Ultrafast Electron Transfer across a Nanocapsular Wall: Coumarins as Donors, Viologen as Acceptor, and Octa Acid Capsule as the Mediator.

Results of our study on ultrafast electron transfer (eT) dynamics from coumarins (coumarin-1, coumarin-480, and coumarin-153) incarcerated within octa acid (OA) capsules as electron donors to methyl viologen dissolved in water as acceptor are presented. Upon photoexcitation, coumarin inside the OA capsule transfers an electron to the acceptor electrostatically attached to the capsule leading to a long-lived radical-ion pair separated by the OA capsular wall. This charge-separated state returns to the neutral ground state via back electron transfer on the nanosecond time scale. This system allows for ultrafast electron transfer processes through a molecular wall from the apolar capsular interior to the highly polar (aqueous) environment on the femtosecond time scale. Employing femtosecond transient absorption spectroscopy, distinct rates of both forward (1-25 ps) and backward eT (700-1200 ps) processes were measured. Further understanding of the energetics is provided using Rehm-Weller analysis for the investigated photoinduced eT reactions. The results provide the rates of the eT across a molecular wall, akin to an isotropic solution, depending on the standard free energy of the reaction. The insights from this work could be utilized in the future design of efficient electron transfer processes across interfaces separating apolar and polar environments.

Electron-transfer dependent photocatalytic hydrogen generation over cross-linked CdSe/TiO2 type-II heterostructure.

Developing type-II heterostructures with a spatial separation of photoexcited electrons and holes is a useful route to promote photocatalytic hydrogen generation. However, few investigations on the charge transfer process across the heterojunction have been carried out, which can allow us to uncover the reaction mechanism. Herein, CdSe quantum dots (QDs) and TiO2 nanocrystals were synthesized and combined in water yielding CdSe/TiO2 type II heterostructures. It was found that mercaptopropionic acid as bifunctional molecules could bind with CdSe and TiO2 to form a cross-linked morphology. The charge carrier dynamics of bare CdSe and CdSe/TiO2 were detected using femtosecond transient absorption spectroscopy. In the presence of TiO2, the average exciton lifetime of CdSe QDs was apparently decreased, owing to the electron transfer from photoexcited CdSe to TiO2. Particularly, the electron-transfer rate from small CdSe QDs (3.0 nm) was much faster than that from big CdSe QDs (4.2 nm). The improved photocatalytic hydrogen generation was observed for CdSe/TiO2 compared to bare CdSe QDs. The enhancement factor for small CdSe QDs was higher than that for big CdSe QDs, which was in good agreement with the electron-transfer rates. This result indicated that the electron transfer between CdSe and TiO2 played an important role in photocatalytic hydrogen generation on CdSe/TiO2 type-II heterostructure. Our study provides a fundamental guidance to construct efficient heterostructured photocatalysts by delicate control of the band alignment.

Strong Visible Absorption and Broad Time Scale Excited-State Relaxation in (Ga(1-x)Zn(x))(N(1-x)O(x)) Nanocrystals.

(Ga(1-x)Zn(x))(N(1-x)O(x)) is a visible absorber of interest for solar fuel generation. We present a first report of soluble (Ga(1-x)Zn(x))(N(1-x)O(x)) nanocrystals (NCs) and their excited-state dynamics over the time window of 10(-13)-10(-4) s. Using transient absorption spectroscopy, we find that excited-state decay in (Ga0.27Zn0.73)(N0.27O0.73) NCs has both a short (<100 ps) and a long-lived component, with a long overall average lifetime of ∼30 µs. We also find that the strength of the visible absorption is comparable to that of direct band gap semiconductors such as GaAs. We discuss how these results may relate to the origin of visible absorption in (Ga(1-x)Zn(x))(N(1-x)O(x)) and its use in solar fuel generation.

Improving learning performance with happiness by interactive scenarios.

Recently, digital learning has attracted a lot of researchers to improve the problems of learning carelessness, low learning ability, lack of concentration, and difficulties in comprehending the logic of math. In this study, a digital learning system based on Kinect somatosensory system is proposed to make children and teenagers happily learn in the course of the games and improve the learning performance. We propose two interactive geometry and puzzle games. The proposed somatosensory games can make learners feel curious and raise their motivation to find solutions for boring problems via abundant physical expressions and interactive operations. The players are asked to select particular operation by gestures and physical expressions within a certain time. By doing so, the learners can feel the fun of game playing and train their logic ability before they are aware. Experimental results demonstrate that the proposed somatosensory system can effectively improve the students' learning performance.

Near infrared light-triggered drug generation and release from gold nanoparticle carriers for photodynamic therapy.

A photoprecursor Pc 227 is covalently bound onto gold nanoparticles (Au NPs) to produce the known photodynamic therapy (PDT) drug Pc 4 upon 660 nm photoirradiation. The photochemical formation of the photoproduct Pc 4 is identified by spectroscopy, chromatography, and mass spectrometry and its PDT efficacy is equal to Pc 4 when administered non-covalently by Au NPs, with the added benefit of improved covalent delivery and targeted NIR-triggered release from the covalent Pc 227-Au NP conjugate, while during transport the attached Pc 227 is quenched by the Au NP and PDT inactivated.

Photophysics of silicon phthalocyanines in aqueous media.

Phthalocyanines have been used as photodynamic therapy (PDT) agents because of their uniquely favorable optical properties and high photostability. They have been shown to be highly successful for the treatment of cancer through efficient singlet-oxygen ((1)O(2)) production. However, due to their hydrophobic properties, the considerations of solubility and cellular location have made understanding their photophysics in vitro and in vivo difficult. Indeed, many quantitative assessments of PDT reagents are undertaken in purely organic solvents, presenting challenges for interpreting observations during practical application in vivo. With steady-state and time-resolved laser spectroscopy, we show that for axial ligated silicon phthalocyanines in aqueous media, both the water:lipophile ratio and the pH have drastic effects on their photophysics, and ultimately dictate their functionality as PDT drugs. We suggest that considering the presented photophysics for PDT drugs in aqueous solutions leads to guidelines for a next generation of even more potent PDT agents.

Ultrafast photoinduced electron transfer between an incarcerated donor and a free acceptor in aqueous solution.

Supramolecular photoinduced electron transfer dynamics between coumarin 153 (C153) and 4,4'-dimethyl viologen dichloride (MV(2+)) across the molecular barrier of a host molecule, octa acid (OA), has been investigated with femtosecond time resolution. The ultrafast electron transfer from C153 to MV(2+) followed excitation with 150 fs laser pulses at a wavelength of 390 nm despite the fact that C153 was incarcerated within an OA(2) capsule. As a result, the photoexcited coumarin did not show any of the typical relaxation dynamics that is usually observed in free solution. Instead, the excited electron was transferred across the molecular wall of the capsuleplex within 20 ps. Likewise, the lifetime of the charge transfer state was short (724 ps), and electron back-transfer reestablished the ground state of the system within 1 ns, showing strong electronic coupling among the excited electron donor, host, and acceptor. When the donor was encapsulated into the host molecule, the electron transfer process showed significantly accelerated dynamics and essentially no solvent relaxation compared with that in free solution. The study was also extended to N-methylpyridinium iodide as the acceptor with similar results.

Contribution of Femtosecond Laser Spectroscopy to the Development of Advanced Optoelectronic Nanomaterials.

Femtosecond laser spectroscopy has now been a powerful technique for over a decade to investigate charge carrier dynamics in nanoscale optoelectronic systems with a temporal resolution of 100 fs (10(-13) s) or better. Both transient absorption and time-resolved photoluminescence spectroscopy are now popular spectroscopic techniques, which are well-established and provide direct insight into the charge carrier dynamics of nanomaterials. In this Perspective, we focus mainly on the developments with regard to studies of semiconductor nanostructures. Controlling the charge carrier dynamics, including hot carrier relaxation, trapping, interfacial carrier transfer, carrier multiplication, and recombination, is essential for successful energy conversion or photocatalysis, to name two major optoelectronic applications. We will show how femtosecond laser spectroscopy evolved into techniques that unveil the dynamic charge carrier properties of semiconductor nanomaterials toward heterostructures and complex nanoarchitectures and that femtosecond time-resolved laser spectroscopy can shine light on the path to novel optoelectronic structures and emergent optoelectronic technologies.

Nanoparticle ζ -potentials.

For over half a century, alternating electric fields have been used to induce particle transport, furnishing the ζ-potential of analytes with sizes ranging from a few nanometers to several micrometers. Concurrent advances in nanotechnology have provided new materials for catalysis, self-assembly, and biomedical applications, all of which benefit from a thorough understanding of particle surface charge. Therefore, the measurement of the ζ-potential via electrophoretic light scattering (ELS) has become essential for nanoparticle (NP) research. However, the interpretation of NP electrophoretic mobility, especially that of ligand-coated NPs, can be a complex undertaking. Despite the inherent intricacy of these data, key concepts from colloidal science can help to distill valuable information from ELS. In this Account, we adopt PEGylated Au NPs as an illustrative example to explore extensions of the classical theories of Smoluchowski, Hückel, and Henry to more contemporary theories for ligand-coated NP systems such as those from Ohshima, and Hill, Saville, and Russel. First, we review the basic experimental considerations necessary to understand NP electrophoretic mobility, identifying when O'Brien and White's numerical solution of the standard electrokinetic model should be adopted over Henry's closed-form analytical approximation. Next, we explore recent developments in the theory of ligand-coated particle electrophoresis, and how one can furnish accurate and meaningful relationships between measured NP mobility, ζ-potential, and surface charge. By identifying key ligand-coated NP parameters (e.g., coating thickness, permeability, molecular mass, and hydrodynamic segment size), we present a systematic method for quantitatively interpreting NP electrophoretic mobility. In addition to reviewing theoretical foundations, we describe our recent results that examine how the unique surface curvature of NPs alters and controls their properties. These data provide guidelines that can expedite the rational design of NPs for advanced uses, such as heterogeneous catalysis and in vivo drug delivery. As a practical demonstration of these concepts, we apply the ligand-coated theory to a recently developed noncovalent PEGylated Au NP drug-delivery system. Our analysis suggests that anion adsorption on the Au NP core may enhance the stability of these NP-drug conjugates in solution. In addition to providing useful nanochemistry insights, the information in this Account will be useful to biomedical and materials engineers, who use ELS and ζ-potentials for understanding NP dynamics.

Measuring electron and hole transfer in core/shell nanoheterostructures.

Using femtosecond transient absorption and time-resolved photoluminescence spectroscopy, we studied the electron versus hole dynamics in photoexcited quasi-type-II heterostructured nanocrystals with fixed CdTe core radii and varying CdSe shell coverage. By choosing the pump wavelength in resonance with the core or the shell states, respectively, we were able to measure the excited electron and hole dynamics selectively. Both, the core- and the shell-excited CdTe/CdSe nanocrystals showed the same spectral emission and photoluminescence lifetimes, indicating that ultrafast electron and hole transfer across the core/shell interface resulted in the identical long-lived charge transfer state. Both charge carriers have subpicosecond transfer rates through the interface, but the subsequent relaxation rates of the hole (τ(dec) ∼ 800 ps) and electron (τ(avg) ∼ 8 ps) are extremely different. On the basis of the presented transient absorption measurements and fitting of the steady-state spectra, we find that the electron transfer occurs in the Marcus inverted region and mixing between the CdTe exciton and charge transfer states takes place and therefore needs to be considered in the analysis.

Emergent properties resulting from type-II band alignment in semiconductor nanoheterostructures.

The development of elegant synthetic methodologies for the preparation of monocomponent nanocrystalline particles has opened many possibilities for the preparation of heterostructured semiconductor nanostructures. Each of the integrated nanodomains is characterized by its individual physical properties, surface chemistry, and morphology, yet, these multicomponent hybrid particles present ideal systems for the investigation of the synergetic properties that arise from the material combination in a non-additive fashion. Of particular interest are type-II heterostructures, where the relative band alignment of their constituent semiconductor materials promotes a spatial separation of the electron and hole following photoexcitation, a highly desirable property for photovoltaic applications. This article highlights recent progress in both synthetic strategies, which allow for material and architectural modulation of novel nanoheterostructures, as well as the experimental work that provides insight into the photophysical properties of type-II heterostructures. The effects of external factors, such as electric fields, temperature, and solvent are explored in conjunction with exciton and multiexciton dynamics and charge transfer processes typical for type-II semiconductor heterostructures.