Modulation of Visible and Near-Infrared Surface Plasmon Resonance of Au Nanoparticles Based on Highly Doped Graphene

We study an active modulation of surface plasmon resonance (SPR) of Au nanoparticles based on highly doped graphene in visible and near-infrared regions. We find that compared to the traditional metal SPR, the SPR of Au nanoparticles based on graphene causes a remarkable blue shift. The field intensity in the gap is redistributed to standing wave. The field intensity of standing wave is about one order of magnitude higher than the traditional model. Moreover, the SPR of Au nanoparticles can be actively modulated by varying the graphene Fermi energy. We find the maximum modulation of field intensity of absorption spectra is more than 21.6 % at λ?=?822?nm and the amount of blue shift is 17.4 nm, which is about 2.14 % of the initial wavelength λ ₀?=?813.4?nm, with increasing monolayer graphene Fermi energy from 1.0 to 1.5 ev. We find that the SPR sensitivity to the refractive index n of the environment is about 642 nm per refractive index unit (RIU). The SPR wavelengths have a big blue shift, which is about 33 nm, with increasing number of graphene layers from 1 to 3, and some shoulders on the absorption spectra are observed in the models with multilayer graphene. Finally, we study the Au nanorod array based on monolayer graphene. We find that the blue shift caused by the graphene increases from 14 to 24 nm, with increasing gap g _y from 10 to 20 nm. Then, it decreases from 24 to 14 nm, with increasing gap g _y from 20 to 50 nm. This study provides a new way for actively modulating the optical and optoelectronic devices.     

Numerical Simulation of Broadband Scattering by Coated and Noncoated Metal Nanostructures Using Discrete Dipole Approximation Method

We suggest numerical method to study the optical response of metal nanostructures. The analysis of optical properties such as scattering and absorption by coated and noncoated nanogeometry has been done using discrete dipole approximation (DDA) method. The core-shell nanogeometry supports surface plasmon resonances, which are highly tunable from 400 to 1100 nm. The tunability of surface plasmon resonance (SPR) highly depends on the structural anisotropy and chosen core-shell material. Further, we have observed that aspect ratio is one of the key parameter to decide the nature and position of the plasmonic peaks and magnitude of optical cross section. We have also shown that coated nanospheroid is a more appropriate geometry as compared to coated nanosphere and noncoated nanospheroid in terms of wide tunability of surface plasmon resonance. The wide tunability in SPR is observed for the effective radii 90 nm core-shell (Au@SiO₂) nanospheroid with aspect ratio 0.1.     

Wavelength-dependent photodamage to <Emphasis Type="Italic">Chlorella</Emphasis> investigated with a new type of multi-color PAM chlorophyll fluorometer

A new type of multi-color PAM chlorophyll fluorometer (Schreiber et al. 2012) was applied for measurements of photodamage to photosystem II (PS II) in optically thin suspensions of Chlorella (200 μg Chl l^?1) in the presence of 1 mM lincomycin. An action spectrum of the relative decrease of F _v/F _m in the 440–625 nm range was measured, which not only showed the expected high activity in the blue, but at a lower level also substantial activity above 540 nm. With the same dilute suspension, a PS II absorption spectrum was derived via measurements of the O-I₁ rise kinetics induced by differently colored strong light at defined incident quantum flux densities. After normalization of the two spectra at 625 nm, the relative extent of photodamage at 440–480 nm proved substantially higher than absorption by PS II, whereas the two spectra were close to identical in the 540–625 nm range. Hence, overall photodamage to PS II appears to consist of two components, one of which is due to light absorbed by PS II pigments, whereas the other one is likely to involve direct light absorption by Mn in the oxygen-evolving complex (Hakala et al. Biochim Biophys Acta 1706:68–80, 2005). Based on this rationale, an action spectrum of the Mn mechanism of photodamage was deconvoluted from the overall action spectrum, declining steeply above 480 nm. An almost identical Mn-spectrum was derived by another approach with the PAR of the various colors being adjusted to give identical rates of PS II turnover, PAR _II. The tentative, basic assumption of negligibly small contribution of the Mn mechanism to photodamage above 540 nm was supported by supplementary measurements using an external 665 nm lamp. 665 nm not only gave about two times PS II turnover as compared to 625 nm, but also about two times photodamage.     

Plasmonic Au-MoO<Subscript>3</Subscript> Colloidal Nanoparticles by Reduction of HAuCl<Subscript>4</Subscript> by Blue MoO<Subscript>x</Subscript> Nanosheets and Observation of the Gasochromic Property

Defective colloids of blue MoO_x nanosheets were prepared by anodizing exfoliation method in water. This colloidal solution exhibits an optical plasmonic absorption band in the infrared region at about 760 nm. Merely mixing HAuCl₄ solution with the MoO_x leads to loss of the blue color, decaying of 760 nm plasmonic peak and simultaneous formation of the gold plasmon absorption peak at 550–570 nm. Some spectral variations in gold plasmonic peak and MoO_x optical band gap were observed for Mo:Au ratio of 10:1, 20:1, 30:1, and 40:1. The size of the gold nanoparticles was in the 5–6 nm range with fcc crystalline structure. X-ray photoelectron spectroscopy (XPS) revealed that the initial solution contains Mo⁵⁺ states and hydroxyl groups, which after reduction, hydroxyl groups are eliminated and the Mo⁵⁺ states converted to Mo⁶⁺. The obtained Au-MoO₃ colloids have a gasochromic property in which they are colored back to blue in the presence of hydrogen gas and the molybdenum oxide absorption peak recovered again. Furthermore, it was observed that both gold and Mo oxide plasmonic peaks redshift by insertion of hydrogen gas which is attributed to change in solution refractive index and formation of defect concentration.     

Plasmonic and Nonlinear Optical Absorption Properties of Ag:ZrO2 Nanocomposite Thin Films

Ag nanoparticles (NPs) embedded in a zirconium oxide matrix in the form of Ag:ZrO₂ nanocomposite (NC) thin films were synthesized by using the sol–gel technique followed by thermal annealing. With the varying of the concentration of Ag precursor and annealing conditions, average sizes (diameters) of Ag nanoparticles (NPs) in the nanocomposite film have been varied from 7 to 20 nm. UV–VIS absorption studies reveal the surface plasmon resonance (SPR)-induced absorption in the visible region, and the SPR peak intensity increases with the increasing of the Ag precursor as well as with the annealing duration. A red shift in SPR peak position with the increase in the Ag precursor concentration confirms the growth of Ag NPs. Surface topographies of these NC films showed that deposited films are dense, uniform, and intact during the variation in annealing conditions. The magnitude and sign of absorptive nonlinearities were measured near the SPR of the Ag NPs with an open-aperture z-scan technique using a nanosecond-pulsed laser. Saturable optical absorption in NC films was identified having saturation intensities in the order of 10¹² W/m². Such values of saturation intensities with the possibility of size-dependent tuning could enable these NC films to be used in nanophotonic applications.     

Speckled SiO2@Au Core–Shell Particles as Surface Enhanced Raman Scattering Probes

Silica particles of ~800 nm size were functionalized using 3-amino propyl triethoxysilane molecules on which gold particles (~20 nm size) were deposited. The resulting particles appeared to form speckled SiO₂@Au core–shell particles. The surface roughness, along with hot spots, due to nanogaps between the gold nanoparticles was responsible for the enhancement of the Raman signal of crystal violet molecules by ~3.2?×?10⁷ and by ~1.42?×?10⁸ of single-wall carbon nanotubes. It has also been observed that the electromagnetic excitation near surface plasmon resonance (SPR) of core–shell particles is more effective than off resonance SPR excitation.     

Theoretical study on phthalocyanine,pyrazinoporphyrazine and their complexation with Mg2+ and Zn2+

We have studied the UV–vis absorption spectra of metal-free phthalocyanine (H₂Pc), metal-free pyrazinoporphyrazine (H₂PyzPz) and their complexes with Mg^2 +  and Zn^2 +  using semiempirical Zerners intermediate neglect of differential overlap and time-dependent density functional theory methods. The predicted absorption spectra of H₂Pc and their complexes are in agreement with a previous experiment report. The calculated results show that the Q band absorption peaks of H₂PyzPz and their complexes are blue-shifted by 40 nm as compared with those of H₂Pc and their complexes, respectively. The frontier molecular orbitals (HOMO and LUMO) of H₂Pc, H₂PyzPz and their metal complexes were investigated as well. The nitrogen atoms in the pyrazine rings stabilise the HOMO more than the LUMO, and the deprotonation of the pyrrole rings induced by the metal coordination destabilises the LUMO more than the HOMO. Because of the increased band gap, the absorption bands of H₂PyzPz and the metal-coordinated compounds are blue-shifted.     

A new silver nanochain SERS analytical platform to detect trace hexametaphosphate with a rhodamine S molecular probe

Using AgNO₃ as the precursor, stable silver nanochain (AgNC) sols, orange‐red in color, were prepared using hydrazine hydrate. A strong surface plasmon resonance Rayleigh scattering (RRS) peak occurred at 420 nm plus two surface plasmon resonance (SPR) absorption peaks at 410 nm and 510 nm. Rhodamine S (RhS) cationic dye was absorbed on the as‐prepared AgNC substrate to obtain a RhS–AgNC surface‐enhanced Raman scattering (SERS) nanoprobe that exhibited a strong SERS peak at 1506 cm^–1 and a strong RRS peak at 375 nm. Upon addition of the analyte sodium hexametaphosphate (HP), it reacted with RhS, which resulted in a decrease in the SERS and RRS peaks that was studied in detail. The decreased SERS and RRS intensities correlated linearly with HP concentration in the range of 0.0125–0.3 µmol/L and 0.05–1.0 µmol/L, with a detection limit of 6 nmol/L and 20 nmol/L HP respectively. Due to advantages of high sensitivity, good selectivity and simple operation, the RhS molecular probes were used to determine HP concentration in real samples. Copyright © 2015 John Wiley & Sons, Ltd.     

Plasmonic Spectral Detection of Carcinoembryonic Antigen by Preventing the Direct Binding of Rhodamine 6G with Au Nanoparticles

Carcinoembryonic antigen (CEA) was used as a separator to prevent the Rhodamine 6G (R6G)-induced aggregation of colloidal gold nanoparticles. The destroyed aggregation has been monitored by measuring the absorption and resonance light scattering peaks corresponding to the longitudinal surface plasmon resonance (SPR) of the chain-like aggregated gold nanoparticles (AuNPs). It was found that the pre-adding of CEA with different concentrations to the gold colloids before mixing them with R6G could lead to the longitudinal SPR peak decrease and blue shift. By analysing the intensity changing and wavelength shifting of the absorption spectra, CEA could be detected in a linear range from 0.2 to 4 ng/mL, and the limit of detection reaches to 0.1 ng/mL. The sensitivity of the CEA concentration dependent shifting and quenching of the plasmonic absorption and scattering corresponding to the AuNPs aggregation presents a well potential application of biologic spectral sensing.     

Tuning the Plasmon of Metallic Nanostructures: From Silver Nanocubes Toward Gold Nanoboxes

One of the most significant advances in nanoscience and nanotechnology was partially driven by plasmonic effect of some noble metal nanostructures with different shapes and sizes. By controlling the geometry of metal nanostructures, their surface plasmon resonance (SPR) peaks could be tuned from the visible to the near-infrared region with various applications in sensors, optoelectronic, nanomedicine, and specifically cancer therapy. In this study, we have prepared gold nanoboxes (NBs) using the galvanic replacement between Ag nanocubes (NCs) and aqueous gold solution. Ultraviolet visible (UVvis) spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD), and transmitting electron microscopy (TEM) were used to characterize silver NCs and gold NBs. The primary silver NCs were synthesized by conventional polyol method at the presence of sodium sulfide to highly tune the shape and size of the NCs. Optimized cubic silver nanostructures were obtained at 90 μl of sodium sulfide injection into the solution. Moreover, the effect of quality of the cubic structure on the shape and uniformity of gold NBs was investigated. Gold NBs with hollow interior structure and SPR peak ranging from 480 to 800 nm were successfully obtained at different injection volumes of HAuCl₄ into the solution. It was demonstrated that increasing the volume of HAuCl₄ solution to about 3 mL can increase the pore number and size until the primary structure collapses into small pieces. It was also found that the concentration of gold NBs and the corresponding SPR peak intensities decrease due to pore size enhancement and decline of charge density on the surface of metal hollow nanostructures.     

Photocatalytic Activity of Ag/TiO2 Nanotube Arrays Enhanced by Surface Plasmon Resonance and Application in Hydrogen Evolution by Water Splitting

TiO₂ nanotube arrays (TiO₂ NTs) were fabricated by anodic oxidation and then Ag nanoparticles (Ag NPs) were assembled in TiO₂ NTs (Ag/TiO₂ NTs) by microwave-assisted chemical reduction. The samples were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), photoluminescence spectrum (PL), UV–vis absorption spectrum (UV–vis), and Raman spectrum, respectively. The results showed that Ag NPs were well dispersed on the surface of TiO₂ NTs with metallic state. The surface plasmon resonance (SPR) effect of Ag NPs could extend the visible light response and enhance the absorption capacity of TiO₂. Furthermore, Ag NPs could also restrain the recombination of photo-generated electron–hole pairs of TiO₂ NTs efficiently. The methylene blue photodegradation experiment proved that the SPR phenomenon had an effect on photoreaction enhancement. The results of photocatalytic water splitting indicated that Ag/TiO₂ NTs samples had better photocatalytic performance than pure TiO₂ NTs. The corresponding hydrogen evolution rate of Ag/TiO₂ NTs prepared with 0.002 M AgNO₃ solution was 3.3 times as that of pure TiO₂ NTs in the test condition. Additionally, the mechanism of catalyst activity enhanced by SPR effect was proposed.     

Triangular Au�CAg Nanoframes with Tunable Surface Plasmon Resonance Signal from Visible to Near-Infrared Region

In recent years, metal hollow nanostructures are intriguing to be synthesized and studied because they exhibit unique surface plasmonic properties. Although many methods for tuning the surface plasmonic absorption peaks of silver nanostructures have been reported, it still remains a great challenge to produce hollow Ag nanostructure with controllable surface plasmon resonance (SPR) via a facile method. In this paper, triangular Au–Ag nanoframes were successfully fabricated using triangular silver nanoplates as templates, through galvanic replacement reaction between the silver nanoplates and HAuCl₄, exhibiting tuneable SPR response from visible (605 nm) to near-infrared region (1,235 nm).     

Strong Near-infrared Avalanche Photoluminescence from Ag Nanowire Arrays

Ag nanowire (NW) arrays with NW diameter d _NW?=?12–120 nm were electrodeposited in anodic aluminum oxide templates. Strong avalanche photoluminescence (PL) from Ag NW arrays with small d _NW were observed near 914 nm by using picosecond laser at the excitation wavelength 808 nm, which is originated from the plasmon-enhanced radiative intraband transitions. The peak PL intensity of the avalanche PL from the sample with small diameter d _NW?=?12 nm is about 10² times stronger than that of the linear PL from the sample with large diameter d _NW?=?120 nm. The opposite excitation polarization dependence and emission polarization distribution of the PL from Ag NW array with d _NW?=?12 nm and d _NW?=?120 nm were also observed.     

Tuning Plasmonic Properties of Truncated Gold Nanospheres by Coating

The influence of TiO₂ coating on resonant properties of gold nanoisland films deposited on silica substrates was studied numerically and in experiments. The model describing plasmonic properties of a metal truncated nanosphere placed on a substrate and covered by a thin dielectric layer has been developed. The model allows calculating a particle polarizability spectrum and, respectively, its surface plasmon resonance (SPR) wavelength for any given cover thickness, particle radius and truncation parameter, and dielectric functions of the particle, the substrate, the coating layer, and the surrounding medium. Dependence of the SPR position calculated for truncated gold nanospheres has coincided with the measured one for the gold nanoisland films covered with titania of different thicknesses. In the experiments, gold films with thickness of 5 nm were deposited on a silica glass substrate, annealed at 500 °C to form nanoislands of 20 nm in diameter, and covered with amorphous titania layers using atomic layer deposition technique. The resulting structures were characterized with scanning electron microscopy and optical absorption spectroscopy. The measured dependence of the SPR position on titania film thickness corresponded to the one calculated for truncated sphere-shaped nanoparticles with the truncation angle of ~50°. We demonstrated the possibility of tuning the SPR position within ~100 nm range by depositing to 30 nm thick titania layer.

     

Photosynthetic energy storage of Photosystems I and II in the spectral range of photosynthetically active radiation in intact sugar maple leaves

The relative activity of Photosystems (PS) I and II in the spectral range between 400 and 720 nm was studied by measuring photosynthetic energy storage (ES) of an intact sugar maple leaf using photoacoustic spectroscopy. ES, determined with a modulated (80 Hz) monochromatic light beam in the presence of saturating intensity of background non-modulated white light, indicated the total energy stored by both photosystems (ES_T). Using background far-red light, ES of PS I (ES_{PS I}) was quantified. ES_{PS II} was derived from ES_T-ES_{PS I}. ES_T dependence on intensity and wavelength of modulated light was studied at 470, 560, 640 and 680 nm. ES_T was maximum in red light and minimum in blue light. It decreased with an increase in modulated light intensity. The ratio ES_{PS II}/ES_{PS I}, measured at 640 nm, remained nearly constant with an increase in modulated light intensity. The relative quantum yield of ES_T spectrum showed two peaks around 610 and 660 nm, and declined sharply after 680 nm, revealing a clear red drop. ES_{PS I} spectrum presented peaks around 610 and 670 nm, and a minimum between 440 and 470 nm. ES_{PS I} was observed beyond 700 nm up to 720 nm, indicating the energy stored by cyclic electron transport. ES_{PS II} spectrum showed broad peaks, around 460, 490, 600 and 660 nm, and a shoulder between 530 and 560 nm. ES_{PS II} was always higher than ES_{PS I} between 400 and 690 nm and reached zero around 700 nm.Abbreviations ES energy storage - ES_{PS I} energy storage of PS I - ES_{PS II} energy storage of PS II - ES_T energy storage of PS I and PS II - PA photoacoustic - PS I Photosystem I - PS II Photosystem II - Q_m PA signal in the absence of any background light - Q_ma PA signal in the presence of background white light - Q_mfrl PA signal in the presence of background far-red light - S/N signal to noise     

Fluorescent (Au@SiO2)SiC Nanohybrids: Influence of Gold Nanoparticle Diameter and SiC Nanoparticle Surface Density

Gold@silica core–shell nanoparticles were prepared with various gold core diameters (ranging from 20 to 150 nm) and silica thicknesses (ranging from 10 to 30 nm). When the gold diameter is increased, the size dispersion became larger, leading to a broader plasmon band. Then, silicon carbide (SiC) nanoparticles were covalently immobilized onto silica to obtain hybrid (Au@SiO₂) SiC nanoparticles. The absorption properties of these hybrid nanoparticles showed that an excess of SiC nanoparticles in the dispersion can be identified by a strong absorption in the UV region. Compared to SiC reference samples, a blue shift of the fluorescence emission, from 582 to 523 nm, was observed, which was previously attributed to the strong surface modification of SiC when immobilized onto silica. Finally, the influence of several elaboration parameters (gold diameter, silica thickness, SiC concentration) on fluorescence enhancement was investigated. It showed that the highest enhancements were obtained with 10 nm silica thickness, low concentration of SiC nanoparticles, and surprisingly, with a 20-nm gold core diameter. This last result could be attributed to the broad plasmon band of big gold colloids. In this case, SiC emission strongly overlapped gold absorption, leading to possible quenching of SiC fluorescence by energy transfer.     

Spectral Investigations on the Fluorescence Quenching of 1,4-dihydroxy-2,3-dimethylanthracene-9,10-dione by Plasmonic Silver Nanoparticles

Silver nanoparticles (Ag NPs) of different sizes have been prepared by Lee and Meisel’s method using trisodium citrate as reducing agent under ultra sonication. Optical absorption and fluorescence emission techniques were employed to investigate the interaction of 1,4-dihydroxy-2,3-dimethyl anthracene-9,10-dione (DHDMAD) with silver nanoparticles. In fluorescence spectroscopic study, we used the DHDMAD and Ag NPs as component molecules for construction of Förster Resonance Energy Transfer (FRET), whereas DHDMAD serve as donor and Ag NPs as acceptor. The surface plasmon resonance (SPR) peak of the prepared silver colloidal solution was observed from 419 nm to 437 nm. The synthesized silver nanoparticles at different heating time intervals were spherical in shape about the size of 25 nm and 55 nm. The fluorescence interaction between silver nanoparticles and DHDMAD confirms the FRET mechanism. According to Förster theory, the distance between silver nanoparticles and DHDMAD and the critical energy transfer distance were calculated and it is increase with heating time.     

UV-absorbing bacteria in coral mucus and their response to simulated temperature elevations

Reef-building corals encompass various strategies to defend against harmful ultraviolet (UV) radiation. Coral mucus contains UV-absorbing compounds and has rich prokaryotic diversity associated with it. In this study, we isolated and characterized the UV-absorbing bacteria from the mucus of the corals Porites lutea and Acropora hyacinthus during the pre-summer and summer seasons. A total of 17 UV-absorbing bacteria were isolated and sequenced. The UV-absorbing bacteria showed UV absorption at wavelengths ranging from λ _max = 333 nm to λ _min = 208 nm. Analysis of the DNA sequences revealed that the majority of the UV-absorbing bacteria belonged to the family Firmicutes and the remaining belonged to the family Proteobacteria (class Gammaproteobacteria). Comparison of the sequences with the curated database yielded four distinct bacterial groups belonging to the genus Bacillus, Staphylococcus, Salinicoccus and Vibrio. The absorption peaks for the UV-absorbing bacteria shifted to the UV-A range (320–400 nm) when they were incubated at higher temperatures. Deciphering the complex relationship between corals and their associated bacteria will help us to understand their adaptive strategies to various stresses.     

Psychological Stress-Induced Lower Serum Zinc and Zinc Redistribution in Rats

In humans, long-term exposure to uncontrollable and unpredictable life stressors is a major precipitant in the development of depressive disorders. There are strong evidences that depression is accompanied by lower serum zinc. The aim of present study is to assess the effects of repeated psychological stress (PS) on the zinc metabolism in rat. The rats were divided into control group and PS group which were subdivided into three subgroups: 7-day group, 14-day group, and recovery group (ten rats in each subgroup). PS model was created by a communication box which contains room A and room B. Rats in room A were only exposed to the responses of rats which were randomly given electrical shock for 30 min in room B. PS was given to rats for 30 min every morning for 14 days. The serum corticosterone (CORT), zinc in serum and tissues, and zinc apparent absorption after PS exposure were investigated. The results showed that the serum CORT increased and serum zinc decreased after 7 and 14 days of PS treatment. The zinc concentration in the liver was increased by 14 days PS exposure, whereas its concentration in the hippocampus was decreased by 7 and 14 days of PS exposure. There were no significant changes in zinc concentration in the heart, spleen, kidney, duodenum, cortex, and cerebellum. A decrease in the zinc apparent absorption was observed in the 7- and 14-day PS groups. The increased serum CORT and liver zinc concentrations and decreased serum zinc and apparent absorption of zinc recovered to normal concentrations 7 days away from PS exposure. The results suggest that PS could induce lower serum zinc, which might be correlated with decreased zinc absorption in the small intestine and increased liver zinc accumulation after PS exposure. The consequent effects of decreased hippocampal and serum zinc and increased CORT concentration after PS exposure on stress-related diseases await further research.