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Multitarget engagement is considered an effective strategy to overcome the threat of bacterial infection, and antimicrobials with multiple mechanisms of action have been successful as natural chemical weaponry. Here, we synthesized a library of photosensitizer-peptoid conjugates (PsPCs) as novel antimicrobial photodynamic therapy (aPDT) agents. The peptoids, linkers, and photosensitizers were varied, and their structure-antimicrobial activity relationships against Escherichia coli were evaluated; PsPC 9 was indicated to be the most promising photoresponsive antimicrobial agent among the synthesized PsPCs. Spectroscopic analyses indicated that 9 generated singlet oxygen upon absorption of visible light (420 nm) while maintaining the weakly helical conformation of the peptoid. Mechanistic studies suggested that damage to the bacterial membrane and cleavage of DNA upon light irradiation were the main causes of bactericidal activity, which was supported by flow cytometry and DNA gel electrophoresis experiments. We demonstrated that the optimal combination of membrane-active peptoids and photosensitizers can generate an efficient aPDT agent that targets multiple sites of bacterial components and kills bacteria by membrane disruption and reactive oxygen species generation.

Despite advances of lanthanide-doped upconversion (UC) materials, the applications such as light-emitting diode and biological imaging are limited by low quantum efficiency. For this context, the understanding of unique interactions between the doped-lanthanides and the host crystals has attracted a huge amount of the researcher's interest. In particular, it was revealed that doping lanthanide ions in a non-centrosymmetric site of host lattice is the cause of relaxation of the Laporte selection rule in the 4f-4f transition of lanthanide ions. One of the layered perovskites CsBiNb

The counterion condensation in the binary mixtures of like-charged polyelectrolytes with two different molecular weights, where both are negatively charged, has been studied by conductance measurement in aqueous medium. Sodium polystyrenesulfonate with two different chain lengths have been selected as model polyelectrolyte and the investigation has been carried out in the absence of any added salt. The specific conductance-polyelectrolyte concentration data were analyzed in the light of the scaling argument for the conformation of polyion chains in solutions to quantify the fractions of free counterions. Effects of polyelectrolyte concentration, molecular weights of the components of the mixture, and solution temperature on the condensation of counterions have been investigated to explore polyion–counterion interaction, and inter- and intra-chain interactions in these polyelectrolyte mixtures. This investigation revealed that the extent of counterion condensation is significantly influenced by the mixture composition, the polyelectrolyte concentration and the temperature. Evaluation of the polyion transference numbers provided important information as to the direction of the motion of the counterions under the action of the applied electric field.

Because of their well-known optical properties, upconversion nanoparticles (UCNPs) are regarded as some of the most promising nanomaterials for bioimaging, biosensors, and solar cells. The nonblinking nature of their upconversion emissions has been a particularly beneficial advantage for live-cell imaging. However, the origin of this unique property has never been seriously investigated. We report, for the first time, the observation of stochastic photon emission (SPEM) in core/shell UCNPs (NaYF4:Yb3+,Er3+/NaYF4) on the microsecond and nanosecond time scales, even under continuous irradiation at 980 nm. This SPEM was attributed to slow “upconversion cycles”. We consider that the conventionally reported, nonblinking nature of UCNP emissions can be attributed to the averaging of SPEMs from multiple Er3+ ions and the low temporal resolution of previous observation. The off-time distribution, which possesses kinetics information for the upconversion pathways, was well fitted to a single exponential indicating...

Upconversion nanoparticles (UCNPs) have attracted enormous interest over the past few years because of their unique optical properties and potential for use in various applications such as bioimaging probes, biosensors, and light-harvesting materials for photovoltaics. The improvement of imaging resolution is one of the most important goals for UCNPs used in biological applications. Super-resolution imaging techniques that overcome the fundamental diffraction limit of light rely on the photochemistry of organic dyes or fluorescent proteins. Here we report our progress toward super-resolution microscopy with UCNPs. We found that the red emission (655 nm) of core/shell UCNPs with the structure NaYF4:Yb3+,Er3+/NaYF4 could be modulated by emission depletion (ED) of the intermediate state that interacts resonantly with an infrared beam (1540 nm). In contrast, the green emission bands (525 and 545 nm) of the UCNPs were less affected by irradiation with the infrared beam. The origin of such distinct behaviors between the green and red emissions was attributed to their different photophysical pathways.

Polystyrene microparticles were covalently impregnated into the networks of functional polyelectrolyte chains designed via a tandem run of three reactions: (i) synthesis of water-soluble polyelectrolyte, (ii) fast azidation and (iii) a &lsquo, click&rsquo, reaction, using the single-catalyst, single-pot strategy at room temperature in mild aqueous media. The model polyelectrolyte sodium polystyrenesulfonate (NaPSS) was synthesized via the well-controlled atom transfer radical polymerization (ATRP) whose halogen living-end was transformed to azide and subsequently coupled with an alkyne carboxylic acid through a &lsquo, reaction using the same ATRP catalyst, throughout. Halogen to azide transformation was fast and followed the radical pathway, which was explained through a plausible mechanism. Finally, the success of microparticle impregnation into the NaPSS network was evaluated through Kaiser assay and imaging. This versatile synthetic procedure, having a reduced number of discrete reaction steps and eliminated intermediate work-ups, has established a fast and simple pathway to design functional polymers required to fabricate stable polymer-particle composites where the particles are impregnated covalently and controllably.

Natural light-harvesting complexes (LHCs) absorb a broad spectrum of sunlight using a collection of photosynthetic pigments whose spatial arrangement is controlled by a protein matrix and exhibit efficient energy transfer. We constructed a novel light-harvesting protein mimic, which absorbs light in the UV to visible region (280-700 nm) by displaying flavone and porphyrin on a peptoid helix. First, an efficient synthesis of 4'-derivatized 7-methoxyflavone (7-MF, 3 and 4) was developed. The flavone-porphyrin-peptoid conjugate (FPPC) was then prepared via Miyaura borylation on a resin-bound peptoid followed by Suzuki coupling between the peptoid and pigment. Circular dichroism spectroscopy indicated that the FPPC underwent helix-to-loop conversion of the peptoid scaffold upon changing the solvent conditions. A distinct intramolecular energy transfer was observed from 7-MF to porphyrin with greater efficiency in the helix than that in the loop conformation of the peptoid, whereas no clear evidence of energy transfer was obtained for unstructured FPPC. We thus demonstrate the value of the helical peptoid, which provided a controlled orientation for 7-MF and porphyrin and modulated the energy transfer efficiency via conformational switching. Our work provides a way to construct a sophisticated LHC mimic with enhanced coverage of the solar spectrum and controllable energy transfer efficiency.

Quantitative imaging of magnetic field distribution was carried out using a pyrene-based magnetosensing exciplex fluorophore, pyrene-(CH2)12-O-(CH2)2-N,N-dimethylaniline (Py-12-O-2-DMA), on a conventional fluorescence microscope with an off-the-shelf LED lamp. No continuous sample supply was required for the process. The solvent system (anisole : DMF, 50 : 50 (v/v)) was carefully selected for monitoring the extent of modulation caused by the external magnetic field. The emission from Py-12-O-2-DMA increased by ca. 1.5 times under an external magnetic field of 50 mT. The pyrene-based reporter was ca. 24.7 times brighter than a previously reported phenanthrene-based complex when excited by using the widely available 355 nm excitation. Moreover, the maximum wavelength up to which Py-12-O-2-DMA could be excited (up to 380 nm) was longer than the wavelength up to which Phen-12-O-2-DMA could be excited. The combined advantages allowed the capture of magnetic field images with a high S/N ratio under milder conditions such as low illumination power, reduced sample concentration, and simpler optical setup. The system was also found to be feasible for 3D magnetic field distribution imaging by two-photon fluorescence microscopy.

Adenosine deaminase (ADA), which catalyzes the irreversible deamination of adenosine to inosine, is related to various human diseases such as tuberculous peritonitis and leukemia. Therefore, the method used to detect ADA activity and screen the effectiveness of various inhibitor candidates has important implications for the diagnosis treatment for various human diseases. A simple and rapid assay method for ADA, based on the enzymatic formation of a luminescent lanthanide complex, is proposed in this study. Inosine, an enzymatic product of ADA with stronger sensitization efficiency for Tb3+ than adenosine, produced a strong luminescence by forming an inosine-Tb3+ complex, and it enabled the direct monitoring of ADA activity in real-time. By introducing only Tb3+ to adenosine and ADA in the buffer, the enhancement of luminescence enabled the detection of a low concentration of ADA (detection limit 1.6 U/L). Moreover, this method could accurately determine the inhibition efficiency (IC50) of the known ADA inhibitor, erhythro-9-(2-hydroxy-3-nonyl)adenine (EHNA), and the inhibition of ADA could be confirmed by the naked eye. Considering its simplicity, this assay could be extended to the high-throughput screening of various ADA inhibitor candidates.

The detection of mycotoxins is crucial because of their toxicity in plants, animals, and humans. It is very important to determine whether food products are contaminated with mycotoxins such as ochratoxin A (OTA), as mycotoxins can survive heat treatments and hydrolysis. In this study, we designed a fluorescence resonance energy transfer (FRET)-based system that exploits antibody-antigen binding to detect mycotoxins more rapidly and easily than other currently available methods. In addition, we were able to effectively counteract the matrix effect in the sample by using a nitrocellulose membrane that enabled fluorescence measurement in coffee samples. The developed FRET on lateral flow immunoassay (FRET-LFI) system was used to detect OTA at a limit of detection (LOD) of 0.64 ng∙mL&minus, 1, and the test can be completed in only 30 min. Moreover, OTA in coffee samples was successfully detected at a LOD of 0.88 ng∙mL&minus, 1, overcoming the matrix effect, owing to the chromatographic properties of the capillary force of the membrane. We believe that the developed system can be used as a powerful tool for the sensitive diagnosis of harmful substances such as mycotoxins and pesticides for environmental and food quality control monitoring.

Herein, we report a siloxane-encapsulated upconversion nanoparticle hybrid composite (SE-UCNP), which exhibits excellent photoluminescence (PL) stability for over 40 days even at an elevated temperature, in high humidity, and in harsh chemicals. The SE-UCNP is synthesized through UV-induced free-radical polymerization of a sol-gel-derived UCNP-containing oligosiloxane resin (UCNP-oligosiloxane). The siloxane matrix with a random network structure by Si-O-Si bonds successfully encapsulates the UCNPs with chemical linkages between the siloxane matrix and organic ligands on UCNPs. This encapsulation results in surface passivation retaining the intrinsic fluorescent properties of UCNPs under severe conditions (e.g., 85 °C/85% relative humidity) and a wide range of pH (from 1 to 14). As an application example, we fabricate a two-color binary microbarcode based on SE-UCNP via a low-cost transfer printing process. Under near-infrared irradiation, the binary sequences in our barcode are readable enough to identify objects using a mobile phone camera. The hybridization of UCNPs with a siloxane matrix provides the capacity for highly stable UCNP-based applications in real environments.

Despite advances of lanthanide-doped upconversion (UC) materials, the applications such as light-emitting diode and biological imaging are limited by low quantum efficiency. For this context, the understanding of unique interactions between the doped-lanthanides and the host crystals has attracted a huge amount of the researcher’s interest. In particular, it was revealed that doping lanthanide ions in a non-centrosymmetric site of host lattice is the cause of relaxation of the Laporte selection rule in the 4f–4f transition of lanthanide ions. One of the layered perovskites CsBiNb2O7 is known to have non-centrosymmetric sites, which would lead to highly bright UC emission. Nevertheless, to our knowledge, there has been no research on the UC comparison between host materials of CsBiNb2O7 with other hosts. In this article, we present the UC intensity comparison of Yb3+–Er3+ ion doped CsBiNb2O7, NaYF4, BaTiO3, and SrTiO3 hosts (the UC in CsBiNb2O7:Er3+,Yb3+ was 2.4 times that of NaYF4:Er3+,Yb3+ and ∼70 times that of SrTiO3:Er3+,Yb3+). After that, we dig into UC, downshifting, and double beam system UC properties. The activator concentration was optimized by varying the doping ratio of Yb3+ and Er3+, and we found out the main reason for the concentration quenching behavior in Er3+ ion doped CsBiNb2O7 is dipole–dipole interaction. In addition, the double excitation experiment indicates that the absorption (4I15/2 → 4I13/2) factor is stronger than the stimulated emission (4I13/2 → 4I15/2) factor in CsBiNb2O7 under 1540 nm laser irradiation.

The level of chloride ions (Cl⁻) in sweat is a recognized biomarker for the genetic disorder cystic fibrosis (CF). The accurate quantitation of chloride ions in sweat is therefore a vital diagnostic tool for this life-threatening disease. In this work, a fluorescent, chloride ion chemosensor was developed by exploiting the strong interaction between silver (Ag+) and chloride ions. Using the concept of ligand displacement, six Ag+-benzimidazole complexes were prepared as candidate chloride ion chemosensors. The Ag+-2-(Furan-2-yl)-1H-benzo[d]imidazole (Ag+-FBI) complex was identified as the optimal sensor owing to its Ag+-FBI high sensitivity (limit of detection = 19 μM), short response time (

We report the excited-state intramolecular charge transfer (ICT) dynamics of 4-dimethylamino-4′-nitrobiphenyl (DNBP) in the reverse micelles (RMs) of bis(2-ethylhexyl) sulfosuccinate sodium salt (AOT) by time-resolved fluorescence and transient absorption spectroscopy. The absorption and emission bands of DNBP in the RMs appeared as blue-shifted from the maximum wavelengths of bulk methanol solution, which can be understood as the decrease of solvent polarity in the RMs. The quantum yield and excited-state lifetime of DNBP in the RMs increase enormously upon the decrease of the micelle size, which is interpreted as the decrease of the micropolarity and the increase of microviscosity in the small RMs. The efficient intersystem crossing to the triplet states and strong phosphorescence of DNBP in the near-infrared region was also observed in the small RMs, which results from the strongly restricted torsional relaxation of biphenyl group in the confined environments of the small RMs. We have observed the site-specific and micelle size-dependent excited-state dynamics of DNBP in the methanol/AOT/isooctane RMs, which may originate from the less homogeneous environment of the confined solvent pools of the RMs than bulk.

Advancements in the fabrication of upconversion nanoparticles (UCNPs) for synthetic control can enable a broad range of applications in biomedical systems. Herein, we experimentally verified the role of the hydrothermal reaction (HR) time in the synthesis of NaYF4:20%Yb3+/3%Er3+ UCNPs on their morphological evolution and phase transformation at different temperatures. Characterizations of the as-prepared UCNPs were conducted using X-ray diffraction (XRD), electron microscopy and spectroscopy, and thermogravimetric and upconversion (UC) luminescence analysis. We demonstrated that determining the optimal HR time, also referred to here as the threshold time, can produce particles with good homogeneity, hexagonal phase, and UC luminescence efficiency. Subsequently, the polymer coated UCNPs maintained their original particle size distribution and luminescence properties, and showed improved dispersibility in a variety of solvents, cellular nontoxicity, in vitro bioimaging, and biocompatibility as compared to the bare UCNP. Besides this, polyacrylic acid conjugated UCNPs (UCNP@PAA) also revealed the strong anticancer effect by conjugating with doxorubicin (DOX) as compared to the free DOX. Based on these findings, we suggest that these particles will be useful in drug-delivery systems and as in vivo bioimaging agents synchronously.

Upconversion nanoparticles (UCNPs) have attracted enormous interest over the past few years because of their unique optical properties and potential for use in various applications such as bioimaging probes, biosensors, and light-harvesting materials for photovoltaics. The improvement of imaging resolution is one of the most important goals for UCNPs used in biological applications. Super-resolution imaging techniques that overcome the fundamental diffraction limit of light rely on the photochemistry of organic dyes or fluorescent proteins. Here we report our progress toward super-resolution microscopy with UCNPs. We found that the red emission (655 nm) of core/shell UCNPs with the structure NaYF

A series of N-methoxyamide derivatives was identified and evaluated as GPR119 agonists. Several N-methoxyamides with thienopyrimidine and pyridine scaffolds showed potent GPR119 agonistic activities. Among them, compound 9c displayed good in vitro activity and potency. Moreover, compound 9c lowered glucose excursion in mice in an oral glucose tolerance test and increased GLP-1 secretion in intestinal cells.

We used a fluorescent chemical indicator of magnetic field to visualize the magnetic field around ferromag- netic nanostructures. The indicator was a chain-linked electron donoracceptor molecule, phenanthrene-(CH2)12-O-(CH2)2- dimethylaniline, that forms spin-correlated radical pairs upon photoexcitation. The magnetic field altered the coherent spin dynamics, yielding an 80% increase in exciplex fluorescence in a 0.1 T magnetic field. The magnetic field distributions were quantified to precision of 1.8 � 10 � 4 T by image analysis and agreed with finite-element nanomagnetic simulations.

The broad linewidths in absorption spectra of photosynthetic complexes obscure information related to their structure and function. Photon echo techniques represent a powerful class of time-resolved electronic spectroscopy that allow researchers to probe the interactions normally hidden under broad linewidths with sufficient time resolution to follow the fastest energy transfer events in light harvesting. Here, we outline the technical approach and applications of two types of photon echo experiments: the photon echo peak shift and two-dimensional (2D) Fourier transform photon echo spectroscopy. We review several extensions of these techniques to photosynthetic complexes. Photon echo peak shift spectroscopy can be used to determine the strength of coupling between a pigment and its surrounding environment including neighboring pigments and to quantify timescales of energy transfer. Two-dimensional spectroscopy yields a frequency-resolved map of absorption and emission processes, allowing coupling interactions and energy transfer pathways to be viewed directly. Furthermore, 2D spectroscopy reveals structural information such as the relative orientations of coupled transitions. Both classes of experiments can be used to probe the quantum mechanical nature of photosynthetic light-harvesting: peak shift experiments allow quantification of correlated energetic fluctuations between pigments, while 2D techniques measure quantum beating directly, both of which indicate the extent of quantum coherence over multiple pigment sites in the protein complex. The mechanistic and structural information obtained by these techniques reveals valuable insights into the design principles of photosynthetic light-harvesting complexes, and a multitude of variations on the methods outlined here.

A time-nonlocal quantum master equation coupled with a perturbative scheme to evaluate the third-order polarization in the phase-matching direction k(s) = -k(1) + k(2) + k(3) is used to efficiently simulate three-pulse photon-echo signals. The present method is capable of describing photon-echo peak shifts including pulse overlap and bath memory effects. In addition, the method treats the non-Markovian evolution of the density matrix and the third-order polarization in a consistent manner, thus is expected to be useful in systems with rapid and complex dynamics. We apply the theoretical method to describe one- and two-color three-pulse photon-echo peak shift experiments performed on a bacterial photosynthetic reaction center and demonstrate that, by properly incorporating the pulse overlap effects, the method can be used to describe simultaneously all peak shift experiments and determine the electronic coupling between the localized Q(y) excitations on the bacteriopheophytin (BPhy) and accessory bateriochlorophyll (BChl) in the reaction center. A value of J = 250 cm(-1) is found for the coupling between BPhy and BChl.

The role of quantum coherence in promoting the efficiency of the initial stages of photosynthesis is an open and intriguing question. We performed a two-color photon echo experiment on a bacterial reaction center that enabled direct visualization of the coherence dynamics in the reaction center. The data revealed long-lasting coherence between two electronic states that are formed by mixing of the bacteriopheophytin and accessory bacteriochlorophyll excited states. This coherence can only be explained by strong correlation between the protein-induced fluctuations in the transition energy of neighboring chromophores. Our results suggest that correlated protein environments preserve electronic coherence in photosynthetic complexes and allow the excitation to move coherently in space, enabling highly efficient energy harvesting and trapping in photosynthesis.

Lanthanide-doped upconverting nanoparticles (UCNPs, NaYF4:Yb(3+),Er(3+)) are well known for emitting visible photons upon absorption of two or more near-infrared (NIR) photons through energy transfer from the sensitizer (Yb(3+)) to the activator (Er(3+)). Of the visible emission bands (two green and one red band), it has been suggested that the red emission results from two competing upconversion pathways where the non-radiative relaxation occurs after the second energy transfer (pathway A, (4)I15/2 → (4)I11/2 → (4)F7/2 → (2)H11/2 → (4)S3/2 → (4)F9/2 → (4)I15/2) or between the first and the second energy transfer (pathway B, (4)I15/2 → (4)I11/2 → (4)I13/2 → (4)F9/2 → (4)I15/2). However, there has been no clear evidence or thorough analysis of the partitioning between the two pathways. We examined the spectra, power dependence, and time profiles of UCNP emission at either 980 nm or 488 nm excitation, to address which pathway is preferred. It turned out that the pathway B is predominant for the red emission over a wide range of excitation powers.

The gas-phase radical-radical reaction dynamics of O(3P) + C3H5 --H(2S) + C3H4O was studied at an average collision energy of 6.4 kcal/mol in a crossed beam configuration. The ground-state atomic oxygen [O(3P)] and allyl radicals (C3H5) were generated by the photolysis of NO2 and the supersonic flash pyrolysis of allyl iodide, respectively. Nascent hydrogen atom products were probed by the vacuum-ultraviolet-laser induced fluorescence spectroscopy in the Lyman-alpha region centered at 121.6 nm. With the aid of the CBS-QB3 level of ab initio theory, it has been found that the barrierless addition of O(3P) to C3H5 forms the energy-rich addition complexes on the lowest doublet potential energy surface, which are predicted to undergo a subsequent direct decomposition step leading to the reaction products H + C3H4O. The major counterpart C3H4O of the probed hydrogen atom is calculated to be acrolein after taking into account the factors of barrier height, reaction enthalpy, and the number of intermediates involved along the reaction pathway. The nascent H-atom Doppler profile analysis shows that the average center-of-mass translational energy of the H + C3H4O products and the fraction of the total available energy released as the translational energy were determined to be 3.83 kcal/mol and 0.054, respectively. On the basis of comparison with statistical calculations, the reaction proceeds through the formation of short-lived addition complexes rather than statistical, long-lived intermediates, and the polyatomic acrolein product is significantly internally excited at the moment of the decomposition.

The radical–radical reaction dynamics of ground-state atomic oxygen [O(3P)] with propargyl radicals (C3H3) has first been investigated by applying laser induced fluorescence spectroscopy in a crossed beam configuration, together with ab initio calculations. A new exothermic channel of O(3P)+C3H3→C3H2+OH was identified and the nascent distributions of OH reaction product in the ground vibrational state (X 2Π:υ″=0) showed substantial rotational excitations with an unusual bimodal feature composed of the low- and high-N″ components. No spin–orbit propensities were observed, whereas the averaged ratios of Π(A′)/Π(A″) were determined to be 0.60±0.28. With the aid of the CBS-QB3 level of ab initio theory it is predicted that on the lowest doublet potential energy surface the reaction proceeds through the addition complexes formed through the barrierless addition of O(3P) to C3H3, and that the counterpart of C3H2 of the probed OH product is cyclopropenylidene (1c-C3H2). On the basis of the comparison with statis...

The reaction dynamics of ground-state atomic oxygen [O(3P)] with allyl radicals (C3H5) has been investigated by applying a combination of crossed beams and laser induced fluorescence techniques. The reactants O(3P) and C3H5 were produced by the photodissociation of NO2 and the supersonic flash pyrolysis of precursor allyl iodide, respectively. A new exothermic channel of O(3P)+C3H5→C3H4+OH was observed and the nascent internal state distributions of the product OH (X 2Π:υ″=0,1) showed substantial bimodal internal excitations of the low- and high-N″ components without Λ-doublet and spin–orbit propensities in the ground and first excited vibrational states. With the aid of the CBS-QB3 level of ab initio theory and Rice–Ramsperger–Kassel–Marcus calculations, it is predicted that on the lowest doublet potential energy surface the major reaction channel of O(3P) with C3H5 is the formation of acrolein (CH2CHCHO)+H, which is consistent with the previous bulk kinetic experiments performed by Gutman et al. [J. Phys. Chem. 94, 3652 (1990)]. The counterpart C3H4 of the probed OH product in the title reaction is calculated to be allene after taking into account the factors of reaction enthalpy, barrier height and the number of intermediates involved along the reaction pathway. On the basis of population analyses and comparison with prior calculations, the statistical picture is not suitable to describe the reactive atom-radical scattering processes, and the dynamics of the title reaction is believed to proceed through two competing dynamical pathways. The major low N″-components with significant vibrational excitation may be described by the direct abstraction process, while the minor but extraordinarily hot rotational distribution of high N″-components implies that some fraction of reactants is sampled to proceed through the indirect short-lived addition-complex forming process.

The reaction of ground-state atomic oxygen (O(3P)) with allyl radical (C3H5) was investigated in the crossed beam configuration. O(3P) and C3H5 were generated by the photodissociation of NO2 and the supersonic flash pyrolysis of allyl iodide, respectively. The nascent internal distributions of the OH(X2Π : v″=0,1) reaction product from the newly observed channel of O(3P)+C3H5→C3H4+OH were probed by laser induced fluorescence (LIF) spectroscopy. The distributions showed significant excitations with an unusual bimodal feature: the low and high rotational components without spin-orbit and Λ-doublet propensities in the ground and first excited vibrational states. On the basis of population analysis and comparison with the ab initio and statistical calculations, the experimental distributions are estimated to be totally non-statistical and suggest that the dynamics of the reaction might be described by two competing mechanisms: a major direct abstraction process and an indirect short-lived addition-complex for...

The correlation of elemental chemistry with the particular long-range order in question cannot be obtained by common conventional characterization techniques. Here we report a study of determining the elemental concentrations of the textured Bragg diffraction peak and the averaged local atomic environment of sputtered CoCrPt films using anomalous x-ray scattering and extended x-ray absorption fine structures. The elemental compositions of the textured peak in these polycrystalline nanostructured films differed from the average global film composition. The higher Cr concentration in the textured peak indicated that a significant amount of Cr did not segregate towards the grain boundaries as a result of the low sputtering temperature and pressure used. The structural observations were consistent with the magnetic results.

We show how long-lasting coherence enhances energy transfer rate in a photosynthetic complex based on an analysis of data collected using a newly developed twocolor electronic coherence photon echo technique and theoretical simulations.

Conventional x-ray diffraction failed to provide correct information on alloying of materials made of elements with close lattice parameters, even for elements commonly accepted to have miscibility. Using anomalous x-ray scattering, we showed that nanostructured NiCo films did not necessarily form solid solution as expected from their phase diagram or suggested by the results of conventional x-ray diffraction.

One- and two-color, three-pulse photon echo peak shift spectroscopy (1C and 2C3PEPS) was used to estimate the electronic coupling between the accessory bacteriochlorophyll (B) and the bacteriopheophytin (H) in the reaction center of the purple photosynthetic bacterium Rhodobacter sphaeroides as approximately 170 +/- 30 cm-1. This is the first direct experimental determination of this parameter; it is within the range of values found in previously published calculations. The 1C3PEPS signal of the Qy band of the bacteriochlorophyll B shows that it is weakly coupled to nuclear motions of the bath, whereas the 1C3PEPS signal of the Qy band of the bacteriopheophytin, H, shows that it is more strongly coupled to the bath, but has minimal inhomogeneous broadening. Our simulations capture the major features of the data with the theoretical framework developed in our group to separately calculate the response functions and population dynamics.

One- and two-color three pulse photon echo peak shift spectroscopy were used to determine that the electronic coupling between the accessory bacteriochlorophyll (B) and the bacteriopheophytin (H) in the reaction center of the purple photosynthetic bacterium Rb. Sphaeroides is ∼170 cm−1.

The B800 band of the reaction center complex of Rhodobacter sphaeroides has been probed with two-dimensional Fourier transform electronic spectroscopy using 40 fs pulses and evidence for coupling within the band will be presented.

The radical-radical reaction dynamics of ground-state atomic oxygen [O(3P)] with propargyl radicals (C3H3) has first been investigated in a crossed beam configuration. The radical reactants O(3P) and C3H3 were produced by the photodissociation of NO2 and the supersonic flash pyrolysis of precursor propargyl bromide, respectively. A new exothermic channel of O(3P) + C3H3 --> C3H2 + OH was identified and the nascent distributions of the product OH in the ground vibrational state (X 2Pi:nu" = 0) showed bimodal rotational excitations composed of the low- and high-N" components without spin-orbit propensities. The averaged ratios of Pi(A')/Pi(A") were determined to be 0.60 +/- 0.28. With the aid of ab initio theory it is predicted that on the lowest doublet potential energy surface, the reaction proceeds via the addition complexes formed through the barrierless addition of O(3P) to C3H3. The common direct abstraction pathway through a collinear geometry does not occur due to the high entrance barrier in our low collision energy regime. In addition, the major reaction channel is calculated to be the formation of propynal (CHCCHO) + H, and the counterpart C3H2 of the probed OH product in the title reaction is cyclopropenylidene (1c-C3H2) after considering the factors of barrier height, reaction enthalpy and structural features of the intermediates formed along the reaction coordinate. On the basis of the statistical prior and rotational surprisal analyses, the ratio of population partitioning for the low- and high-N" is found to be about 1:2, and the reaction is described in terms of two competing addition-complex mechanisms: a major short-lived dynamic complex and a minor long-lived statistical complex. The observed unusual reaction mechanism stands in sharp contrast with the reaction of O(3P) with allyl radical (C3H5), a second significant conjugated hydrocarbon radical, which shows totally dynamic processes [J. Chem. Phys. 117, 2017 (2002)], and should be understood based upon the characteristic electronic structures and reactivity of the intermediates on the potential energy surface.

The radical-radical oxidation reaction, O(3P)+C3H3 (propargyl)-->H(2S)+C3H2O (propynal), was investigated using vacuum-ultraviolet laser-induced fluorescence spectroscopy in a crossed-beam configuration, together with ab initio and statistical calculations. The barrierless addition of O(3P) to C3H3 is calculated to form energy-rich addition complexes on the lowest doublet potential energy surface, which subsequently undergo direct decomposition steps leading to the major reaction products, H+C3H(2)O (propynal). According to the nascent H-atom Doppler-profile analysis, the average translational energy of the products and the fraction of the average transitional energy to the total available energy were determined to be 5.09+/-0.36 kcal/mol and 0.077, respectively. On the basis of a comparison with statistical prior calculations, the reaction mechanism and the significant internal excitation of the polyatomic propynal product can be rationalized in terms of the formation of highly activated, short-lived addition-complex intermediates and the adiabaticity of the excess available energy along the reaction coordinate.

We present ab initio calculations of the reaction of ground-state atomic oxygen [O((3)P)] with a propargyl (C(3)H(3)) radical based on the application of the density-functional method and the complete basis-set model. It has been predicted that the barrierless addition of O((3)P) to C(3)H(3) on the lowest doublet potential-energy surface produces several energy-rich intermediates, which undergo subsequent isomerization and decomposition steps to generate various exothermic reaction products: C(2)H(3)+CO, C(3)H(2)O+H, C(3)H(2)+OH, C(2)H(2)+CHO, C(2)H(2)O+CH, C(2)HO+CH(2), and CH(2)O+C(2)H. The respective reaction pathways are examined extensively with the aid of statistical Rice-Ramsperger-Kassel-Marcus calculations, suggesting that the primary reaction channel is the formation of propynal (CHCCHO)+H. For the minor C(3)H(2)+OH channel, which has been reported in recent gas-phase crossed-beam experiments [H. Lee et al., J. Chem. Phys. 119, 9337 (2003); 120, 2215 (2004)], a comparison on the basis of prior statistical calculations is made with the nascent rotational state distributions of the OH products to elucidate the mechanistic and dynamic characteristics at the molecular level.