基于光学成像技术的单颗粒电化学研究

光学显微镜技术具有高时空分辨率、高通量、高灵敏度、非接触等优点,十分适合于微观、异相界面的电子转移过程研究,因而在单颗粒电化学分析中展现出良好的应用前景.结合本课题组的研究工作,本文主要介绍了单分子荧光显微镜、表面等离激元共振显微镜、暗场显微镜及电化学发光四种光学显微技术在单纳米粒子电化学研究方面取得的最新研究进展,最...     

Functionalized Ag nanoparticles with tunable optical properties for selective protein analysis

We present a preparation procedure for small sized biocompatibly coated Ag nanoparticles with tunable surface plasmon resonances. The conditions were optimised with respect to the resonance Raman signal enhancement of heme proteins and to the preservation of the native protein structure.     

Polymer films on metals investigated by optical second harmonic generation

In two different types of experiments, polymer films on gold substrates were investigated by optical second harmonic generation (SHG). Thickness dependent ex situ measurements on Langmuir-Blodgett films of the octadecylammonium salt of polyamic acid (PACS) show a preferential orientation of the polymer molecules. In situ SHG experiments were performed to monitor the growth of polyamic acid films deposited from the gas phase. Pyromellitic dianhydride (PMDA), 4,4-oxydianiline (ODA), and 4,4-diaminodiphenyl disulfide (DAPS) served as monomers. Similar to the Langmuir-Blodgett films, an oriented growth is observed. The thickness dependence of the SHG signal is strongly dependent on the interfacial chemistry which is very different for the two amines used as monomers. Based on a comprehensive three layer model, the relation between the structure of the films and the SHG signal is discussed.     

Size dependent macrophage responses and toxicological effects of Ag nanoparticles

The immune-response of macrophages is an important area of investigation since it represents the major pathway by which early-stage defense barriers are established in skin, lungs, and mucosal systems to counteract foreign objects. In this study, we have examined the size-dependent inflammatory and toxicological effects of nanostructured silver particles (nano-Ag) on macrophage immune cells.     

Optical second harmonic generation spectroscopy from Ag(001) using s-polarized excitation

The s- and p-polarized second harmonic generation (SHG) from Ag(001) under electrochemical control was measured as a function of the sample orientation about its surface normal. Our experiments were performed over a range of second harmonic photon energies surrounding the onset of interband transitions, and for different values of the applied potential on either side of the potential of zero charge. We used only s-polarized incident light to eliminate most of the susceptibilities that usually contribute to SHG, leaving two bulk-derived contributions (ζ, which depends upon the crystal orientation, and γ, which is insensitive to crystal orientation), and one surface susceptibility (χ_zxx). Our results suggest that, of these, χ_zxx is less significant, with ζ being considerably larger than γ. Both of these show little spectral variation. Even more surprising is the result that γ demonstrates a sensitivity to changes in the applied potential. This could be associated with changes in the characteristics of electron scattering by the surface barrier, which would indirectly influence the dynamics of electrons in the bulk.     

In situ second harmonic generation studies from covered Ag(111) electrodes

The second harmonic response of Ag(111) electrodes has been studied in the presence of adsorbates. Two different kind of systems have been investigated: films of biphenyl derivatives and halide adsorbates. The presence of the adsorbates is shown to affect markedly the isotropic response of the interface, while the anisotropic part seems to be generated solely by the metal.Dedicated to Prof. Wolf Vielstich on the occasion of his 80^th birthday in recognition of his numerous contributions to interfacial electrochemistry     

Quantitative measurement and interpretation of optical second harmonic generation from molecular interfaces

Second harmonic generation (SHG) has been proven a uniquely effective technique in the investigation of molecular structure and conformations, as well as dynamics of molecular interfaces. The ability to apply SHG to molecular interface studies depends on the ability to abstract quantitative information from the measurable quantities in the actual SHG experiments. In this review, we try to assess recent developments in the SHG experimental methodologies towards quantitative analysis of the nonlinear optical properties of the achiral molecular interfaces with rotational isotropy along the interface normal. These developments include the methodology for orientational analysis of the SHG experimental data, the experimental approaches for more accurate SHG measurements, and a novel treatment of the symmetry properties of the molecular polarizability tensors in association with the experimentally measurable quantities. In the end, the recent developments on the problem of surface versus bulk contribution in SHG surface studies is discussed. These developments can put SHG on a more solid foundation for molecular interface studies, and to pave the way for better understanding and application of SHG surface studies in general.     

Origin of the photoinduced optical second harmonic generation arising in N-phenyl microcrystalline films

Photoinduced second-order nonlinear optical effects, particularly optical second harmonic generation (SHG) of N-phenyls with different numbers of aromatic rings deposited on glass substrates were studied. As a fundamental beam, a 5-ps pulsed Nd:YAG laser was used. Quantum chemical time-dependent density functional theory (TDDFT) simulations of the nonlinear optical properties were performed. The first-order hyperpolarizabilities of isolated molecules were calculated, under the influence of a polarized pumping beam, to evaluate the role played by the nanointerfaces separating the microcrystallites and the amorphous environment. Consideration was performed within a framework of steady-state Langevin order parameters for amorphous-like films. A strong dependence of the photoinduced SHG versus the number of aromatic rings determining the degree of film crystallinity was shown. A comparison of experimental data and theoretically evaluated results shows that for the photoinduced first-order nonlinear optical effect the dominant contribution is an amorphous-like structural component, unlike the transport properties, where the crucial role is played by the nanointerface region. This may reflect a specific feature of the multiphoton processes in such types of nanointerfaces because of nanoconfined effects.     

Cone motion viscosity and optical second harmonic generation of ferroelectric liquid crystalline dendrimers

We report second harmonic generation in a ferroelectric liquid crystalline trimer and ferroelectric liquid crystalline dendrimers of first, second and third generation. Thin cells were filled with the compounds by capillary forces at elevated temperature, and cooled from the surface stabilized ferroelectric state to below the glass transition temperature, while kept in an electric field. The cone motion viscosity and the threshold electric field for unwinding of the helix axis of the chiral tilted smectic mesophases were studied separately at elevated temperature, and these data were used to optimize the preparation of the films. The measured response time was between 0.3 and 3ms, which corresponds to a cone motion viscosity between 0.5 and 50 Pa s. Second harmonic generation was studied both at elevated temperature with an electric field and at room temperature with and without electric field. The first generation dendrimer exhibited a strong increase in the second order non-linear optical response with time at room temperature. The d ₂₃-coefficient of this dendrimer was approximately four times larger than for the other macromolecules and was 0.045 pm V^-1. The relatively large d-coefficient of the first generation dendrimer is ascribed to crystallization, which improved the orientation of the molecular dipoles.     

Cone motion viscosity and optical second harmonic generation of ferroelectric liquid crystalline dendrimers

We report second harmonic generation in a ferroelectric liquid crystalline trimer and ferroelectric liquid crystalline dendrimers of first, second and third generation. Thin cells were filled with the compounds by capillary forces at elevated temperature, and cooled from the surface stabilized ferroelectric state to below the glass transition temperature, while kept in an electric field. The cone motion viscosity and the threshold electric field for unwinding of the helix axis of the chiral tilted smectic mesophases were studied separately at elevated temperature, and these data were used to optimize the preparation of the films. The measured response time was between 0.3 and 3ms, which corresponds to a cone motion viscosity between 0.5 and 50 Pa s. Second harmonic generation was studied both at elevated temperature with an electric field and at room temperature with and without electric field. The first generation dendrimer exhibited a strong increase in the second order non-linear optical response with time at room temperature. The d₂₃-coefficient of this dendrimer was approximately four times larger than for the other macromolecules and was 0.045 pm V^-1. The relatively large d-coefficient of the first generation dendrimer is ascribed to crystallization, which improved the orientation of the molecular dipoles.     

Ultrafast nonlinear optical response of Ag nanoparticles embedded in mesoporous thin films

Highly dispersed silver nanoparticles embedded in mesoporous thin films (MTFs) have been synthesized by modification of the interior surface of mesoporous silica with ethylenediamine moieties, which provided the coordination sites for the Ag ions, and subsequent reduction under hydrogen atmosphere. TEM observations show the mesoporous parent films have effectively controlled the growth of the synthesized silver nanoparticles. The composite films had an ultrafast nonlinear response time, as fast as 200 fs, and a third-order nonlinear optical susceptibility of 0.94 × 10^?10 esu, which was enhanced by the local field enhancement effect that was present when the silver nanoparticles were embedded in the surrounding dielectric matrix. The origin of the ultrafast nonlinear response and the enhanced nonlinearity of the composite films are attributed to the intraband transition of the free electrons near the Fermi surface of the incorporated silver nanoparticles.     

两种形貌GdPO_4纳米粒子的制备和光学性质研究

以Gd2O3、H3PO4为原料,聚乙二醇(PEG)为结构导向剂,通过改变沉淀剂NaOH的用量,制备了棒状、丝状的GdPO4纳米粒子,用X射线衍射仪(XRD)、X射线能量扩散光谱仪(EDS)、透射电子显微镜(TEM)、X射线光电子能谱仪(XPS)、富里叶变换红外光谱仪(FT-IR)对样品进行表征,研究了样品的激光拉曼散射光谱(Raman)、光致发光(PL)性质。结果表明,两种不同形貌的GdPO4纳米粒子具有不同的光学活性,PEG的浓度以及它和Gd3+、H+的配位作用对棒状GdPO4纳米粒子的形成有重要的影响。     

“Small-particle limit” in the second harmonic generation from noble metal nanoparticles

In this paper, we have probed the origin of SHG in copper nanoparticles by polarization-resolved hyper-Rayleigh scattering (HRS). Results obtained with various sizes of copper nanoparticles at four different wavelengths covering the wavelength range 738–1907 nm reveal that the origin of second harmonic generation (SHG) in these particles is purely dipolar in nature as long as the size (d) of the particles remains smaller compared to the wavelength (λ) of light (“small-particle limit”). However, contribution of the higher order multipoles coupled with retardation effect becomes apparent with an increase in the d/λ ratio. We have identified the “small-particle limit” in the second harmonic generation from noble metal nanoparticles by evaluating the critical d/λ ratio at which the retardation effect sets in the noble metal nanoparticles. We have found that the second-order nonlinear optical property of copper nanoparticles closely resembles that of gold, but not that of silver.     

Significant enhancement of the optical second harmonic generation in a poled azopolymer thin grating

Nonlinear optical properties of an electrically poled surface relief grating inscribed on a thin film of azopolymer have been investigated. The linear and nonlinear optical far-field diffraction patterns of the grating are compared, and they show a clear angular separation of the fundamental (lambda = 1.064 mum) and second harmonic generated beams that are diffracted at different angles. The intensity of the zero order transmitted second harmonic generation (SHG) beam from inscribed surface relief grating (SRG) areas has been recorded using the Maker fringe technique and compared to the response from flat areas that were only poled. Poled gratings exhibit a sharp second harmonic generation enhancement for coupling angles of theta(i) = +/-52 degrees due to a quasi-phase matching process. A simple phenomenological model allows one to explain both the second harmonic intensity generated from the thin polar film and the dispersion curve observed under "pp" polarization due to the mismatch of the angular coupling condition: this gives us a good indication of the intensity enhancement of the SHG beam in the forward direction.     

Theoretical and experimental study of optical second harmonic generation in new chiral thiolates salts

The second harmonic generation ability of new chiral thiolate salts is investigated. Aromatic thiolate anions ArS⁻ are expected from semi-empirical calculations with PM3 parameterization of the MNDO Hamiltonian to possess higher intrinsic polarizabilities than the parent neutral thiols ArSH.

Salts associating (hyper)polarizable aromatic thiolate anions with chiral cations, which ensure the noncentrosymmetry necessary to have second-order nonlinear optical effects have been synthesized. The first hyperpolarizabilities, β, of the salts are measured using hyper-Rayleigh scattering technique. Second harmonic generation powder tests (Kurtz and Perry method) carried out on various salts studied, were positive indicating that these materials crystallize in noncentrosymmetric space groups.     

Preparation and nonlinear optical properties of novel Y-type polyesters with highly enhanced thermal stability of second harmonic generation

3,4-Di-(2′-hydroxyethoxy)benzylidenemalononitrile (3) was prepared and condensed with terephthaloyl chloride and adipoyl chloride to yield novel Y-type polyesters (4-5) containing 3,4-dioxybenzylidenemalononitrile groups as NLO-chromophores, which constituted parts of the polymer main-chains. The resulting polymers 4-5 are soluble in common organic solvents such as acetone and N,N-dimethylformamide. They showed thermal stability up to 300 °C in thermogravimetric analysis with glass-transition temperatures obtained from differential scanning calorimetry in the range 89-91 °C. The second harmonic generation (SHG) coefficients (d₃₃) of poled polymer films at the 1064 nm fundamental wavelength were around 2.47 pm/V. The dipole alignment exhibited high thermal stability even at 10 °C higher than T_g, and there is no SHG decay below 100 °C due to the partial main-chain character of polymer structure, which is acceptable for NLO device applications.     

Imaging chirality with surface second harmonic generation microscopy

Chirality is a fundamental construct in nature which arises from an antisymmetric arrangement of atoms, molecules, or larger structures, resulting in the formation of nonsuperimposable mirror images. Bulk chiral effects can easily be measured using circular dichroism (CD) or optical rotary dispersion (ORD). However, the imaging of chirality originating from molecular surface films cannot be obtained with these linear optical methods. By using chiral second harmonic generation (C-SHG), with its inherent surface sensitivity and ability to discriminate between the symmetry of surface adsorbed species in combination with a counter-propagating optical geometry, we have developed the first nonlinear chiral microscope. In the study presented here, the intrinsic chirality of R- and S-(+)-1,1'-bi-2-naphthol (RBN, SBN) has been used to image a patterned planar supported lipid bilayer (PSLB) of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) using C-SHG. Spatial resolution of the patterned PSLB is visible when either RBN or SBN is intercalated into the membrane. No image is observed when a racemic mixture of RBN and SBN is present. The C-SHG images are compared with those obtained from fluorescence microscopy to verify the C-SHG imaging technique. The results presented here demonstrate that C-SHG possesses the requisite surface selectivity and sensitivity to detect interfacial chirality and provides a direct route for the visualization of chirality originating from molecular surface films.     

Invited Lecture. Studies of liquid crystal monolayers and films by optical second harmonic generation

It is shown that optical second harmonic generation can be used to probe a number of important properties of liquid crystals: second order non-linearity of liquid crystal molecules, polar ordering and orientation of liquid crystal monolayers at various interfaces, and bulk alignment of molecules in supported and freely suspended films. Surface effects on bulk alignment can also be investigated.     

Morphology and optical properties of thin silica films containing bimetallic Ag/Au nanoparticles

We have studied the optical spectra in the UV and visible regions, the morphology by scanning electron microscopy (SEM), and the X-ray photoelectron spectra (XPS) of bimetallic Ag/Au nanoparticles incorporated into transparent silicate films in the sol-gel transition stage. The bimetallic nanoparticles, obtained by a combination of photoreduction and thermal reduction, form structures of the alloy or core-shell type. Translated from Teoreticheskaya i éksperimental'naya Khimiya, Vol. 44, No. 6, pp. 348–353, November–December, 2008.     

Communication: Reactions and adsorption at the surface of silver nanoparticles probed by second harmonic generation

Even though nanoparticles have dimensions much smaller than the optical wavelength and shapes commonly with inversion symmetry, we show, for the first time, direct experimental evidence that second harmonic generation (SHG) can be detected from the surface layer of metallic nanoparticles, in this case 40 nm radius Ag particles. The SH intensity detected is shown to substantially decrease upon chemical bonding of thiol molecules to the Ag particle surface. The surface generated SH intensity can be used for probing properties and processes at the nanoparticle surface.