Electrochemical,thermal,and photophysical properties of novel two-photon absorption chromophores

Electrochemical, thermal, and photophysical properties of novel two- （BPODPA）, four- （BBPOPA）, and six-branch （TBPOA） triphenylamine chromophores are studied. The decomposition temperature of chro- mophores reaches 373 - 412 ℃. The electrochemical properties is explored by cyclic voltammetry. The ionization potential of chromophores is in the range of 5.14 - 5.18 eV. Excitation at 400 nm reveals emission peaks at 483 - 487 nm and the fluorescence quantum yields are 0.73 - 0.75 in CH2Cl2. Two-photon absorption （TPA） properties of chromophores are measured by nonlinear transmission method. The maximum TPA cross-section values are measured at 758 nm to be 20369 GM （1 GM=10^-50 cm^4 -s/photon） for TBPOA, 7024 GM for BBPOPA, and 1227 GM for BPODPA, respectively. When pumped with 800-nm laser irradiation, chromophores show strong two-photon excited blue-green fluorescence at 502 - 518 nm. These results provide a basis for understanding the electronic and optical properties of the conjugated multi-branch chromoohore in terms of the underlying molecular and electronic structures.     

Dendrimer molecules with record large two-photon absorption cross section

We report what is to our knowledge a record high value for an intrinsic two-photon absorption (TPA) cross section, sigma(2) = 11 x 10(-47)> cm>(4)> s photon(-1) molecule(-1), measured with femtosecond pulses in a new dendrimer molecule comprising 29 repeat units of 4, 4(?)-bis(diphenylamino)stilbene chromophore. We measure the dependence of TPA on excitation wavelength in three consecutive generations of the dendrimer and show that the maximum sigma(2) value increases faster than the total number of stilbene chromophores. This result indicates that it is possible to obtain even larger sigma(2) values in higher generations of this dendrimer family.     

电多极相互作用引起的静态能量传递中施主发光衰减与受主浓度的关系

本文指出,通常用于描述电多极相互作用引起的静态传递模型中时间足够长时施主发光衰减规律的表示式exp[-γt-CA(X0t)3/s)Г(1-3/s)]应该用exp[-γt-CA·A(CA)(X0t)2/sГ(1-3/s)]/(1-CA)来代替;文中还指出,静态有序阶段的时间上限由X0t相似文献   

First-principles study on the effect of micro-modified D-A-π-A dyes with triphenylamine acting as a donor on its photoelectric properties

A triphenylamine-based dye sensitizer–the electron donor, added with the embellishment, was designed and analyzed, to serve as a backup molecule for the sensitized solar cells (DSSCs). For a more realistic performance, five sensitizer molecules (ND, NDSH-1～4) with triphenylamine (TPA) units as election donors (D), 4-benzo[c] [1, 2, 5] thiadiazol segment as acting as auxiliary acceptors (A), 4-ylethynyl as bridge (π) and benzoic acid as the electron acceptor (A) were explored in dichloromethane solvent by the methods of Density functional theory (DFT) and Time-dependent density functional theory (TD-DFT). Meanwhile, to understand the working process of DSSCs more systematically, these dyes adsorbed on (TiO₂)₁₆ were further explored. Finally, the effects of triphenylamine modification are summarized and disclosed from the phenomenon of simulation. The results show that the nitrogen-substituted hexyloxy dye exhibits a very narrow band gap and has a distinct red-shifted absorption band compared to the experimental dye ND.     

Measurement of the W-->taunu production cross section in pp collisions at square root s=1.8 TeV

We report on a measurement of sigma(pp-->W+X)B(W-->taunu) in pp collisions at sqrt[s]=1.8 TeV at the Fermilab Tevatron. The measurement is based on an integrated luminosity (lum) of 18 pb-1 of data collected with the D0 detector during 1994-1995. We find that sigma(pp-->W+X)B(W-->taunu)=2.22+/-0.09 (stat)+/-0. 10 (syst)+/-0.10 (lum) nb. Lepton universality predicts that the ratio of the tau and electron electroweak charged current couplings to the W boson, gWtau/gWe, be unity. We find gWtau/gWe=0.980+/-0.031, in agreement with lepton universality.     

Theoretical study of one‐ and two‐photon absorption properties of expanded donor–acceptor calix[4]arenes

Two types of donor(D)–acceptor(A) calix[4]arenes have been theoretically studied using DFT//B3LYP/6‐31G(d) method and ZINDO/CISD method. The calculations show that the substitution of C? C by the conjugation bridge C?C and N?N plays an important part in altering one‐photon absorption (OPA) and two‐photon absorption (TPA) properties. The maximum OPA wavelengths of all studied compounds are less than 400 nm, which means high transparency. The geometry of the calixarenes strongly influences the TPA properties of the studied compounds. In addition, the nitro derivatives have a wider TPA response range than other non‐nitro derivatives. The tetrasubstituted calix[4]arenes (type B calixarenes) have a larger TPA cross‐section values than the bisubstituted calix[4]arenes (type A calixarenes). Copyright © 2009 John Wiley & Sons, Ltd.     

Theoretical and experimental investigation of (13)C relayed (2)H-(2)H-COSY 2D experiments: application to the analysis of weakly aligned solutes

We describe new NMR 2D experiments denoted DECADENCY for DEuterium CArbon DEuterium Nuclear Correlation spectroscopY dedicated to the analysis of anisotropic deuterium spectra. They belong to the class of X-relayed Y,Y-COSY 2D experiments that was initially explored in the case of a (1)H-X-(1)H fragment (I(X)=1/2) in isotropic medium. DECADENCY 2D experiments permit to correlate the quadrupolar doublets associated with two inequivalent deuterium nuclei in an oriented CD(2) fragment through heteronuclear polarization transfers. Two kinds of pulse sequences are described here using either a double INEPT-type or DEPT-type process. DECADENCY 2D experiments provide an interesting alternative to (2)H-(2)H COSY experiments when the geminal (2)H-(2)H total coupling (scalar and dipolar) is null or too small to provide visible cross-correlation peaks. Such a situation is typically observed for geminal deuteriums in prochiral or chiral molecules dissolved in chiral liquid crystals. The efficiency of these techniques is illustrated using dideuterated prochiral molecules, the phenyl[(2)H(2)]methanol and the 1-chloro[1-(2)H(2)]nonane, both dissolved in organic solutions of poly-gamma-benzyl-l-glutamate. The advantages of each sequence are presented and discussed. It is shown that the relative sign of the quadrupolar doublets can be determined.     

Simultaneous measurement of the ratio R=B(t --> Wb)/B(t --> Wq) and the top-quark pair production cross section with the D0 detector at sqrt(s) = 1.96 TeV

We present the first simultaneous measurement of the ratio of branching fractions, R=B(t --> Wb)/B(t --> Wq), with q being a d, s, or b quark, and the top-quark pair production cross section sigma(tt[over]) in the lepton plus jets channel using 0.9 fb(-1) of pp[over] collision data at sqrt(s)=1.96 TeV collected with the D0 detector. We extract R and sigma(tt[over]) by analyzing samples of events with 0, 1, and > or =2 identified b jets. We measure R=0.97(+0.09)/(-0.08)(stat+syst) and sigma(tt[over])=8.18(+0.09)(-0.84)(stat+syst) +/- 0.50(lumi) pb, in agreement with the standard model prediction.     

Measurement of the tt[over] production cross section in pp[over] collisions at sqrt(s)=1.96 TeV

We measure the tt[over] production cross section in pp[over] collisions at sqrt(s)=1.96 TeV in the lepton + jets channel. Two complementary methods discriminate between signal and background: b tagging and a kinematic likelihood discriminant. Based on 0.9 fb(-1) of data collected by the D0 detector at the Fermilab Tevatron Collider, we measure sigma(tt[over])=7.62+/-0.85 pb, assuming the current world average m(t)=172.6 GeV. We compare our cross section measurement with theory predictions to determine a value for the top-quark mass of 170+/-7 GeV.     

FRET Studies of the Interaction of Dimeric Cyanine Dyes with DNA

Fluorescence Resonance Energy Transfer (FRET) is a powerful tool to determine distances between chromophores bound to macromolecules, since the efficiency of the energy transfer from an initially excited donor to an acceptor strongly depends on the distance between the two dye molecules. The structure of the noncovalent complex of double-strand DNA (dsDNA) with thiazol orange dimers (TOTO) allows FRET analysis of two intercalated chromophores. By intercalation of two different TOTO dyes we observe an energy transfer from TOTO-1 as donor and TOTO-3 as acceptor. In this manner we are able to determine the mean distance between two proximate TOTO molecules bound to dsDNA. Thus the maximum number of binding positions for this type of intercalation dyes in the dsDNA can be obtained. Furthermore the dependency of the acceptor emission on the donor concentration is analysed. The emission of TOTO-3 reaches a maximum when the acceptor-to-donor ratio is 1:10.     

Measurement of the Raman cross section of O(2)(a(1)D(g))

Two different measurement methods are described that indicate that the Raman cross section of O(2)(a(1)D(g)), sigma(a)= (0.45+/-0.02) sigma(X), where sigma(X) is the Raman cross section of O(2)(X(3)?(g)(-)). Spontaneous Raman scattering is a potentially useful technique for measuring the singlet O(2)yield in high-power oxygen iodine lasers. For the full potential of this method to be realized, one must determine sigma(O)(2(a)) to measure the yield directly.     

共轭聚合物单分子构象和能量转移特性研究

利用基于宽场显微光学系统的单分子散焦成像技术测量了不同构象poly[2,7-(9,9-dioctylfluorene)-alt-4,7-bis(thiophen-2-yl)benzo-2,1,3-thiadiazole](PFO-DBT)共轭聚合物单分子的光物理与动力学特性.通过分析共轭聚合物单分子的荧光轨迹和对应的发射偶极取向变化识别共轭聚合物单分子发光单元,发现延伸构象下的单分子呈现多发色团发光特性,而折叠构象下的单分子保持高效链间能量转移,呈现单个发色团发光特性.共轭聚合物单分子构象对能量转移效率的影响可用于研究基于共轭聚合物的光电器件和分子器件.     

Intramolecular charge transfer in donor‐bridge‐acceptor compounds with paired linearly conjugated or cross‐conjugated pathways

An understanding of intramolecular charge transfer in 2‐D linearly conjugated and cross‐conjugated compounds is necessary for the rational design of molecular electronics, improved solar energy devices, semi‐conducting polymers, and materials with nonlinear optical properties. In this work, the femtosecond transient absorption spectra and kinetics of several donor‐bridge‐acceptor compounds containing cross‐conjugated or linearly conjugated bridging groups were obtained. The veratrole group was used as the donor, and the phthalimide group was used as an acceptor. 2‐D conjugation was achieved by involving two bridging groups arranged cyclically between the donor and acceptor. The donor and acceptor were bridged by m‐phenylene in the cross‐conjugated compounds or 2,5‐thiophene in the linearly conjugated compounds. We found slower charge separation times and slower charge recombination times in the compounds containing cyclic cross‐conjugated bridging groups than in those containing the cyclic linearly conjugated groups in polar solvent. Charge separation rates that were found to be dependent on solvent were observed in the donor‐bridge‐acceptor compounds. Copyright © 2014 John Wiley & Sons, Ltd.     

Measurements of the branching fractions for psi(3770)-->D(0)D[over ](0), D+D-, DD[over ], and the resonance parameters of psi(3770) and psi(2S)

We measure the branching fractions for psi(3770)-->D(0)D[over ](0), D+D-, DD[over ], and non-DD[over ] to be (46.7+/-4.7+/-2.3)%, (36.9+/-3.7+/-2.8)%, (83.6+/-7.3+/-4.2)%, and (16.4+/-7.3+/-4.2)%, respectively. The resonance parameters of psi(3770) and psi(2S) are measured to be M_(psi(3770))=3772.2+/-0.7+/-0.3 MeV, Gamma_(psi(3770))(tot)=26.9+/-2.4+/-0.3 MeV, and Gamma_(psi(3770))(ee)=251+/-26+/-11 eV; M_(psi(2S))=3685.5+/-0.0+/-0.3 MeV, Gamma_(psi(2S))(tot)=331+/-58+/-2 keV, and Gamma_(psi(2S))(ee)=2.330+/-0.036+/-0.110 keV. We also measure the light hadron R value to be R(uds)=2.262+/-0.054+/-0.109 in the energy region from 3.660 to 3.872 GeV.     

Ex vivo magnetic resonance imaging of rat spinal cord at 9.4 T

The magnetic resonance (MR) properties of the rat spinal cord were characterized at the T9 level with ex vivo experiments performed at 9.4 T. The inherent endogenous contrast parameters, proton density (PD), longitudinal and transverse relaxation times T1 and T2, and magnetization transfer ratio (MTR) were measured separately for the grey matter (GM) and white matter (WM). Analysis of the measurements indicated that these tissues have statistically different proton densities with means PD(GM)=54.8+/-2.5% versus PD(WM)=45.2+/-2.4%, and different T1 values with means T1GM=2.28+/-0.23 s versus T1WM=1.97+/-0.21 s. The corresponding values for T2 were T2GM=31.8+/-4.9 ms versus T2WM=29.5+/-4.9 ms, and the difference was insignificant. The difference between MTR(GM)=31.2+/-6.1% and MTR(WM)=33.1+/-5.9% was also insignificant. These results collectively suggest that PD and T1 are the two most important parameters that determine the observed contrast on spinal cord images acquired at 9.4 T. Therefore, in MR imaging studies of spinal cord at this field strength, these parameters need to be considered not only in optimizing the protocols but also in signal enhancement strategies involving exogenous contrast agents.     

Experimental and Theoretical Studies of the Spectroscopic Properties of Chalcone Derivatives

Newly synthesized, differently substituted chalcones (1,3-diaryl-2-propen-1-ones) have been studied using steady-state and time-resolved techniques combined with quantum-chemical modelling. To explore spectroscopic structure - property relationships the substituent (acceptor moiety) was chosen according to systematic variation in the Hammett parameter. It was shown that photophysical properties of the studied donor-acceptor (D-A) molecules can be predicted in terms of a simple model from the properties of individual chromophores (composite-model of decoupled moieties: donor (D) and acceptor (A)). The results of spectroscopic measurements also indicate that for investigated D-A fluorophores in medium-polar solvent, the initially populated, locally excited (LE) state (where the fundamental role plays donor moiety (D*-A)) reacts further to produce intramolecular charge transfer (ICT) state. Additionally, the experimental absorption (M _ge ) and fluorescence (M _eg ) transition dipole moments were calculated on the basis of spectroscopic data and compared with results of our quantum-chemical calculations. The absorption transition dipole moment was found to vary linearly with the Hammett substituent coefficient (σ).     

Acetylene-Substituted Two-Photon Absorbing Molecules With Rigid Elongated Pi-Conjugation: Synthesis,Spectroscopic Properties and Two-Photon Fluorescence Cell Imaging Applications

Two asymmetrical molecules with substituted acetylene as central rigid elongated conjugation are reported as potential chromophores for two-photon microscopic imaging. These molecules consist of a typical D–π–A structure, have different donors (D), the same π-conjugated center (π) and the same acceptor (A). Structural characterization and spectroscopic properties, including single-photon (linear) absorption, quantum yields, single-photon fluorescence, and two-photon absorption spectra, were studied in solvents with different polarity. These acetylene-substituted molecules were found to have high two-photon absorption cross-sections (for example, 690 GM for molecule 1 in toluene), which were determined by a two-photon induced fluorescence method using a femtosecond Ti: sapphire laser as excitation source. Single- and two-photon cellular imaging experiments demonstrate that the substituted acetylene derivatives could be one kind of promising two-photon fluorescence probes for cellular imaging.     

Measurement of sigma Lambda b0/sigma B0 x B(Lambda b0-->Lambda c+pi-)/B(B0-->D+pi-) in pp collisions at square root s=1.96 TeV

We present the first observation of the baryon decay Lambda b0-->Lambda c+pi- followed by Lambda c+-->pK-pi+ in 106 pb-1 pp collisions at square root s=1.96 TeV in the CDF experiment. In order to reduce systematic error, the measured rate for Lambda b0 decay is normalized to the kinematically similar meson decay B0-->D+pi- followed by D+-->pi+K-pi+. We report the ratio of production cross sections (sigma) times the ratio of branching fractions (B) for the momentum region integrated above pT>6 GeV/c and pseudorapidity range |eta|<1.3: sigma(pp-->Lambda b0X)/sigma(pp-->B0X)xB(Lambda b0-->Lambda c+pi-)/B(B0-->D+pi-)=0.82+/-0.08(stat)+/-0.11(syst)+/-0.22[B(Lambda c+-->pK-pi+)].     

RbH(X1∑+,v=O～2)能级与H2碰撞振动能量转移

利用积分时间分辨荧光光谱方法,研究了RbH(X1∑+,v=0～2)与H2间的振动碰撞能量转移.在Rb-H2混合样品池中,泵浦激光双光子激发Rb原子至6D态,Rb(6D)与H2反应生成RbH(x1∑+)分子,探测激光延迟泵浦激光20 ns,通过激光感应荧光光谱(LIF)的测量,确定了X1∑+(v=0～2,J)原生态的转动...     

Modulated conjugation as a means for attaining a record high intrinsic hyperpolarizability

We report on a series of chromophores that have been synthesized with a modulated conjugation path between donor and acceptor. Hyper-Rayleigh scattering measurements of the best molecule show an enhanced intrinsic hyperpolarizability that breaches the apparent limit of all previously studied molecules.