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Predicting the reaction kinetics, that is, how fast a reaction can happen in a solution, is essential information for many processes, such as industrial chemical manufacturing, refining, synthesis and separation of petroleum products, environmental processes in air and water, biological reactions in cells, biosensing, and drug delivery. Collision theory was originally developed to explain the reaction kinetics of gas reactions with no dilution. For a reaction in a diluted inert gas solution or a diluted liquid solution, diffusion often dominates the collision process. Thus, it is necessary to include diffusion in such a calculation. Traditionally, the classical Smoluchowski rate is used as a starting point to predict the collision frequency of two molecules in a diluted solution. In this report, a different collision model is derived from the adsorption of molecules on a flat surface. A surprising result is obtained, showing that the reaction order for bimolecular reactions should be 2 and 1/3 instead of 2, following a fractal reaction kinetics.

A physical chemistry lab for undergraduate students described in this report is about applying kinetic models to analyze the spread of COVID-19 in the United States and obtain the reproduction numbers. The susceptible-infectious-recovery (SIR) model and the SIR-vaccinated (SIRV) model are explained to the students and are used to analyze the COVID-19 spread data from U.S. Centers for Disease Control and Prevention (CDC). The basic reproduction number R0 and the real-time reproduction number Rt of COVID-19 are extracted by fitting the data with the models, which explains the spreading kinetics and provides a prediction of the spreading trend in a given state. The procedure outlined here shows the differences between the SIR model and the SIRV model. The SIRV model considers the effect of vaccination which helps explain the later stages of the ongoing pandemic. The predictive power of the models is also shown giving the students some certainty in the predictions they made for the following months.

It is an unavoidable question raised by Albert Einstein if quantum theory is complete. The wavefunctions of elements are now constructed from fitting the experimental data which has made quantum chemistry empirical for almost all elements and molecules. It is our best interest to come up with a simpler model to fit the data regardless of our wish to understand reality in a more intuitive and accurate way than classical quantum mechanics. In this manuscript, I proposed an equation that quantizes the energies orders of magnitude faster than classical quantum mechanics. I assumed that the energy density distributions along space and time in a quantum system are uniform according to the 1st law of thermodynamics. Thus, the complementary energy contributions are added to the classical solutions of the 1D particle in a box problem, making the energy density a complex distribution function over space and time. Then the concept is extended to the free rotation problem with an equation significantly different than the classical Schrödinger equation. This new equation is inspired by the energy conservation method used in solving classical mechanics problems such as the pendulum problem. The picturized energy distribution functions and associated time evolution are described in movies for comparison between example classical wave functions and the energy density functions. The radial wavefunctions for the hydrogen atom and harmonic oscillator are derived. We can see that the new equation is much simpler than Schrödinger equation in obtaining consistent quantized rotational and vibrational energy levels. Thus, it has the potential to be widely used to free up computational pressure in modern quantum chemistry calculations.

Research output can be evaluated with productivity and impact, which are quantified by the numbers of publications and citations, respectively. The H-index unifies both factors. However, as an extensive variable, it grows with quantity of research output and favors senior researchers over juniors. In this report, by analyzing the data of the world top 2% scientists (n = 179,597) from an online database, we found that H-index follows power laws with both impact and productivity in a minimalist fitting with only one free parameter. We propose intensive indices (QN and QC) to measure quality research by comparing the actual H-index of a researcher with the power-law fitted H-indices from the top 2% scientists with the same numbers of publications and citations respectively. We further calculated a dynamic research quality (Q1=QN/QC) and a reduced index (Q2=(QNQC)0.5) to evaluate research quality over time. We rationalized that the power law dependency of quality research is due to its heterogeneous production pathways that require extra effort with respect to "regular” research output. A major advantage of these indices is that they are relative to the academic peers with similar accomplishments in publications and citations, and therefore, are independent of career stages. Another advantage is that the average indices are close to 1.0, giving an easily comprehensible physical significance of the indices.

Predicting the reaction kinetics, that is, how fast a reaction can happen in a solution, is essential information for many processes, such as industrial chemical manufacturing, refining, synthesis and separation of petroleum products, environmental processes in air and water, biological reactions in cells, biosensing, and drug delivery. Collision theory was originally developed to explain the reaction kinetics of gas reactions with no dilution. For a reaction in a diluted inert gas solution or a diluted liquid solution, diffusion often dominates the collision process. Thus, it is necessary to include diffusion in such a calculation. Traditionally the classical Smoluchowski rate is used as a starting point to predict the collision frequency of two molecules in a diluted solution. In this report, a different collision model is derived from the adsorption of molecules on a flat surface. A surprising result is obtained showing that the reaction order for biomolecular reaction should be 2 and 1/3 instead of 2, following a fractal reaction kinetics.

Predicting the reaction kinetics, that is, how fast a reaction can happen in a solution, is essential information for many processes, such as industrial chemical manufacturing, refining, synthesis and separation of petroleum products, environmental processes in air and water, biological reactions in cells, biosensing, and drug delivery. Collision theory was originally developed to explain the reaction kinetics of gas reactions with no dilution. For a reaction in a diluted inert gas solution or a diluted liquid solution, diffusion often dominates the collision process. Thus, it is necessary to include diffusion in such a calculation. Traditionally the classical Smoluchowski rate is used as a starting point to predict the collision frequency of two molecules in a diluted solution. In this report, a different collision model is derived from the adsorption of molecules on a flat surface. A surprising result is obtained showing that the reaction order for biomolecular reaction should be 2 and 1/3 instead of 2, following a fractal reaction kinetics.

Predicting the reaction kinetics, i.e., how fast a reaction can happen in a solution, is essential information for many processes, such as industrial chemical manufacturing, refining, synthesis and separation of petroleum products, environmental processes in air and water, biological reactions in cells, biosensing, and drug delivery. Collision theory was originally developed to explain the reaction kinetics of gas reactions with no dilution. For a reaction in a diluted inert gas solution or a diluted liquid solution, diffusion often dominates the collision process. Thus, it is necessary to include diffusion in such a calculation. Traditionally the classical Smoluchowski rate is used as a starting point to predict the collision frequency of two molecules in a diluted solution. In this report, a different collision model is derived from the adsorption of molecules on a flat surface and used to explain the collision frequency more intuitively than the Smoluchowski model in diluted solution.

Bioimaging in the near-infrared window is of great importance to study the dynamic processes in vivo with deep penetration, high spatiotemporal resolution, and minimal tissue absorption, scattering...

Automated in-field methods for measuring dissolved reactive phosphorus (DRP) over a large concentration range are in high demand for the purpose of better understanding the biogeochemistry of phosphorus in the river-estuary-coast continuum to the open ocean. Here, an automated portable and robust analyzer was described for the determination of nanomolar to micromolar levels of DRP in natural waters. The quantification of DRP was based on classic phosphomolybdenum blue (PMB) chemistry. All the components of the analyzer were computer-controlled using LabVIEW-based laboratory-programmed software. When equipped with a 3 cm Z-type flow cell, the system demonstrated linearity with concentrations up to 12 μmol L-1, a sampling rate of 20 h-1, a limit of detection of 0.11 μmol L-1, and relative standard deviations (RSDs) of 0.4-4.6% (n = 11-576). When a solid-phase extraction cartridge was combined with the analyzer, the PMB formed from the sample was automatically concentrated on the hydrophilic-lipophilic balanced sorbent. The concentrated PMB compound was eluted with NaOH solution and measured in the spectrophotometric system. Under optimal conditions, the nanomolar-level mode afforded a sampling rate of 8 h-1, a limit of detection of 1.7 nmol L-1, and RSDs of 3.0-5.7% (n = 11-120). The system exhibited advantages that included a wide linear range, high sensitivity and reproducibility, low reagent consumption, and insignificant interference from salinity, silicate, arsenate, and other P-containing compounds. The system was successfully applied for discrete sample analysis, fixed site online monitoring, and the real-time underway measurement of DRP in riverine-estuarine-coastal waters.

Mixed halide lead perovskite such as methylammonium lead iodide bromides MAPb(BrxI1-x)3 have emerged as one of the most promising materials of future solar cells, offering high power conversion efficiencies and bandgap tunability. Among other factors, the reversible phase segregation under even low light intensities is still limiting their potential use. During this process, the material segregates locally into iodide-rich and bromide-rich phases, lowering the effective bandgap energy. While several studies have been done to illuminate the mechanism and suppression of phase segregation, fundamental aspects remain unclear. Phase compositions after segregation vary extensively between different studies and the exact amounts of phases often remain unmentioned. For iodide-rich phases, the end-point compositions at around x=0.2 are widely accepted but the proportion of the phase is difficult to measure. In this report, we observe the phase segregation using spectroscopic ellipsometry, a powerful, nondestructive technique that has been employed in the study of film degradation before. We obtained dynamic ellipsometric measurements from x=0.5 mixed halide lead perovskite thin films protected by a polystyrene layer under green laser light with a power density of ~11 W/cm2. Changes in the bandgap region can be correlated to the changes in composition caused by phase segregation, allowing for the kinetics to be observed. Time constants between 1.7(± 0.7)×10-3 s-1 for the segregation and 1.5(± 0.6)×10-4 s-1 for recovery were calculated. We expect ellipsometry to serve as a complementary technique to other spectroscopies in studying mixed-halide lead perovskites phase segregation in the future.

In this manuscript, I speculated that the energy density distributions along space and time in a quantum system are uniform. Thus, the complementary energy contributions are added to the classical solutions of the 1D particle in a box problem, making the energy density a complex distribution function over space and time. Then the concept is extended to the free rotation problem with a Hamiltonian slightly different than the classical Schrödinger equation. The picturized energy distribution functions and associated time evolution are described in movies for comparison between example classical wave functions and the energy density functions. The wave functions for the hydrogen atom are then guessed based on the historical solutions.

Here an analytical solution of Fick’s 2nd law is used to predict the diffusion and the stochastic adsorption of single diluted solute molecules on flat and patterned surfaces. The equations are then compared to the results of several numerical Monte Carlo simulations using a random walk model. The 1D diffusion simulations clarify that the dependence of the solute-surface collision rate on the observation-time (measurement time resolution) is because of the multiple collisions of the same molecules over different time regions. It also surprisingly suggests that due to the self-mimetic fractal function of diffusion, the equation should be corrected by a factor of two. The absorption rate of solute on an adsorptive surface is found to follow a power-law decay function due to an evolving concentration gradient near the surface along with the depletion of the bulk solute molecules on the surface, for example, in a self-assembled monolayer adsorption kinetics. Thus, the analytical equations developed to calculate the collision at a fixed measuring frequency can be extended to map the whole curve over time. In the last section of this work, 3D diffusion simulations suggest that the analytical solution is valid to predict the adsorption rate of the bulk solute to a small group of adsorptive target molecules/area on a bouncing surface, which is a critical process in analyzing the kinetics of many bio-sensing platforms.

Mixed-halide lead perovskites (MHPs) are promising materials for photovoltaics and optoelectronics due to their highly tunable bandgaps. However, they phase-segregate under continuous illumination and/or electric field, whose mechanism is still under debate. Herein, we systematically measure the phase-segregation behavior of CH3NH3Pb(BrxI1-x)3 MHPs as a function of excitation intensity and nominal halide ratio by in situ photoluminescence micro-spectroscopy. We encapsulate the MHPs with a layer of polystyrene polymer film to isolate them from the effects of the immediate atmosphere. Under this passivated condition, the phase segregation of the MHPs is very different from those without polymer passivation reported in the literature. The initial phase segregation to I-rich and Br-rich phase is observed followed by the formation of a new mixed-halide phase within several seconds that has not been reported before. We observe that the photothermal effect is amplified at the small-size I-rich domains which significantly changes the local phase segregation in the otherwise uniform film as early as milliseconds after illumination.

Molecular orientation within organic solids limits the range of applicable surface reactions, with reactive functionalities often recessed and inaccessible to adsorbates. To induce reactivity in heretofore inert orientations of acenes, a defect-mediated mechanism is utilized to functionalize thin-film phase pentacene. This mechanism was demonstrated via correlation of reaction data to defect density, determined via polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS) and atomic force microscopy (AFM). By controllably varying the amount of grain boundaries in the acene films, the reaction can be varied from near zero to coverage exceeding a monolayer. The extensive coverage suggests that the reaction propagates from the defects throughout the grains, a prediction borne out via direct observation of reaction progression along the surface from a single dislocation (via scanning electron microscopy). The results support a mechanism whereby the reaction is initialized at the defect si...

The development of a multipurpose integrated syringe-pump-based environmental-water analyzer ( iSEA) and its application for spectrophotometric determination of ammonium is presented. The iSEA consists of a mini-syringe pump equipped with a selection valve and laboratory-programmed software written by LabVIEW. The chemistry is based on a modified indophenol method using o-phenylphenol. The effect of reagent concentrations and sample temperatures was evaluated. This fully automated analyzer had a detection limit of 0.12 μM with sample throughput of 12 h-1. Relative standard deviations at different concentrations (0-20 μM) were 0.23-3.36% ( n = 3-11) and 1.0% ( n = 144, in 24 h of continuous measurement, ∼5 μM). Calibration curves were linear ( R2 = 0.9998) over the range of 0-20 and 0-70 μM for the detection at 700 and 600 nm, respectively. The iSEA was applied in continuous real-time monitoring of ammonium variations in a river for 24 h and 14 days. A total of 1802 samples were measured, and only 0.4% was outlier data (≥3 sigma residuals). Measurements of reference materials and different aqueous samples ( n = 26) showed no significant difference between results obtained by reference and present methods. The system is compact (18 cm × 22 cm × 24 cm), portable (4.8 kg), and robust (high-resolution real-time monitoring in harsh environments) and consumes a small amount of chemicals (20-30 μL/run) and sample/standards (2.9 mL/run).

Though surface modifications of organic thin films dramatically improve optoelectronic device performance, chemistry at organic surfaces presents new challenges that are not seen in conventional inorganic surfaces. This work demonstrates that the subsurface of pentacene remains highly accessible, even to large adsorbates, and that three distinct reaction regimes (surface, subsurface, and bulk) are accessed within the narrow thermal range of 30-75 °C. Progression of this transition is quantitatively measured via polarization modulation infrared reflection absorption spectroscopy, and atomic force microscopy is used to measure the thin-film morphology. Together, they reveal the close relationship between the extent of the reaction and the morphology changes. Finally, the reaction kinetics of the pentacene thin film is measured with a series of adsorbates that have different reactivity and diffusivity in the thin film. The results suggest that reaction kinetics in the thin film is controlled by both the reactivity and the adsorbate diffusivity in the thin-film lattice, which is very different than the traditional solution kinetics that is dominated by the chemical activation barriers. Combined, these experiments guide efforts toward rationally functionalizing the surfaces of organic semiconductors to enable the next generation of flexible devices.

This article describes the design and synthesis of donor-bridge-acceptor-based semiconducting polymer dots (Pdots) that exhibit narrow-band emissions, ultrahigh brightness, and large Stokes shifts in the near-infrared (NIR) region. We systematically investigated the effect of π-bridges on the fluorescence quantum yields of the donor-bridge-acceptor-based Pdots. The Pdots could be excited by a 488 or 532 nm laser and have a high fluorescence quantum yield of 33% with a Stokes shift of more than 200 nm. The emission full width at half-maximum of the Pdots can be as narrow as 29 nm, about 2.5 times narrower than that of inorganic quantum dots at the same emission wavelength region. The average per-particle brightness of the Pdots is at least 3 times larger than that of the commercially available quantum dots. The excellent biocompatibility of these Pdots was demonstrated in vivo, and their specific cellular labeling capability was also approved by different cell lines. By taking advantage of the durable brightness and remarkable stability of these NIR fluorescent Pdots, we performed in vivo microangiography imaging on living zebrafish embryos and long-term tumor monitoring on mice. We anticipate these donor-bridge-acceptor-based NIR-fluorescent Pdots with narrow-band emissions to find broad use in a variety of multiplexed biological applications.

Patterning semiconducting materials are important for many applications such as microelectronics, displays, and photodetectors. Lead halide perovskites are an emerging class of semiconducting materials that can be patterned via solution-based methods. Here we report an all-benchtop patterning strategy by first generating a patterned surface with contrasting wettabilities to organic solvents that have been used in the perovskite precursor solution then spin-coating the solution onto the patterned surface. The precursor solution only stays in the area with higher affinity (wettability). We applied sequential sunlight-initiated thiol-ene reactions to functionalize (and pattern) both glass and conductive fluorine-doped tin oxide (FTO) transparent glass surfaces. The functionalized surfaces were measured with the solvent contact angles of water and different organic solvents and were further characterized by XPS, selective fluorescence staining, and selective DNA adsorption. By simply spin-coating and baking the perovskite precursor solution on the patterned substrates, we obtained perovskite thin-film microarrays. The spin-coated perovskite arrays were characterized by XRD, AFM, and SEM. We concluded that Patterned substrate prepared via sequential sunlight-initiated thiol-ene click reactions is suitable to fabricate perovskite arrays via the benchtop process. In addition, the same patterned substrates can be reused several times until a favorable perovskite microarray is acquired. Among a few conditions we have tested, DMSO solvent and modified FTO surfaces with alternatively carboxylic acid and alkane is the best combination to obtain high-quality perovskite microarrays. The solvent contact angle of DMSO on carboxylic acid-modified FTO surface is nearly zero and 65±3o on octadecane modified FTO surface.

A revised article has been accepted by ACS Applied Materials and Interfaces. The photoluminescence (PL) of organolead halide perovskites (OHPs) is sensitive to its surface conditions, especially surface defect states, making the PL of small OHP crystals an effective way to report their surface states. At the ensemble level, when averaging a lot of nanocrystals, the photoexcitation of OHP nanorods under inert nitrogen (N2) atmosphere leads to PL decline, while subsequent exposure to oxygen (O2) results to reversible PL recovery. At the single-particle level, individual OHP nanorods photoblinks, whose probability is dependent on both the excitation intensity and the O2 concentration. Combining the two sets of information, we are able to quantitatively evaluating the interaction between a single surface defect and a single O2 molecule using a kinetic model. This model provides fundamental insights that could help reconcile the contradicting views on the interactions of molecular O2 with OHP materials and help design a suitable OHP interface for a variety of applications in photovoltaics and optoelectronics.

We demonstrate a two-step data analysis method to increase the accuracy of single-molecule Forster Resonance Energy Transfer (smFRET) experiments. Most current smFRET studies are at a time resolution on the millisecond level. When the system also contains molecular dynamics on the millisecond level, simulations show that large errors are present (e.g., > 40%) because false state assignment becomes significant during data analysis. We introduce and confirm an additional step after normal smFRET data analysis that is able to reduce the error (e.g., < 10%). The idea is to use Monte Carlo simulation to search ideal smFRET trajectories and compare them to the experimental data. Using a mathematical model, we are able to find the matches between these two sets, and back guess the hidden rate constants in the experimental results.

YOYO-1 is a commonly used cyanine dye for DNA staining that is fluorescently bright in DNA but very dim in water. The major assumption of its excited electron decay pathway is thermal relaxation via the rotation at a bridging methine that connects the two moieties of the molecule, i.e. photo-isomerization. In this report, we use femtosecond transient absorption spectroscopy to directly measure the excited electron decay, the hole refill, and the hot ground state rise and decay. The data suggest that the first step of the photo-isomerization involves a charge transfer to quench the holes and vibrational activation of the molecules to a hot ground state.

YOYO-1 is a commonly used cyanine dye for DNA staining that is fluorescently bright in DNA but very dim in water. The major assumption of its excited electron decay pathway is thermal relaxation via the rotation at a bridging methine that connects the two moieties of the molecule, i.e. photo-isomerization. In this report, we use femtosecond transient absorption spectroscopy to directly measure the excited electron decay, the hole refill, and the hot ground state rise and decay. The data suggest that the first step of the photo-isomerization involves a charge transfer to quench the holes and vibrational activation of the molecules to a hot ground state.

The tunable nature of weak polyelectrolyte multilayers makes them ideal candidates for drug loading and delivery, water filtration, and separations, yet the lateral transport of charged molecules in these systems remains largely unexplored at the single molecule level. We report the direct measurement of the charge-dependent, pH-tunable, multimodal interaction of single charged molecules with a weak polyelectrolyte multilayer thin film, a 10 bilayer film of poly(acrylic acid) and poly(allylamine hydrochloride) PAA/PAH. Using fluorescence microscopy and single-molecule tracking, two modes of interaction were detected: (1) adsorption, characterized by the molecule remaining immobilized in a subresolution region and (2) diffusion trajectories characteristic of hopping (D ∼ 10(-9) cm(2)/s). Radius of gyration evolution analysis and comparison with simulated trajectories confirmed the coexistence of the two transport modes in the same single molecule trajectories. A mechanistic explanation for the probe and condition mediated dynamics is proposed based on a combination of electrostatics and a reversible, pH-induced alteration of the nanoscopic structure of the film. Our results are in good agreement with ensemble studies conducted on similar films, confirm a previously-unobserved hopping mechanism for charged molecules in polyelectrolyte multilayers, and demonstrate that single molecule spectroscopy can offer mechanistic insight into the role of electrostatics and nanoscale tunability of transport in weak polyelectrolyte multilayers.

We demonstrate the application of super-localization microscopy to identify sequence-specific portions of single-stranded DNA (ssDNA) with sequence resolution of 50 nucleotides, corresponding to a spatial resolution of 30 nm. Super-resolution imaging was achieved using a variation of a single-molecule localization method, termed as ‘motion blur’ point accumulation for imaging in nanoscale topography (mbPAINT). The target ssDNA molecules were immobilized on the substrate. Short, dye-labeled, and complementary ssDNA molecules stochastically bound to the target ssDNA, with repeated binding events allowing super-resolution. Sequence specificity was demonstrated via the use of a control, non-complementary probe. The results support the possibility of employing relatively inexpensive short ssDNAs to identify gene sequence specificity with improved resolution in comparison to the existing methods.

We demonstrate the formation of molecular monolayers of π-conjugated organic molecules on nanocrystalline TiO(2) surfaces through the thermal grafting of benzyl and aryl halides. X-ray photoelectron spectroscopy and Fourier-transform infrared spectroscopy were used to characterize the reactivity of aryl and benzyl chlorides, bromides, and iodides with TiO(2) surfaces, along with controls consisting of nonhalogenated compounds. Our results show that benzyl and aryl halides follow a similar reactivity trend (IBrClH). While the ability to graft benzyl halides is consistent with the well-known Williamson ether synthesis, the grafting of aryl halides has no similar precedent. The unique reactivity of the TiO(2) surface is demonstrated using nuclear magnetic resonance spectroscopy to compare the surface reactions with the liquid-phase interactions of benzyl and aryl iodides with tert-butanol and -butoxide anion. While the aryl iodides show no detectable reactivity with a tert-butanol/tert-butoxide mixture, they react with TiO(2) within 2 h at 50 °C. Atomic force microscopy studies show that grafting of 4-iodo-1-(trifluoromethyl)benzene onto the rutile TiO(2)(110) surface leads to a very uniform, homogeneous molecular layer with a thickness of ∼0.45 nm, demonstrating formation of a self-terminating molecular monolayer. Thermal grafting of aryl iodides provides a facile route to link π-conjugated molecules to TiO(2) surfaces with the shortest possible linkage between the conjugated electron system and the TiO(2).

Herein we introduce a novel strategy based on capillary force lithography (CFL) to fabricate asymmetric polymeric ring structures by applying both shear and nomal forces to a poly(dimethylsiloxane) stamp. The mechanism for the formation of asymmetric rings is caused by the deflection of cylindrical PDMS pillars due to the shear load, which is therefore termed deflected CFL (dCFL). The asymmetric polymeric rings could be readily transferred to an underlying gold layer to generate split ring structures with tunable opening angles. Asymmetric structures based upon trigular and square-shaped pillars were also fabricated. These elements were formed into periodic arrays over surface areas as large as 1 cm(2) and may have optical and electromagnetic applications.

Here, we present a simple platform for the use of the enhanced emission of 16-mercaptohexadecanoic acid (16-MHA) capped CdSe quantum dots (QDs) as a probe for ultrasensitive copper(II) detection. In this study, the photoluminescence (PL) of the QDs was first enhanced by Ag nanoprisms which were self-assembled on Si surfaces and then further increased by photobrightening. Using this approach, the control and different analytes could be readily probed all on a single platform using fluorescence microscopy. The enhanced PL intensity of CdSe QDs was selectively quenched in the presence of Cu(2+), accompanied by the emergence of a new red-shifted luminescence band. The quenching mechanism was found to be due to a cation exchange mechanism as confirmed by X-ray photoelectron spectroscopy (XPS) measurements. Herein, we have demonstrated that this simple methodology can offer a rapid and reliable detection of Cu(2+) with a detection limit as low as 5 nM and a dynamic range up to 100 muM in a fixed fast reaction time of 5 min. The potential applications of this technique were tested in two ways, for mixed-ion solutions and in physiological fluids, and both experiments exhibited good selectivity toward Cu(2+).

Herein, we demonstrate the controlled formation of two-dimensional periodic arrays of ring-shaped nanostructures assembled from CdSe semiconductor quantum dots (QDs). The patterns were fabricated by using an evaporative templating method. This involves the introduction of an aqueous solution containing both quantum dots and polystyrene microspheres onto the surface of a planar hydrophilic glass substrate. The quantum dots became confined to the meniscus of the microspheres during evaporation, which drove ring assembly via capillary forces at the polystyrene sphere/glass substrate interface. The geometric parameters for nanoring formation could be controlled by tuning the size of the microspheres and the concentration of the QDs employed. This allowed hexagonal arrays of nanorings to be formed with thicknesses ranging from single dot necklaces to thick multilayer structures over surface areas of many square millimeters. Moreover, the diameter of the ring structures could be simultaneously controlled. A simple model was employed to explain the forces involved in the formation of nanoparticle nanorings.

Catalytic hydrogenation of nitrate (NO3−) in water on Pd−Cu ensembles has been denoted as a promising denitridation method, but its hydrogenation selectivity remains challenging. In this study, the hydrogenation selectivity of nitrate on the Pd−Cu/TiO2 systems was discussed mainly concerning the size effect of Pd−Cu ensembles in a gas−liquid cocurrent flow system. Demonstrated by their TEM images, homogeneous morphologies as well as narrow size distributions of Pd−Cu ensembles on titania have been prepared by a facile photodeposition process, and the size of the ensembles was controlled and varied with the total metal loadings. The different XRD patterns and XPS spectra of Pd−Cu/TiO2 catalysts from their corresponding monometallic counterparts suggested the formation of Pd−Cu complex on the surface of TiO2. It is first indicated that the hydrogenation selectivity of nitrate generally depends on the size of active phase with critical size of approximately 3.5 nm, below which NO2− becomes the predominant pr...

Supported metal catalysts have been used extensively in many current industrial processes. The morphology of coated metal on a support is usually an important factor affecting the efficiency of the catalyst. In this study, the investigation is focused on a photocatalytic process to coat silver clusters on titania (P-25 TiO2) with an emphasis on the morphology control of coated silver clusters. For the first time, the particle size and the deployment intervals of silver clusters are controlled with an innovative method that involves the in-situ formation of water-insoluble transitory species such as AgBr, AgCl, or Ag2O on the surface of titanium dioxide. Experimental results demonstrated that the transitory particles function as physical spacers, which temporarily occupy some of the active site on the titanium dioxide surface and act as reservoirs for Ag+ ions to keep the local Ag+ concentration on TiO2 extremely low. The silver clusters coated on titania are found to be stable in the spherical silver-3c s...

We directly measure the dynamics of the HIV trans-activation response (TAR)-DNA hairpin with multiple loops using single-molecule Förster resonance energy transfer (smFRET) methods. Multiple FRET states are identified that correspond to intermediate melting states of the hairpin. The stability of each intermediate state is calculated from the smFRET data. The results indicate that hairpin unfolding obeys a "fraying and peeling" mechanism, and evidence for the collapse of the ends of the hairpin during folding is observed. These results suggest a possible biological function for hairpin loops serving as additional fraying centers to increase unfolding rates in otherwise stable systems. The experimental and analytical approaches developed in this article provide useful tools for studying the mechanism of multistate DNA hairpin dynamics and of other general systems with multiple parallel pathways of chemical reactions.

Photolithographically generated patterns have been created on immobilized CdSe QD thin films by fine-tuning their optical properties (intensity and emission wavelength) postsynthetically. These optically modified QDs show enhanced selectivity for binding of different ligands, affording the ability to fabricate optically reconfigurable surfaces for display or sensing applications. The patterns may be readily generated with any typical optical lithographic approach.