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1.
J Phys Chem B ; 2020 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-32603114

RESUMO

When a solute molecule is placed in solution, is it acceptable to presume that its electronic structure is essentially the same as that in the gas phase? In this paper, we address this question from a simulation perspective for the case of the sodium dimer cation (Na2+) molecule in both liquid Ar and liquid tetrahydrofuran (THF). In previous work, we showed that, when local specific interactions between a solute and solvent are energetically on the order of a hydrogen bond, the solvent can become part of the chemical identity of the solute. Here, using mixed quantum/classical molecular dynamics simulations, we see that, for the Na2+ molecule, solute-solvent interactions lead to two stable, chemically distinct coordination states (Na(THF)4-Na(THF)5+ and Na(THF)5-Na(THF)5+) that are not only stable themselves as gas-phase molecules but that also have a completely new electronic structure with important implications for the excited-state photodissociation of this molecule in the condensed phase. Furthermore, we show through a set of comparative classical simulations that treating the solute's bonding electron explicitly quantum mechanically is necessary to understand both the ground-state dynamics and chemical identity of this simple diatomic molecule; even use of the quantum-derived potential of mean force is insufficient to describe the behavior of the molecule classically. Finally, we calculate the results of a proposed transient hole-burning experiment that could be used to spectroscopically disentangle the presence of the different coordination states.

2.
J Chem Theory Comput ; 16(2): 1263-1270, 2020 Feb 11.
Artigo em Inglês | MEDLINE | ID: mdl-31914315

RESUMO

There has been a great deal of recent controversy over the structure of the hydrated electron and whether it occupies a cavity or contains a significant number of interior waters (noncavity). The questions we address in this work are, from a free energy perspective, how different are these proposed structures? Do the different structures all lie along a single continuum, or are there significant differences (i.e., free energy barriers) between them? To address these questions, we have performed a series of one-electron calculations using umbrella sampling with quantum biased molecular dynamics along a coordinate that directly reflects the number of water molecules in the hydrated electron's interior. We verify that a standard cavity model of the hydrated electron behaves essentially as a hard sphere: the model is dominated by repulsion at short range such that water is expelled from a local volume around the electron, leading to a water solvation shell like that of a pseudohalide ion. The repulsion is much larger than thermal energies near room temperature, explaining why such models exhibit properties with little temperature dependence. On the other hand, our calculations reveal that a noncavity model is highly fluxional, meaning that thermal motions cause the number of interior waters to fluctuate from effectively zero (i.e., a cavity-type electron) to potentially above the bulk water density. The energetic contributions in the noncavity model are still repulsive in the sense that they favor cavity formation, so the fluctuations in structure are driven largely by entropy: the entropic cost for expelling water from a region of space is large enough that some water is still driven into the electron's interior. As the temperature is lowered and entropy becomes less important, the noncavity electron's structure is predicted to become more cavity-like, consistent with the observed temperature dependence of the hydrated electron's properties. Thus, we argue that although the specific noncavity model we study overestimates the preponderance of fluctuations involving interior water molecules, with appropriate refinements to correctly capture the true average number of interior waters and molar solvation volume, a fluxional model likely makes the most sense for understanding the various experimental properties of the hydrated electron.

3.
J Phys Chem Lett ; : 4929-4934, 2019 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-31382748

RESUMO

Despite the fact that molecular doping of semiconducting polymers has emerged as a valuable strategy for improving the performance of organic electronic devices, the fundamental dopant-polymer interactions are not fully understood. Here we use 2-D grazing incidence wide-angle X-ray scattering (GIWAXS) to demonstrate that adding oxidizing small-molecule dopants, such as 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) and FeCl3, into the amorphous conjugated polymer, regiorandom poly(3-hexylthiophene-2,5-diyl) (RRa-P3HT), improves polymer ordering and induces a change in domain orientation from isotropic to mostly edge-on. Doping thus causes RRa-P3HT to behave similarly to the more ordered regioregular P3HT. By comparing the optical, electrical, and structural properties of RRa-P3HT films doped with F4TNCQ and FeCl3 and those infiltrated with 7,7,8,8-tetracyanoquinodimethane (TCNQ), which occupies a similar volume as F4TCNQ but does not dope RRa-P3HT, we show that the increased ordering results not from the ability of the dopant to fill space but instead from the need to delocalize charge on the polymer in more than one dimension.

4.
Faraday Discuss ; 216(0): 339-362, 2019 Jul 11.
Artigo em Inglês | MEDLINE | ID: mdl-31038132

RESUMO

It is generally presumed that the vast majority of carriers created by chemical doping of semiconducting polymer films are coulombically trapped by the counteranion, with only a small fraction that are free and responsible for the increased conductivity essential for organic electronic applications. At higher doping levels, it is also possible for bipolarons to form, which are expected to be less conductive than single polarons. Unfortunately, there is no simple way to distinguish free polarons, trapped polarons and bipolarons using steady-state spectroscopy. Thus, in this work, we use ultrafast transient absorption spectroscopy to study the dynamics of polarons in 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TNCQ)-doped films of poly(3-hexylthiophene-2,5-diyl) (P3HT) as a function of dopant concentration and excitation wavelength. When exciting on the red side of the polaron P1 transition, our transient absorption spectra and kinetics match well with what is expected for free 2-D-delocalized polarons; the measurements are not consistent with a recent theory of doped conjugated polymer electronic structure that suggests that the half-filled state lies deeper in the conduction band rather than in the bandgap. As we tune the excitation wavelength to the blue, our measurements reveal an increasing amount of slower transient kinetics that are consistent with the presence of coulombically-trapped polarons rather than bipolarons. Taking advantage of their distinct ultrafast relaxation kinetics as a type of action spectroscopy, we are able to extract the steady-state absorption spectra of free and trapped polarons as a function of dopant concentration. By comparing the results to theoretical models, we determine that in F4TCNQ-doped P3HT films, trapped polarons sit ∼0.4 nm away from the anion while free polarons reside between 0.7 and 0.9 nm from the counteranion. Perhaps counterintuitively, the ratio of trapped to free polarons increases at higher doping levels, an observation that is consistent with a plateau in the concentration-dependent conductivity of F4TCNQ-doped P3HT films.

5.
Adv Mater ; 31(11): e1805647, 2019 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-30672037

RESUMO

One of the most effective ways to tune the electronic properties of conjugated polymers is to dope them with small-molecule oxidizing agents, creating holes on the polymer and molecular anions. Undesirably, strong electrostatic attraction from the anions of most dopants localizes the holes created on the polymer, reducing their mobility. Here, a new strategy utilizing a substituted boron cluster as a molecular dopant for conjugated polymers is employed. By designing the cluster to have a high redox potential and steric protection of the core-localized electron density, highly delocalized polarons with mobilities equivalent to films doped with no anions present are obtained. AC Hall effect measurements show that P3HT films doped with these boron clusters have conductivities and polaron mobilities roughly an order of magnitude higher than films doped with F4 TCNQ, even though the boron-cluster-doped films have poor crystallinity. Moreover, the number of free carriers approximately matches the number of boron clusters, yielding a doping efficiency of ≈100%. These results suggest that shielding the polaron from the anion is a critically important aspect for producing high carrier mobility, and that the high polymer crystallinity required with dopants such as F4 TCNQ is primarily to keep the counterions far from the polymer backbone.

6.
J Phys Chem Lett ; 9(17): 5173-5178, 2018 Sep 06.
Artigo em Inglês | MEDLINE | ID: mdl-30129761

RESUMO

One of the outstanding puzzles in the photoelectron spectroscopy of water anion clusters, which serve as precursors to the hydrated electron, is that the excess electron has multiple vertical detachment energies (VDEs), with different groups seeing different distributions of VDEs. We have studied the photoelectron spectroscopy of water cluster anions using simulation techniques designed to mimic the different ways that water cluster anions are produced experimentally. Our simulations take advantage of density functional theory-based Born-Oppenheimer molecular dynamics with an optimally tuned range-separated hybrid functional that is shown to give outstanding accuracy for calculating electron binding energies for this system. We find that our simulations are able to accurately reproduce the experimentally observed VDEs for cluster anions of different sizes, with different VDE distributions observed depending on how the water cluster anions are prepared. For cluster anion sizes up to 20 water molecules, we see that the excess electron always resides on the surface of the cluster and that the different discrete VDEs result from the discrete number of hydrogen bonds made to the electron by water molecules on the surface. Clusters that are less thermally equilibrated have surface waters that tend to make single H-bonds to the electron, resulting in lower VDEs, while clusters that are more thermally equilibrated have surface waters that prefer to make two H-bonds to the electron, resulting in higher VDEs.

7.
Nat Chem ; 10(9): 910-916, 2018 09.
Artigo em Inglês | MEDLINE | ID: mdl-29785032

RESUMO

For solution-phase chemical reactions, the solvent is often considered simply as a medium to allow the reactants to encounter each other by diffusion. Although examples of direct solvent effects on molecular solutes exist, such as the compression of solute bonding electrons due to Pauli repulsion interactions, the solvent is not usually considered a part of the chemical species of interest. We show, using quantum simulations of Na2, that when there are local specific interactions between a solute and solvent that are energetically on the same order as a hydrogen bond, the solvent controls not only the bond dynamics but also the chemical identity of the solute. In tetrahydrofuran, dative bonding interactions between the solvent and Na atoms lead to unique coordination states that must cross a free energy barrier of ~8 kBT-undergoing a chemical reaction-to interconvert. Each coordination state has its own dynamics and spectroscopic signatures, highlighting the importance of considering the solvent in the identity of condensed-phase chemical systems.

9.
J Chem Phys ; 147(7): 074503, 2017 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-28830174

RESUMO

We use one-electron non-adiabatic mixed quantum/classical simulations to explore the temperature dependence of both the ground-state structure and the excited-state relaxation dynamics of the hydrated electron. We compare the results for both the traditional cavity picture and a more recent non-cavity model of the hydrated electron and make definite predictions for distinguishing between the different possible structural models in future experiments. We find that the traditional cavity model shows no temperature-dependent change in structure at constant density, leading to a predicted resonance Raman spectrum that is essentially temperature-independent. In contrast, the non-cavity model predicts a blue-shift in the hydrated electron's resonance Raman O-H stretch with increasing temperature. The lack of a temperature-dependent ground-state structural change of the cavity model also leads to a prediction of little change with temperature of both the excited-state lifetime and hot ground-state cooling time of the hydrated electron following photoexcitation. This is in sharp contrast to the predictions of the non-cavity model, where both the excited-state lifetime and hot ground-state cooling time are expected to decrease significantly with increasing temperature. These simulation-based predictions should be directly testable by the results of future time-resolved photoelectron spectroscopy experiments. Finally, the temperature-dependent differences in predicted excited-state lifetime and hot ground-state cooling time of the two models also lead to different predicted pump-probe transient absorption spectroscopy of the hydrated electron as a function of temperature. We perform such experiments and describe them in Paper II [E. P. Farr et al., J. Chem. Phys. 147, 074504 (2017)], and find changes in the excited-state lifetime and hot ground-state cooling time with temperature that match well with the predictions of the non-cavity model. In particular, the experiments reveal stimulated emission from the excited state with an amplitude and lifetime that decreases with increasing temperature, a result in contrast to the lack of stimulated emission predicted by the cavity model but in good agreement with the non-cavity model. Overall, until ab initio calculations describing the non-adiabatic excited-state dynamics of an excess electron with hundreds of water molecules at a variety of temperatures become computationally feasible, the simulations presented here provide a definitive route for connecting the predictions of cavity and non-cavity models of the hydrated electron with future experiments.

10.
J Chem Phys ; 147(7): 074504, 2017 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-28830177

RESUMO

The structure of the hydrated electron, particularly whether it exists primarily within a cavity or encompasses interior water molecules, has been the subject of much recent debate. In Paper I [C.-C. Zho et al., J. Chem. Phys. 147, 074503 (2017)], we found that mixed quantum/classical simulations with cavity and non-cavity pseudopotentials gave different predictions for the temperature dependence of the rate of the photoexcited hydrated electron's relaxation back to the ground state. In this paper, we measure the ultrafast transient absorption spectroscopy of the photoexcited hydrated electron as a function of temperature to confront the predictions of our simulations. The ultrafast spectroscopy clearly shows faster relaxation dynamics at higher temperatures. In particular, the transient absorption data show a clear excess bleach beyond that of the equilibrium hydrated electron's ground-state absorption that can only be explained by stimulated emission. This stimulated emission component, which is consistent with the experimentally known fluorescence spectrum of the hydrated electron, decreases in both amplitude and lifetime as the temperature is increased. We use a kinetic model to globally fit the temperature-dependent transient absorption data at multiple temperatures ranging from 0 to 45 °C. We find the room-temperature lifetime of the excited-state hydrated electron to be 137±40 fs, in close agreement with recent time-resolved photoelectron spectroscopy (TRPES) experiments and in strong support of the "non-adiabatic" picture of the hydrated electron's excited-state relaxation. Moreover, we find that the excited-state lifetime is strongly temperature dependent, changing by slightly more than a factor of two over the 45 °C temperature range explored. This temperature dependence of the lifetime, along with a faster rate of ground-state cooling with increasing bulk temperature, should be directly observable by future TRPES experiments. Our data also suggest that the red side of the hydrated electron's fluorescence spectrum should significantly decrease with increasing temperature. Overall, our results are not consistent with the nearly complete lack of temperature dependence predicted by traditional cavity models of the hydrated electron but instead agree qualitatively and nearly quantitatively with the temperature-dependent structural changes predicted by the non-cavity hydrated electron model.

11.
J Phys Chem B ; 120(49): 12604-12614, 2016 12 15.
Artigo em Inglês | MEDLINE | ID: mdl-27973828

RESUMO

We use nonadiabatic mixed quantum/classical molecular dynamics to simulate recent time-resolved photoelectron spectroscopy (TRPES) experiments on the hydrated electron, and compare the results for both a cavity and a noncavity simulation model to experiment. We find that cavity-model hydrated electrons show an "adiabatic" relaxation mechanism, with ground-state cooling that is fast on the time scale of the internal conversion, a feature that is in contrast to the TRPES experiments. A noncavity hydrated electron model, however, displays a "nonadiabatic" relaxation mechanism, with rapid internal conversion followed by slower ground-state cooling, in good qualitative agreement with experiment. We also show that the experimentally observed early time red shift and loss of anisotropy of the excited-state TRPES peak are consistent with hydrated electron models with homogeneously broadened absorption spectra, but not with those with inhomogeneously broadened absorption spectra. Finally, we find that a decreasing photoionization cross section upon cooling causes the excited-state TRPES peak to decay faster than the underlying radiationless relaxation process, so that the experimentally observed 60-75 fs peak decay corresponds to an actual excited-state lifetime of the hydrated electron that is more likely ∼100 fs.

12.
J Phys Chem Lett ; 7(16): 3192-8, 2016 Aug 18.
Artigo em Inglês | MEDLINE | ID: mdl-27479028

RESUMO

The properties of the hydrated electron at the air/water interface are computed for both a cavity and a noncavity model using mixed quantum/classical molecular dynamics simulation. We take advantage of our recently developed formalism for umbrella sampling with a restrained quantum expectation value to calculate free-energy profiles of the hydrated electron's position relative to the water surface. We show that it is critical to use an instantaneous description of the air/water interface rather than the Gibbs' dividing surface to obtain accurate potentials of mean force. We find that noncavity electrons, which prefer to encompass several water molecules, avoid the interface where water molecules are scarce. In contrast, cavity models of the hydrated electron, which prefer to expel water, have a local free-energy minimum near the interface. When the cavity electron occupies this minimum, its absorption spectrum is quite red-shifted, its binding energy is significantly lowered, and its dynamics speed up quite a bit compared with the bulk, features that have not been found by experiment. The surface activity of the electron therefore serves as a useful test of cavity versus noncavity electron solvation.

13.
J Chem Theory Comput ; 12(10): 5117-5131, 2016 Oct 11.
Artigo em Inglês | MEDLINE | ID: mdl-27576177

RESUMO

The hydrated electron, e-(aq), has often served as a model system to understand the influence of condensed-phase environments on electronic structure and dynamics. Despite over 50 years of study, however, the basic structure of e-(aq) is still the subject of controversy. In particular, the structure of e-(aq) was long assumed to be an electron localized within a solvent cavity, in a manner similar to halide solvation. Recently, however, we suggested that e-(aq) occupies a region of enhanced water density with little or no discernible cavity. The potential we developed was only subtly different from those that give rise to a cavity solvation motif, which suggests that the driving forces for noncavity solvation involve subtle electron-water attractive interactions at close distances. This leads to the question of how dispersion interactions are treated in simulations of the hydrated electron. Most dispersion potentials are ad hoc or are not designed to account for the type of close-contact electron-water overlap that might occur in the condensed phase, and where short-range dynamic electron correlation is important. To address this, in this paper we develop a procedure to calculate the potential energy surface between a single water molecule and an excess electron with high-level CCSD(T) electronic structure theory. By decomposing the electron-water potential into its constituent energetic contributions, we find that short-range electron correlation provides an attraction of comparable magnitude to the mean-field interactions between the electron and water. Furthermore, we find that by reoptimizing a popular cavity-forming one-electron model potential to better capture these attractive short-range interactions, the enhanced description of correlation predicts a noncavity e-(aq) with calculated properties in better agreement with experiment. Although much attention has been placed on the importance of long-range dispersion interactions in water cluster anions, our study reveals that largely unexplored short-range correlation effects are crucial in dictating the solvation structure of the condensed-phase hydrated electron.

14.
J Phys Chem B ; 120(26): 6215-24, 2016 07 07.
Artigo em Inglês | MEDLINE | ID: mdl-27079171

RESUMO

Poly(fluorene-alt-thiophene) (PFT) is a conjugated polyelectrolyte that self-assembles into rod-like micelles in water, with the conjugated polymer backbone running along the length of the micelle. At modest concentrations (∼10 mg/mL in aqueous solutions), PFT forms hydrogels, and this work focuses on understanding the structure and intermolecular interactions in those gel networks. The network structure can be directly visualized using cryo electron microscopy. Oscillatory rheology studies further tell us about connectivity within the gel network, and the data are consistent with a picture where polymer chains bridge between micelles to hold the network together. Addition of tetrahydrofuran (THF) to the gels breaks those connections, but once the THF is removed, the gel becomes stronger than it was before, presumably due to the creation of a more interconnected nanoscale architecture. Small polymer oligomers can also passivate the bridging polymer chains, breaking connections between micelles and dramatically weakening the hydrogel network. Fits to solution-phase small-angle X-ray scattering data using a Dammin bead model support the hypothesis of a bridging connection between PFT micelles, even in dilute aqueous solutions. Finally, time-resolved microwave conductivity measurements on dried samples show an increase in carrier mobility after THF annealing of the PFT gel, likely due to increased connectivity within the polymer network.


Assuntos
Hidrogéis/química , Polieletrólitos/química , Microscopia Crioeletrônica , Eletricidade , Furanos/química , Cinética , Micelas , Micro-Ondas , Modelos Químicos , Reologia , Espalhamento a Baixo Ângulo , Soluções/química , Substâncias Viscoelásticas/química , Água/química , Difração de Raios X
15.
ACS Med Chem Lett ; 7(3): 217-22, 2016 Mar 10.
Artigo em Inglês | MEDLINE | ID: mdl-26985301

RESUMO

A novel series of potent and selective hexokinase 2 (HK2) inhibitors, 2,6-disubstituted glucosamines, has been identified based on HTS hits, exemplified by compound 1. Inhibitor-bound crystal structures revealed that the HK2 enzyme could adopt an "induced-fit" conformation. The SAR study led to the identification of potent HK2 inhibitors, such as compound 34 with greater than 100-fold selectivity over HK1. Compound 25 inhibits in situ glycolysis in a UM-UC-3 bladder tumor cell line via (13)CNMR measurement of [3-(13)C]lactate produced from [1,6-(13)C2]glucose added to the cell culture.

16.
J Phys Chem Lett ; 6(23): 4786-93, 2015 Dec 03.
Artigo em Inglês | MEDLINE | ID: mdl-26554820

RESUMO

We demonstrate that solution-sequential processing (SqP) can yield heavily doped pristine-quality films when used to infiltrate the molecular dopant 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) into pure poly(3-hexylthiophene) (P3HT) polymer layers. Profilometry measurements show that the SqP method produces doped films with essentially the same surface roughness as pristine films, and 2-D grazing-incidence wide-angle X-ray scattering (GIWAXS) confirms that SqP preserves both the size and orientation of the pristine polymer's crystallites. Unlike traditional blend-cast F4TCNQ/P3HT doped films, our sequentially processed layers have tunable and reproducible conductivities reaching as high as 5.5 S/cm even when measured over macroscopic (>1 cm) distances. The high conductivity and superb film quality allow for meaningful Hall effect measurements, which reveal p-type conduction and carrier concentrations tunable from 10(16) to 10(20) cm(-3) and hole mobilities ranging from ∼0.003 to 0.02 cm(2) V(-1) s(-1) at room temperature over the doping levels examined.

17.
ACS Appl Mater Interfaces ; 7(45): 25247-58, 2015 Nov 18.
Artigo em Inglês | MEDLINE | ID: mdl-26488157

RESUMO

Although it is known that evaporated metals can penetrate into films of various organic molecules that are a few nanometers thick, there has been little work aimed at exploring the interaction of the common electrode metals used in devices with fullerene derivatives, such as organic photovoltaics (OPVs) or perovskite solar cells that use fullerenes as electron transport layers. In this paper, we show that when commonly used electrode metals (e.g., Au, Ag, Al, Ca, etc.) are evaporated onto films of fullerene derivatives (such as [6,6]-phenyl-C61-butyric acid methyl ester (PCBM)), the metal penetrates many tens of nanometers into the fullerene layer. This penetration decreases the effective electrical thickness of fullerene-based sandwich structure devices, as measured by the device's geometric capacitance, and thus significantly alters the device physics. For the case of Au/PCBM, the metal penetrates a remarkable 70 nm into the fullerene, and we see penetration of similar magnitude in a wide variety of fullerene derivative/evaporated metal combinations. Moreover, using transmission electron microscopy to observed cross-sections of the films, we show that when gold is evaporated onto poly(3-hexylthiophene) (P3HT)/PCBM sequentially processed OPV quasi-bilayers, Au nanoparticles with diameters of ∼3-20 nm are formed and are dispersed entirely throughout the fullerene-rich overlayer. The plasmonic absorption and scattering from these nanoparticles are readily evident in the optical transmission spectrum, demonstrating that the interpenetrated metal significantly alters the optical properties of fullerene-rich active layers. This opens a number of possibilities in terms of contact engineering and light management so that metal penetration in devices that use fullerene derivatives could be used to advantage, making it critical that researchers are aware of the electronic and optical consequences of exposing fullerene-derivative films to evaporated electrode metals.


Assuntos
Eletroquímica/instrumentação , Fulerenos/química , Metais/química , Nanoestruturas/química , Eletricidade , Eletrodos , Ésteres/química , Nanoestruturas/ultraestrutura , Semicondutores , Volatilização
18.
Science ; 348(6241): 1340-3, 2015 Jun 19.
Artigo em Inglês | MEDLINE | ID: mdl-26089510

RESUMO

The efficiency of biological photosynthesis results from the exquisite organization of photoactive elements that promote rapid movement of charge carriers out of a critical recombination range. If synthetic organic photovoltaic materials could mimic this assembly, charge separation and collection could be markedly enhanced. We show that micelle-forming cationic semiconducting polymers can coassemble in water with cationic fullerene derivatives to create photoinduced electron-transfer cascades that lead to exceptionally long-lived polarons. The stability of the polarons depends on the organization of the polymer-fullerene assembly. Properly designed assemblies can produce separated polaronic charges that are stable for days or weeks in aqueous solution.


Assuntos
Fulerenos/química , Fotossíntese , Polímeros/química , Transporte de Elétrons , Semicondutores
19.
Nanoscale ; 6(9): 4652-8, 2014 May 07.
Artigo em Inglês | MEDLINE | ID: mdl-24647752

RESUMO

We report the design and synthesis of a nano-container consisting of mesoporous silica nanoparticles with the pore openings covered by "snap-top" caps that are opened by near-IR light. A photo transducer molecule that is a reducing agent in an excited electronic state is covalently attached to the system. Near IR two-photon excitation causes inter-molecular electron transfer that reduces a disulfide bond holding the cap in place, thus allowing the cargo molecules to escape. We describe the operation of the "snap-top" release mechanism by both one- and two-photon activation. This system presents a proof of concept of a near-IR photoredox-induced nanoparticle delivery system that may lead to a new type of photodynamic drug release therapy.


Assuntos
Portadores de Fármacos/química , Nanopartículas/química , Transporte de Elétrons , Raios Infravermelhos , Oxirredução , Fótons , Fármacos Fotossensibilizantes/química , Porosidade , Rodaminas/química , Dióxido de Silício/química
20.
J Chem Theory Comput ; 10(10): 4661-71, 2014 Oct 14.
Artigo em Inglês | MEDLINE | ID: mdl-26588157

RESUMO

We introduce a new simulation method called Coupled-Perturbed Quantum Umbrella Sampling that extends the classical umbrella sampling approach to reaction coordinates involving quantum mechanical degrees of freedom. The central idea in our method is to solve coupled-perturbed equations to find the response of the quantum system's wave function along a reaction coordinate of interest. This allows for propagation of the system's dynamics under the influence of a quantum biasing umbrella potential and provides a method to rigorously undo the effects of the bias to compute equilibrium ensemble averages. In this way, one can drag electrons into regions of high free energy where they would otherwise not go, thus enabling chemistry by fiat. We demonstrate the applicability of our method for two condensed-phase systems of interest. First, we consider the interaction of a hydrated electron with an aqueous sodium cation, and we calculate a potential of mean force that shows that an e(-):Na(+) contact pair is the thermodynamically favored product starting from either a neutral sodium atom or the separate cation and electron species. Second, we present the first determination of a hydrated electron's free-energy profile relative to an air/water interface. For the particular model parameters used, we find that the hydrated electron is more thermodynamically stable in the bulk rather than at the interface. Our analysis suggests that the primary driving force keeping the electron away from the interface is the long-range electron-solvent polarization interaction rather than the short-range details of the chosen pseudopotential.

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