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At least 1,063 records · Page 59

Modulation of a solid-state reversible fluorescent photoswitching based on a controllable photochromic pyrazolones

A novel solid-state reversible fluorescence photoswitching system (FPS) based on photochromism of photochromic pyrazolones has been developed by employing phosphor Sr{sub 2}P{sub 2}O{sub 7} co-doped with europium ion and chlorine ion (Sr{sub 2}P{sub 2}O{sub 7}–EC) and 1,3-diphenyl-4-(3-chlorobenzal)-5-hydroxypyrazole-4-phenylsemicarbazone (1a) as the fluorescence dye and the photochromic compound, respectively. With carefully selected components, the absorption band of the keto-form photochromic pyrazolones well overlaps with the emission peak of Sr{sub 2}P{sub 2}O{sub 7}–EC. The fluorescence emission intensity of Sr{sub 2}P{sub 2}O{sub 7}–EC is efficiently modulated by the photoisomerization of 1a with controlling the exposure time in the solid state. The fluorescence photoswitching system displayed high fluorescence quenching efficiency and remarkable fatigue resistance. It can be repeated 7 cycles without observable the changes of emission intensity. A fluorescence quenching efficiency can be achieved with a reversible colour change from white to yellow. - Graphical abstract: A novel fluorescence photoswitching system based on doping inorganic fluorescence dye into photochromic pyrazolones was constructed successfully. Its fluorescence emission could be efficiently modulated by the photoisomerization of pyrazolones. - Highlights: • A solid-state fluorescence photoswitching material was prepared. • Photoswitching is due to energy transfer between pyrazolone and fluorescence dye. • It exhibits excellent fluorescence contrast and fatigue resistance in the solid state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhancement of photocatalytic properties of Bi{sub 2}WO{sub 6} nanoparticles by Pt deposition

Graphical abstract: - Highlights: • Pt/Bi{sub 2}WO{sub 6} was used for photocatalytic degradation of methyl orange dye. • Photocatalytic degradation was dependent on wt% of Pt reaction time, and weight of catalyst. • Kinetic study revealed that the photocatalytic degradation of methyl orange dye followed the first order. • Catalyst re-use revealed the present photocatalyst remain effective and active after five cycles. - Abstract: Bi{sub 2}WO{sub 6} nanoparticles were prepared using a hydrothermal method, and Pt was immobilized on the surface of Bi{sub 2}WO{sub 6} via a photo-assisted deposition (PAD) method. The samples produced were characterized using X-ray diffraction, ultraviolet and visible spectroscopy, photoluminescence emission spectra, transmission electron microscopy, extended X-ray absorption fine structure, and surface area measurements. Furthermore, the catalytic performance of the Bi{sub 2}WO{sub 6} and Pt/Bi{sub 2}WO{sub 6} samples was examined in the degradation of methyl orange dye (MO) under visible light. The extended X-ray absorption fine structure (EXAFS) results, which showed the presence of peaks assigned to the Pt–Pt at approximately 2.50 Å, indicate the formation of nanoscale Pt features. The UV–vis spectral analysis detected a red shift after loading the Pt into the Bi{sub 2}WO{sub 6}. The maximum degradation efficiency achieved was 100% with 0.3 Pt/Bi{sub 2}WO{sub 6} as the photocatalyst after a 30-min reaction time. The catalyst could be reused without any loss in activity for the first five cycles.

36 MATERIALS SCIENCE↗

Facile synthesis of pompon-like ZnO-Ag nanocomposites and their enhanced photocatalytic performance

Graphical abstract: - Highlights: • Pompon-like ZnO-Ag was prepared via heterothermal and photodeposition method. • Pompon-like ZnO-Ag is a excellent photocatalyst for degradation of azo dyes. • The photocatalytic and wetting properties were studied upon UV irradiation. • The discoloring efficiency of ZnO-Ag heterostructure toward to azo dyes is 99.1%. - Abstract: A series of pompon-like ZnO-Ag nanocomposites were prepared by hydrothermal method and photochemical deposition technique. Several characterizations indicated the successful deposition of Ag nanoparticles on ZnO. As a whole, the as-prepared composites present pompon-like nanostructures with a diameter of ∼10 μm. In detail, the nanostructural, chemical and optical properties were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), infrared spectroscopy (IR), ultra-visible spectra (UV). The photocatalytic degradation experiments under UV irradiation using Methyl Orange (MO) as a model dye were executed here. The relative results demonstrated that the pompon-like ZnO-Ag nanocomposite with a suitable content of Ag nanoparticles (about 4.82 wt%) has the highest photochemical activity, and the removal ratio of MO was 99.1% after 0.5 h adsorption and subsequent 2 h photodegradation processes. The excellent photocatalytic performance was attributed to the high surface areas of ZnO nanostructure and effectively separation of photo-generated charge on flower-like ZnO by employing Ag nanoparticles as a conductor.

36 MATERIALS SCIENCE↗

In-situ growth of zinc tungstate nanorods on graphene for enhanced photocatalytic performance

Graphical abstract: Graphene/ZnWO{sub 4} (G–ZnWO{sub 4}) nanorod composite photocatalysts were prepared by a simple one-step method. Namely, the reduction of graphene oxide and the growth of ZnWO{sub 4} nanorod occurred simultaneously in one single process. An enhancement in the photocatalytic activities were observed in G–ZnWO{sub 4} composites compared with pure ZnWO{sub 4} under UV light irradiation. - Highlights: • Graphene–ZnWO{sub 4} composite photocatalyst was prepared for the first time. • The as-prepared composite photocatalysts show high activity for dye degradation. • Effect of graphene amount on the photocatalytic activity was investigated. - Abstract: Graphene–zinc tungstate (G–ZnWO{sub 4}) hybrid photocatalysts were prepared by an in-situ growth method in which the reduction of graphene oxide (GO) and the growth of ZnWO{sub 4} crystals occurred simultaneously. The materials were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, UV–vis diffuse reflectance spectroscopy and X-ray photoelectron spectroscopy. The photocatalytic activity was investigated by the degradation of dye methylene blue (MB). An enhancement in the photocatalytic activity was observed for G–ZnWO{sub 4} hybrids compared with pure ZnWO{sub 4} under UV light. This improvement was attributed to the following two reasons: increased migration efficiency of photo-induced electrons and increased adsorption activity for dye molecules. The effect of the amount of graphene on the photocatalytic activity was also investigated. Results showed that there was an optimum amount of 2%.

36 MATERIALS SCIENCE↗

Soft chemical synthesis of Ag{sub 3}SbS{sub 3} with efficient and recyclable visible light photocatalytic properties

Highlights: • Highly crystalline Ag{sub 3}SbS{sub 3} synthesized using soft chemical approach. • First time report of photocatalytic activity of Ag{sub 3}SbS{sub 3}. • Ag{sub 3}SbS{sub 3} degraded the harmful organic dyes rapidly under visible radiation. • Pseudo first order kinetics have been followed in these sets of reactions. • Up to 90% of Methylene Blue degraded even after 4th cycle of catalyst reuse. • Structure of catalyst is intact after reuse. • As the catalyst is heavy, its separation after use is quite simple. - Abstract: Application of Ag{sub 3}SbS{sub 3}, obtained by soft chemical approach involving rapid reaction of air stable metal–thiourea complexes in ethylene glycol medium, as visible light photocatalyst for the degradation of dye solutions was investigated. Ag{sub 3}SbS{sub 3} was confirmed by high resolution powder X-ray diffraction pattern and its no defined morphology was present in SEM images. From UV–vis spectroscopy measurements, optical band gap of 1.77 eV was deduced for Ag{sub 3}SbS{sub 3}. Rapid degradation kinetics and recyclability was exhibited by Ag{sub 3}SbS{sub 3} towards Methylene Blue, Methyl Orange, Malachite Green, and Rhodamine 6G dye solutions under visible radiation. All these processes followed pseudo first order kinetics. High surface area (6.39 m{sup 2}/g), with mesopores (3.81 nm), arising from solvent mediated synthesis of Ag{sub 3}SbS{sub 3} has been correlated to its catalytic activity.

36 MATERIALS SCIENCE↗

Enhanced visible light photocatalytic activity of porous LaMnO{sub 3} sub-micron particles in the degradation of rose bengal

Highlights: • The monodispersed LaMnO{sub 3} microstructure was prepared by hydrothermal method. • The growth of different shaped LaMnO{sub 3} particles was obtained by varying annealing temperatures. • Porous LaMnO{sub 3} microstructure possessed superior photocatalytic activity in rose bengal dye. • The morphology and high surface area influence the enhanced photocatalytic activity. - Abstract: A perovskite LaMnO{sub 3} micro/nanostructure is a promising high-efficiency photocatalytic materials for the removal of various organic pollutants. This study presents the preparation of sub-micron LaMnO{sub 3} particles with polyvinyl pyrrolidone (PVP) as a structure directing agent to control the primary morphology and aggregations. Furthermore, the sample was annealed at different temperatures to improve the crystallinity and perovskite phase formations. The possible formation mechanism was explained based on the annealing temperatures. An attempt has been made to study the effect of different morphologies of LaMnO{sub 3} particles for the degradation of RB dye under visible light irradiation. The removal efficiency of 95% for RB dye in 60 min evidences the superior degradation capability of highly porous LaMnO{sub 3} particles. The photocatalytic activity not only depends on porous structure, but also strongly based on crystallinity, and specific surface area of LaMnO{sub 3} particles. Hence, the porous morphology displays a superior photocatalytic activity than other LaMnO{sub 3} microstructures.

36 MATERIALS SCIENCE↗

Influence of Fluorine incorporation on the photocatalytic activity of Tin Oxide thin films

Highlights: • Fluorine doped SnO{sub 2} thin films prepared by a facile homemade jet nebulizer spray pyrolysis technique. • XRD, XPS, PL, FESEM, AFM studies support the discussions. • The photocatalytic activities of the prepared tin oxide (TO) and FTO thin films for the degradation of MB aqueous solution were tested. . - Abstract: This work reports the photocatalytic activity of undoped tin oxide (TO) and F doped tin oxide (FTO) thin films for MB dye degradation under visible light irradiation. A facile homemade jet nebulizer spray pyrolysis technique was employed to prepare these samples. The results indicate that FTO film exhibits superior photocatalytic activity compared to TO film. Dye degradation of nearly 95% is achieved using FTO film at 90 min whereas TO film degrades only 78% of dye molecules in the same time interval. This enhancement for FTO films might be due to the generation of large number of free electrons caused by the fluorine incorporation. The mechanism behind the enhancement of photocatalytic activity of FTO films is discussed elaborately with the aid of optical and PL studies. The structure, composition and morphology of the samples were analyzed using XRD, XPS, FTIR, FESEM and AFM. The incorporation of F into SnO{sub 2} lattice is confirmed through FTIR analysis.

36 MATERIALS SCIENCE↗

Room temperature synthesis of urea based imidazole functionalised ZnO nanorods and their photocatalytic application

Highlights: • Imidazole functionalised ZnO nanorods obtained at room temperature. • Functionalised ZnO nanorods degrade Rh B dye by 84% under Hg lamp illumination. • Rh B dye photocatalysis by functionalised ZnO nanorods follow 1st order kinetics. - Abstract: ZnO, a well known photocatalyst due to its wide band gap, is used for environmental remediation applications. Under present investigation, two urea based imidazole functionalised compounds R and S were synthesised and then used as structure directing agent to further synthesise surface functionalised ZnO nanorods at room temperature (30–40 °C) by simple chemical precipitation route. R: Zn(NO{sub 3}){sub 2}·6H{sub 2}O: NaOH used in two ratios i.e. 1:2:4 and 1:1:1 to synthesise R functionalised ZnO nanorods i.e. R1 and R2 respectively while S: Zn(NO{sub 3}){sub 2}·6H{sub 2}O: NaOH used in 1:2:4 ratio to synthesise S functionalised ZnO nanoparticles i.e. S1. R functionalized ZnO nanorods (R1) have length, breadth, zeta potential and surface area as 330 nm, 19 nm, 34.6 mV and 134 m{sup 2}/g respectively. Rhodamine B dye was degraded as 84% and 63% by R-ZnO (R1) and S-ZnO (S1) respectively under UV lamp for 3 h which is more than twice for R1 in comparison to R.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Thin-film semiconductor perspective of organometal trihalide perovskite materials for high-efficiency solar cells

Organolead trihalide perovskites (OTPs) are arising as a new generation of low-cost active materials for solar cells with efficiency rocketing from 3.5% to over 20% within only five years. From “dye” in dye sensitized solar cells to “hole conductors” and “electron conductors” in mesoscopic heterojunction solar cells, there has been a dramatic conceptual evolution on the function of OTPs in photovoltaic devices. OTPs were originally used as dyes in Gratzel cells, achieving a high efficiency above 15% which, however, did not manifest the excellent charge transport properties of OTPs. An analogy of OTPs to traditional semiconductors was drawn after the demonstration of highly efficient planar heterojunction structure OTP devices and the observation of their excellent bipolar transport properties with a large diffusion length exceeding 100 nm in CH 3 NH 3 PbI 3 (MAPbI 3 ) polycrystalline thin films. Here, this review aims to provide the most recent advances in the understanding of the origin of the high OTP device efficiency. Specifically we will focus on reviewing the progress in understanding 1) the characterization of fantastic optoelectronic property of OTPs, 2) the unusual defect physics that originate the optoelectronic property; 3) morphology control of the perovskite film from fabrication process and film post-treatment, and 4) device interface and charge transport layers that dramatically impact device efficiency in the OTP thin film devices; 5) photocurrent hysteresis; 6) tandem solar cells; 7) stability of the perovskite materials and solar cell devices.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Comparative analysis of new crystal and plastic scintillators for fast and thermal neutron detection

This paper considers scintillation and physical properties of efficient organic scintillators tested as single crystals and as components of plastics with pulse shape discrimination (PSD). For the first time, single crystals of 9,9-dimethyl-2-phenyl-9H-fluorene (PhF) were grown for studies of the basic scintillation properties of this new compound. Comparison to classical organic crystals, like anthracene, trans-stilbene, and p-terphenyl, and to more recently introduced organic glass showed that the new crystal belongs to a group of the most efficient scintillators, with light output exceeding that of trans-stilbene and PSD comparable to that of p-terphenyl. Furthermore, additional studies were conducted to evaluate scintillation performance and physical properties, like hardness and dye leaching, of plastic scintillators prepared with PhF, organic glass, and liquid diisopropylnaphthalene (DIPN) that were considered as examples for potential replacement of PPO (2,5-diphenyloxazole) in current commercial PSD plastic scintillators. Comparison of the highest performing plastic scintillators prepared with these dyes shows that PhF formulations produced a record light output (LO) increase of 69 % relative to EJ-200. Similar improvements obtained with 6 Li-loaded formulations showed that future development of PSD plastics should not be limited to use of PPO but must involve the search and exploration of new efficient dyes that may lead to discovery of much brighter organic scintillators with improved physical properties required for fast and thermal neutron detection, fast neutron spectroscopy, and antineutrino detection applications.

9,9-dimethyl-2-phenyl-9H-fluorene↗

Use of high throughput screening methods to study dual-functional crosslinkable latexes

Herein, structure-formulation-property relationships for crosslinkable core-shell latexes were studied initially using high throughput screening methods and then using conventional experimental methods to determine optimum coating formulations. Two approaches that are used within coatings technology to improve sustainability are reduction in volatile organic compounds (VOC) and reduction in energy needed to cure coatings. Hybrid crosslinkable core-shell latexes have shown potential in meeting these challenges where film properties provided by particle coalescence are not sufficient and chemical crosslinking is needed. However, with numerous parameters involved such as latex particle architecture, nature and amount of crosslinker, and curing conditions, the screening of formulations via conventional coating testing methods becomes laborious and time-consuming. The results from high-throughput dye extraction and puncture testing were compared to data from conventional testing methods such as chemical resistance (MEK double rubs), pendulum hardness, and tensile testing to identify correlations. The dye extraction results have shown a strong correlation to solvent resistance and pendulum hardness data whereas toughness from puncture testing data correlated to tensile testing. Both high throughput dye extraction and puncture testing methods can be used for the accelerated screening of crosslinkable coating formulations to optimize curing parameters to achieve the best coating performance.

36 MATERIALS SCIENCE↗

Drug discovery efforts at George Mason University

With over 39,000 students, and research expenditures in excess of $200 million, George Mason University (GMU) is the largest R1 (Carnegie Classification of very high research activity) university in Virginia. Mason scientists have been involved in the discovery and development of novel diagnostics and therapeutics in areas as diverse as infectious diseases and cancer. Below are highlights of the efforts being led by Mason researchers in the drug discovery arena. To enable targeted cellular delivery, and non-biomedical applications, Veneziano and colleagues have developed a synthesis strategy that enables the design of self-assembling DNA nanoparticles (DNA origami) with prescribed shape and size in the 10 to 100 nm range. The nanoparticles can be loaded with molecules of interest such as drugs, proteins and peptides, and are a promising new addition to the drug delivery platforms currently in use. The investigators also recently used the DNA origami nanoparticles to fine tune the spatial presentation of immunogens to study the impact on B cell activation. These studies are an important step towards the rational design of vaccines for a variety of infectious agents. To elucidate the parameters for optimizing the delivery efficiency of lipid nanoparticles (LNPs), Buschmann, Paige and colleagues have devised methods for predicting and experimentally validating the pKa of LNPs based on the structure of the ionizable lipids used to formulate the LNPs. These studies may pave the way for the development of new LNP delivery vehicles that have reduced systemic distribution and improved endosomal release of their cargo post administration. To better understand protein-protein interactions and identify potential drug targets that disrupt such interactions, Luchini and colleagues have developed a methodology that identifies contact points between proteins using small molecule dyes. The dye molecules noncovalently bind to the accessible surfaces of a protein complex with very high affinity, but are excluded from contact regions. When the complex is denatured and digested with trypsin, the exposed regions covered by the dye do not get cleaved by the enzyme, whereas the contact points are digested. The resulting fragments can then be identified using mass spectrometry. The data generated can serve as the basis for designing small molecules and peptides that can disrupt the formation of protein complexes involved in disease processes. For example, using peptides based on the interleukin 1 receptor accessory protein (IL-1RAcP), Luchini, Liotta, Paige and colleagues disrupted the formation of IL-1/IL-R/IL-1RAcP complex and demonstrated that the inhibition of complex formation reduced the inflammatory response to IL-1B. Working on the discovery of novel antimicrobial agents, Bishop, van Hoek and colleagues have discovered a number of antimicrobial peptides from reptiles and other species. DRGN-1, is a synthetic peptide based on a histone H1-derived peptide that they had identified from Komodo Dragon plasma. DRGN-1 was shown to disrupt bacterial biofilms and promote wound healing in an animal model. The peptide, along with others, is being developed and tested in preclinical studies. Other research by van Hoek and colleagues focuses on in silico antimicrobial peptide discovery, screening of small molecules for antibacterial properties, as well as assessment of diffusible signal factors (DFS) as future therapeutics. The above examples provide insight into the cutting-edge studies undertaken by GMU scientists to develop novel methodologies and platform technologies important to drug discovery.

59 BASIC BIOLOGICAL SCIENCES↗

Use of a combined effect model approach for discriminating between ABCB1- and ABCC1-type efflux activities in native bivalve gill tissue

Aquatic organisms, such as bivalves, employ ATP binding cassette (ABC) transporters for efflux of potentially toxic chemicals. Anthropogenic water contaminants can, as chemosensitizers, disrupt efflux transporter function enabling other, putatively toxic compounds to enter the organism. Applying rapid amplification of cDNA ends (RACE) PCR we identified complete cDNAs encoding ABCB1- and ABCC1-type transporter homologs from zebra mussel providing the molecular basis for expression of both transporter types in zebra mussel gills. Further, efflux activities of both transporter types in gills were indicated with dye accumulation assays where efflux of the dye calcein-am was sensitive to both ABCB1- (reversin 205, verapamil) and ABCC1- (MK571) type specific inhibitors. The assumption that different inhibitors targeted different efflux pump types was confirmed when comparing measured effects of binary inhibitor compound mixtures in dye accumulation assays with predictions from mixture effect models. Effects by the MK571/reversin 205 mixture corresponded better with independent action, whereas reversin 205/verapamil joint effects were better predicted by the concentration addition model indicating different and equal targets, respectively. The binary mixture approach was further applied to identify the efflux pump type targeted by environmentally relevant chemosensitizing compounds. Pentachlorophenol and musk ketone, which were selected after a pre-screen of twelve compounds that previously had been identified as chemosensitizers, showed mixture effects that corresponded better with concentration addition when combined with reversine 205 but with independent action predictions when combined with MK571 indicating targeting of an ABCB1-type efflux pump by these compounds. - Highlights: • Sequences and function of ABC efflux transporters in bivalve gills were explored. • Full length Dreissena polymorpha abcb1 and abcc1 cDNA sequences were identified. • A mixture effect design with inhibitors was applied in transporter activity assays. • ABCB1- and ABCC-type efflux activities were distinguished in native gill tissue. • Inhibitory action of environmental chemicals targeted ABCB1-type efflux activity.

60 APPLIED LIFE SCIENCES↗

Nanoconfinement and Mass Transport in Silica Mesopores: the Role of Charge at the Single Molecule and Single Pore Levels

Polarization-dependent single molecule tracking was employed to simultaneously probe the translational and orientational diffusion of four perylene diimide (PDI) dyes, having different lengths and charges, within the one-dimensional (1D) nanoscale pores of surfactant-templated mesoporous silica films. The wide-field fluorescence videos acquired reveal that a significant fraction of the molecules follow 1D pathways and exhibit highly polarized fluorescence, consistent with their orientational confinement. Single-frame step size distributions prepared from these data were fit to a new model that accurately describes the distribution for 1D Fickian diffusion in the presence of finite localization precision. Average diffusion coefficients obtained from mean square displacement (D MSD ) data were 20–100% larger for the two uncharged PDIs compared to the charged PDIs, reflecting electrostatic interactions of the latter with oppositely charged sites on the cationic surfactant headgroups and deprotonated silanol sites on the pore walls. Polarization-dependent tracking data show that the longest uncharged PDI was most strongly confined, while the three shorter dyes were less confined. The cationic PDI produced a wobbling angle distribution that was broader than the others, suggesting it explores more of the pore diameter. In conclusion, the results provide new knowledge on the mechanisms by which the dye molecules interact with the pore-filling medium and the pore surfaces, helping to elucidate the factors controlling the rate of mass transport.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cyanine-Incorporated Amorphous Polymeric Carbon Dots for Optical Reactive Oxygen Species Sensing

Reactive oxygen species (ROS) are common cellular oxidants that when overproduced by cellular stressors cause harm to cells. Detection of ROS is of utmost importance to understanding a wide variety of cellular function and toxicity mechanisms. Conventional ROS fluorescence assays involve using a single dye to visualize the ROS quantity. Herein, we describe ROS-sensitive, fluorescent-dye-incorporated carbon dots with dual fluorescence capabilities and good biocompatibility. Carbon dots (CDs) made of citric acid and urea were synthesized with incorporated cyanine-3-amine (Cy3), a bright red fluorescent dye, to create Cy3-CDs. Additionally, to get Cy3 into the ROS-sensitive form, this work demonstrated that Cy3 alone and Cy3 within carbon dots can be electrochemically reduced to their colorless ROS-sensitive form. Cy3, CDs, and Cy3-CDs are all responsive to additions of superoxide, leading to an increase in the fluorescence. Overall, this work examines how O 2 •– and additional oxidizers interact with CDs, Cy3, and Cy3-CDs, and molecular-level hypotheses are explored that will inform the design of future carbon dot-based ROS sensors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Using Surface Amide Couplings to Assemble Photocathodes for Solar Fuel Production Applications

A facile surface-amide coupling method was examined to attach dye and catalyst molecules to silatrane-decorated NiO electrodes. Using this method, electrodes with a push-pull dye were assembled, and characterized by photoelectrochemistry and transient absorption spectroscopy. The dye-sensitized electrodes exhibited hole injection into NiO and good photoelectrochemical stability in water, highlighting the stability of the silatrane anchoring group and the amide linkage. The amide coupling protocol was further applied to electrodes that contain a molecular proton reduction catalyst for use in photocathode architectures. Evidence for catalyst reduction was observed during hotoelectrochemical measurements and via fs-transient absorption spectroscopy demonstrating the possibility for application in photocathodes.

solar fuels, photocathode, Nickel oxide, silatrane↗

Clusters of Nanoscale Liposomes Modulate the Release of Encapsulated Species and Mimic the Compartmentalization Intrinsic in Cell Structures

We report the ability to place a high concentration of liposomes in a confined volume as a multicompartment cluster that mimics biological cells and allows for the modulation of release of encapsulated species. The formation of these coated multicompartmental structures is achieved by first binding liposomes into clusters before encapsulating them within a two-dimensional metal–organic framework composed of tannic acid coordinated with a metal ion. The essential feature is a molecularly thin skin over a ssystem of clustered liposomes in a pouch. The structural features of these pouches are revealed by small-angle scattering and electron microscopy. Through cryogenic electron microscopy, clusters with intact liposomes are observed that appear to be encapsulated within a pouch. Small-angle X-ray scattering shows the emergence of a relatively weak Bragg peak at q = 0.125 Å–1, possibly indicating the attachment of the bilayers of adjacent liposomes. The metal–phenolic network (MPN) forms a nanosized conformal coating around liposome clusters, resulting in the reduced release rate of the encapsulated rhodamine B dye. We further show the possibility of communication between the adjacent nanocompartments in the cluster by demonstrating enhanced energy transfer using fluorescence resonance energy transfer (FRET) experiments where the lipophilic donor dye 3,3'-dioctadecyloxacarbocyanine perchlorate (DiO) incorporated within one liposomal compartment transfers energy upon excitation to the lipophilic acceptor dye 1,1'-dioctadecyl-3,3,3',3'-tetramethylindocarbocyanine perchlorate (DiI) in a neighboring liposomal compartment due to their close proximity within the multicompartmental cluster. As a result, these observations have significance in adapting these multicompartmental structures that mimic biological cells for cascade reactions and as new depot drug delivery systems.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Simulating One-Photon Absorption and Resonance Raman Scattering Spectra Using Analytical Excited State Energy Gradients within Time-Dependent Density Functional Theory

A parallel implementation of analytical time-dependent density functional theory gradients is presented for the quantum chemistry program NWChem. The implementation is based on the Lagrangian approach developed by Furche and Ahlrichs. To validate our implementation, we first calculate the Stokes shifts for a range of organic dye molecules using a diverse set of exchange-correlation functionals (traditional density functionals, global hybrids, and range-separated hybrids) followed by simulations of the one-photon absorption and resonance Raman scattering spectrum of the phenoxyl radical, the well-studied dye molecule rhodamine 6G, and a molecular host–guest complex (TTFcCBPQT 4+ ). The study of organic dye molecules illustrates that B3LYP and CAM-B3LYP generally give the best agreement with experimentally determined Stokes shifts unless the excited state is a charge transfer state. Absorption, resonance Raman, and fluorescence simulations for the phenoxyl radical indicate that explicit solvation may be required for accurate characterization. For the host–guest complex and rhodamine 6G, it is demonstrated that absorption spectra can be simulated in good agreement with experimental data for most exchange-correlation functionals. Finally, however, because one-photon absorption spectra generally lack well-resolved vibrational features, resonance Raman simulations are necessary to evaluate the accuracy of the exchange-correlation functional for describing a potential energy surface.

Environmental Molecular Sciences Laboratory↗