively on the molecules specific position in the nanoscopic setting. Using an extended dipole approximation, we are able to divide Delta epsilon(m)= -QW(m) in two factors, where Q depends only on the molecular species and accounts for all nonresonant electronic transitions contributing to the dispersion while W-m is a geometry factor expressing the site dependence of the shift in a given molecular structure. The ability of our approach to predict absorption spectra is demonstrated using the example of polycrystalline films of 3,4,9,10-perylenetetracarboxylic diimide (PTCDI).
The simulation of the optical properties of supramolecular aggregates requires the development of methods, which are able to treat a large number of coupled chromophores interacting with the environment. Since it is currently not possible to treat large systems by quantum chemistry, the Frenkel exciton model is a valuable alternative. In this work we show how the Frenkel exciton model can be extended in order to explain the excitonic spectra of a specific double-walled tubular dye aggregate explicitly taking into account dispersive energy shifts of ground and excited states due to van der Waals interaction with all surrounding molecules. The experimentally observed splitting is well explained by the site-dependent energy shift of molecules placed at the inner or outer side of the double-walled tube, respectively. Therefore we can conclude that inclusion of the site-dependent dispersive effect in the theoretical description of optical properties of nanoscaled dye aggregates is mandatory.
The simulation of the optical properties of supramolecular aggregates requires the development of methods, which are able to treat a large number of coupled chromophores interacting with the environment. Since it is currently not possible to treat large systems by quantum chemistry, the Frenkel exciton model is a valuable alternative. In this work we show how the Frenkel exciton model can be extended in order to explain the excitonic spectra of a specific double-walled tubular dye aggregate explicitly taking into account dispersive energy shifts of ground and excited states due to van der Waals interaction with all surrounding molecules. The experimentally observed splitting is well explained by the site-dependent energy shift of molecules placed at the inner or outer side of the double-walled tube, respectively. Therefore we can conclude that inclusion of the site-dependent dispersive effect in the theoretical description of optical properties of nanoscaled dye aggregates is mandatory.