Shift In Emission Spectra Research Articles

Solvent-Slaved Dynamic Processes Observed by Tryptophan Phosphorescence of Human Serum Albumin

Despite extensive experimental and computational efforts to understand the nature of the hierarchy of protein fluctuations and the modulating role of the protein hydration shell, a detailed microscopic description of the dynamics of the protein-solvent system has yet to be achieved. By using single tryptophan protein phosphorescence, we follow site-specific internal protein dynamics over a broad temperature range and demonstrate three independent dynamic processes. Process I is seen at temperatures below the bulk solvent Tg, has low activation energy, and is likely due to fast vibrations that may be enabled by water mobility on the protein surface. Process II is observed above 170 K, with activation energy typical of β relaxations in a glass; it has the same temperature dependence as fluctuations of hydration shell waters. Process III is observed at T > 200 K; it has super-Arrhenius temperature dependence and closely follows the primary relaxation of the bulk. The fluorescence of pyranine bound to the protein reports on the mobility of water in the hydration shell; it reveals a shift in emission spectra with increasing temperature, indicative of a changing H-bond network at the surface of the protein. These results support a model of solvent-slaved protein dynamics.

"Watching" the Dark State in Ultrafast Nonadiabatic Photoisomerization Process of a Light-Driven Molecular Rotary Motor.

Photoisomerization dynamics of a light-driven molecular rotary motor, 9-(2-methyl-2,3-dihydro-1H-cyclopenta[a]naphthalen-1-ylidene)-9H-fluorene, is investigated with trajectory surface-hopping dynamics at the semiempirical OM2/MRCI level. The rapid population decay of the S1 excited state for the M isomer is observed, with two different decay time scales (500 fs and 1.0 ps). By weighting the contributions of fast and slow decay trajectories, the averaged lifetime of the S1 excited state is about 710 fs. The calculated quantum yield of the M-to-P photoisomerization of this molecular rotary motor is about 59.9%. After the S0 → S1 excitation, the dynamical process of electronic decay is followed by twisting about the central C═C double bond and the motion of pyramidalization at the carbon atom of the stator-axle linkage. Although two S0/S1 minimum-energy conical intersections are obtained at the OM2/MRCI level, only one conical intersection is found to be responsible for the nonadiabatic dynamics. The existence of "dark state" in the molecular rotary motor is confirmed through the simulated time-resolved fluorescence emission spectrum. Both quenching and red shift of fluorescence emission spectrum observed by Conyard et al. [ Conyard, J.; Addison, K.; Heisler, I. A.; Cnossen, A.; Browne, W. R.; Feringa, B. L.; Meech, S. R. Nat. Chem. 2012 , 4 , 547 - 551 ; Conyard, J.; Conssen, A.; Browne, W. R.; Feringa, B. L.; Meech, S. R. J. Am. Chem. Soc. 2014 , 136 , 9692 - 9700 ] are well understood. We find that this "dark state" in the molecular rotary motor is not a new electronic state, but the "dark region" with low oscillator strength on the initial S1 state.

Abnormal temperature dependent luminescence behavior of CaSrSiO4:Eu2+ phosphors synthesized via sol-gel strategy

A silicate based crystal doped with Eu2+ phosphors have been synthesized by sol-gel method using propylene glycol modified silane (PGMS). The structural and luminescence properties of the as-prepared samples were well characterized by using x-ray diffractometer (XRD) & photoluminescence spectroscopy. Thermal stability of the prepared phosphors was also measured and analyzed in detail. The results revealed a new fact that longer wavelength emission band position is relatively more sensitive to the sample temperature for higher dopant concentrations when compared to the other emission bands. Such observations were not found in the samples prepared by solid phase reaction method. The CaSrSiO4 phosphor doped with 3 mol % of Eu2+ showed unique optical properties that consist of a shift in emission spectrum towards shorter wavelength along with a decreased band width (FWHM). The emission color tunability with the increase in temperature and concentration of the CaSrSiO4 phosphor were also discussed by CIE chromaticity diagram.

Spectroscopic properties of diketopyrrolopyrrole derivatives with long alkyl chains

The diketopyrrolopyrrole derivatives with long alkyl chains were synthesised and spectrally characterised. Experimental spectroscopic techniques were supplemented by the DFT calculations of equilibrium geometries, normal mode frequencies and time-dependent DFT simulated UV–vis spectra. Comparison between the symmetrical and unsymmetrical substitution of alkyl chains resulted in some changes like bathochromic shift of absorption, excitation and emission spectra, significant reduction of molar absorption coefficient in UV–vis range, increase of fluorescence quantum yield, and slight increase of fluorescence lifetimes. The influence of the length of the alkyl chain on the properties of material was also discussed. The experimental spectroscopic data together with the calculated results show that presence of the alkyl substituent at the nitrogen atom influences more on the properties of the investigated DPPs than the length of attached chain.

A new fluorescence chemosensor for Zn2+with a remarkable red shift in emission spectra

A new fluorescent chemosensor with a remarkable red shift in emission spectra based on naphthalene groups for quantification of zinc ions was synthesized and investigated.

Physico-chemical properties of β-diketone phosphorus-containing dendrimers

Protolytic, absorbance and fluorescence properties of β-diketone phosphorus-containing dendrimers based on cyclotriphosphazene core were studied. Dendrimer solutions in acetone are characterized by intense absorbance band at ≈ 340 nm (ε340≈ 8.5·104L/mol·сm) and fluorescence band with maximum at 440 nm. Position of these maxima does not change in various solvents, unlike the bands of monomer β-diketone. It was found that dendrimer aggregation is accompanied by appearance of a second absorbance band ε400≈ 4.5·103L/mol·сm, by red shift of emission spectra ∆λ ≈ 10 nm and also by decrease in surface tension of acetone solution. Ability of dendrimer aggregates to solubilize organic substrates was observed with the fluorescent indicator acridine.

Synthesis and Photoluminescence of Red to Near-Infrared-Emitting CdTe( x) Se(1−x) /CdZnS Core/Shell Quantum Dots.

Red to near-infrared (NIR)-emitting ternary-alloyed CdTe (x) Se(1−x) (x = 0–0.3) quantum dots (QDs) with tetrapod and dot morphologies have been synthesized by a facile method using oleic acid (OA) as single capping agent. The controlled dot-shaped and tetrapod-shaped CdTe( x) Se(1−x) QDs can be successfully obtained by adjusting the content of Te element. It is clear that CdTe (x) Se(1−x) QDs display the tunable emission peaks from the visible light (613.4 nm) to the NIR range (791.6 nm). With an inorganic CdZnS shell coated on the surface of CdTe(0.1)Se(0.9) cores, the stability and PL efficiency of the resulting core/shell QDs can be improved dramatically, accompanied with the red-shift of emission peaks to longer wavelength (795.6 nm). Peculiarly, a large blue shift of emission spectrum of CdTe(0.3)Se(0.7)/CdZnS core/shell QDs is observed, which is mainly ascribed to the shrink of the size of QDs by the fracture of tetrapod arms.

Effect of transition metal ion (Nb5+) doping on the luminescence properties of self-activated Ca2AgZn2V3O12 phosphors

Ca2AgZn2V3O12 self-activated vanadate phosphors were synthesized via a citrate assisted sol-gel method. The phase formation of the garnet structure was verified by X-ray diffraction (XRD) and Rietveld refinement analyses. From XRD patters, it is clear that the prepared samples were crystallized in cubic phase with a space group Ia3¯ d (230). The photoluminescence excitation spectrum showed a broad band in the UV region and a broad emission spectrum was observed in the wavelength range of 400–750 nm. The doping of transition metal ion (Nb5+) in the vanadium site changed the luminescence properties. Doping of Nb5+ ions increased the VO bond length from 1.7016 to 1.7148 Å which causes the increase in luminescence intensity and the red shift of emission spectrum. The increase in the luminescence intensity may also be attributed to the emission from Nb5+ ions. The thermal stability of the materials was measured and the activation energy was found to be 0.254 eV. The luminescence decay time was also measured and the values were found to be 158 and 154 μs for undoped and doped samples, respectively. The prepared phosphors exhibited a greenish yellow emission under UV excitation, indicating that they can be potential candidates for the application in UV-based WLEDs.

Dynamics of Single-Molecule Stokes Shifts: Influence of Conformation and Environment.

We report on time-dependent Stokes shift measurements of single molecules. Excitation and emission spectroscopy were applied to study the temporal Stokes shift evolution of single perylene diimide molecules embedded in a polymer matrix on the time scale of seconds. The Stokes shift varied between individual molecules as well as for single molecules undergoing different conformations and geometries. From the distribution and temporal evolution of Stokes shifts, we unravel the interplay of nanoenvironment and molecular conformation. We found that Stokes shift fluctuations are related to simultaneous and unidirectional shifts of both emission and excitation spectra.

Improved spatial calibration for the CXRS system on EAST.

A Charge eXchange Recombination Spectroscopy (CXRS) diagnostic system has been developed to measure profiles of ion temperature and rotation since 2014 on EAST. Several techniques have been developed to improve the spatial calibration of the CXRS diagnostic. The sightline location was obtained by measuring the coordinates of three points on each sightline using an articulated flexible coordinate measuring arm when the vessel was accessible. After vacuum pumping, the effect of pressure change in the vacuum vessel was evaluated by observing the movement of the light spot from back-illuminated sightlines on the first wall using the newly developed articulated inspection arm. In addition, the rotation of the periscope after vacuum pumping was derived by using the Doppler shift of neutral beam emission spectra without magnetic field. Combining these techniques, improved spatial calibration was implemented to provide a complete and accurate description of the EAST CXRS system. Due to the effects of the change of air pressure, a ∼0.4° periscope rotation, yielding a ∼20 mm movement of the major radius of observation positions to the lower field side, was derived. Results of Zeeman splitting of neutral beam emission spectra with magnetic field also showed good agreement with the calibration results.

Intravital multiphoton photoconversion with a cell membrane dye.

Photoconversion, an irreversible shift in a fluorophore emission spectrum after light exposure, is a powerful tool for marking cellular and subcellular compartments and tracking their dynamics in vivo. This paper reports on the photoconversion properties of Di-8-ANEPPS, a commercially available membrane dye. When illuminated with near-infrared femtosecond laser pulses, Di-8-ANEPPS undergoes multiphoton photoconversion as indicated by the supralinear dependence of the conversion rate ρpc on the incident power (ρpc∝Iexc2.27), and by the ability to photoconvert a thin optical section in a three-dimensional matrix. The characteristic emission spectrum changed from red to blue, and ratiometric analysis on single cells in vitro revealed a 65-fold increase in the blue to red wavelength ratio after photoconversion. The spectral shift is preserved in vivo for hours, making Di-8-ANEPPS a useful dye for intravital cell marking and tracking applications.

Effects of silver nanoparticles doping on morphology and luminescence behaviour of ferroelectric liquid crystals Langmuir–Blodgett films

ABSTRACTWe report the deposition of Langmuir–Blodgett (LB) thin films of low-weight dispersed composite systems of ferroelectric liquid crystals (FLCs)–functionalised silver (Ag) nanoparticles. Because of their amphiphilic nature the molecules form stable Langmuir monolayers, which were transferred to silicon substrates. We noticed that absorption wave numbers are present for each bond constituting FLC–nanoparticles composite system, ensuring a complete transfer of molecules from water sub-phase. XRD showed intense peaks at 2θ = 3.2° due to the layer structure of FLC molecules. We infer from the morphology of LB films that doping of nanoparticles do not provide any hindrance to SmC* layer structure of FLC molecules. The photoluminescence study indicates blue shift in emission spectra and peak intensity increases with Ag nanoparticles concentration.

Spectroscopic properties of Ce3+-doped borosilicate glasses under UV excitation

Li2O⿿BaO⿿La2O3⿿Al2O3⿿B2O3⿿SiO2 glasses doped with Ce3+ ion have been synthesized by melt-quenching method and the transmission, excitation, emission spectra and lifetime have been measured. A broad absorption band is observed in UV region, and it exhibits an intense blue emission which ascribes to 5d⿿4f electronic transition of Ce3+ ion under UV excitation. The emission intensity of Ce3+ ion in the borosilicate glasses decreases and the emission maximum of Ce3+ ion shifts to longer wavelength with the decreasing B2O3/SiO2 ratio. It could be found there are the existence of cerium concentration quenching phenomenon and the red shift of emission spectra of Ce3+-doped borosilicate glasses with the increase of Ce2O3 content. A fast luminescence decay time of about 26.6ns can be obtained in Ce3+-doped borosilicate glass, which indicates the potential applications of Li2O⿿BaO⿿La2O3⿿Al2O3⿿B2O3⿿SiO2 glasses doped with Ce3+ ion in radiation detection.

Narrow Red Emission Band Fluoride Phosphor KNaSiF6:Mn(4+) for Warm White Light-Emitting Diodes.

Red phosphors AMF6:Mn(4+) (A = Na, K, Cs, Ba, Rb; M = Si, Ti, Ge) have been widely studied due to the narrow red emission bands around 630 nm. The different emission of the zero-phonon line (ZPL) may affect the color rendering index of white light-emitting diodes (WLED). The primary reason behind the emergence and intensity of ZPL, taking KNaSiF6:Mn(4+) as an example, was investigated here. The effects of pressure on crystal structure and luminescence were determined experimentally and theoretically. The increase of band gap, red shift of emission spectrum and blue shift of excitation spectrum were observed with higher applied pressure. The angles of ∠FMnF and ∠FMF(M = Si, Ti, Ge) were found clearly distorted from 180° in MF6(2-) octahedron with strong ZPL intensity. The larger distorted SiF6(2-) octahedron, the stronger ZPL intensity. This research provides a new perspective to address the ZPL intensity problem of the hexafluorosilicate phosphors caused by crystal distortion and pressure-dependence of the luminescence. The efficacy of the device featuring from Y3Al5O12:Ce(3+) (YAG) and KNaSiF6:Mn(4+) phosphor was 118 lm/W with the color temperature of 3455 K. These results reveal that KNaSiF6:Mn(4+) presents good luminescent properties and could be a potential candidate material for application in back-lighting systems.

Anomalous Orange Light-Emitting (Sr,Ba)2SiO4:Eu(2+) Phosphors for Warm White LEDs.

Phosphors with sufficient red emission component are necessary for warm white light-emitting diodes. In this work on (Sr,Ba)2(1-x)Eu2xSiO4 phosphors, (Sr,Ba)1.5Eu0.5SiO4 achieved 75% of an internal quantum efficiency under excitation by blue light. Surprisingly, the (Sr,Ba)1.5Eu0.5SiO4 exhibited orange emission, against the well-known traditional green-yellow emission of (Sr,Ba)2SiO4:Eu(2+). Moreover, the concentration quenching of Eu(2+) in (Sr,Ba)2SiO4 was abnormally unobvious. With the help of calculations based on the density functional theory, it was discovered that the distinct local environment of luminescence centers rather than usual explanation such as self-absorption or intensified crystal field splitting, is responsible to the interesting red shifts in excitation and emission spectra. The refinement analysis based on X-ray diffraction revealed that the unequal distribution of Eu(2+) to two crystallographic sites caused low concentration of Eu(2+) at the 9-coordination site, inhibiting the concentration quenching. The (Sr,Ba)1.5Eu0.5SiO4 phosphor has warmer emission than the commercial Y3Al5O12:Ce(3+). This study also promotes research on the effect of site occupancy and the local environment of luminescence centers.

Synthesis and Characterization of Rhodamine B Embedded in MCM-41

Rhodamine B, a familiar organic dye, was embedded in mesoporous silica (MCM-41) that had been modified by (3-aminopropyl) triethoxysilane (APTES) through chemical bonding method. The materials were investigated by small angle X-ray diffraction (XRD), transmission electron microcopy (TEM), fourier transform infrared spectrometry (FT-IR), and photoluminescence spectroscopy (PL). The structure of the composites was characterized by XRD, which reveals that the mesoporous structure is maintained and the functional groups have been introduced into the mesostructure. The TEM photograph of the sample future shows that the ordered mesoporous structure is maintained after grafting. The FT-IR spectra improve that RhB has been successfully introduced into the mesoporous silica. The PL spectra of the product indicate that the emission spectrum shift to lower wavelength after grafting.

Studies of InAs/GaAs quantum dot laser grown by gas source molecular beam epitaxy

We reported on growth conditions of InAs/GaAs quantum dots laser grown by gas source molecular beam epitaxy. It was found that the uniformity and size of dots had a close collection with growth temperature and thicknesses of InAs layer. As the increase of growth temperature, the emission wavelength kept red shift and line width of emission spectra also increased. Good uniformity of QD could be easily obtained with a relative lower growth temperature of 425 °C. At a higher growth temperature of 500 °C, a wider tunable region of 129.9 nm was observed by adjusting the thicknesses of InAs layers. Comparison with a normal capping process, the growth interruption of capping materials would not lead to the formed dots collapse. An available growth temperature of 425 °C was obtained to achieve good performances of InAs/GaAs quantum dot laser, which had one facet power more than 103 mW under continuous wave mode.

Absorption Spectra and Electron-Vibration Coupling of Ti:Sapphire From First Principles

First-principles calculations are performed to study the absorption spectra and electron-vibration coupling of titanium-doped sapphire (Ti:Al2O3). Geometry optimization shows a local structure relaxation after the doping of Ti. Electronic band structure calculation shows that five additional dopant energy bands are observed around the band gap of Al2O3, and are attributed to the five localized d orbitals of the Ti dopant. The optical absorption spectra are then predicted by averaging the oscillator strength during a 4 ps first-principles molecular dynamics (MD) trajectory, and the spectra agree well with the experimental results. Electron-vibration coupling is further investigated by studying the response of the ground and excited states to the Eg vibrational mode, for which a configuration coordinate diagram is obtained. Stokes shift effect is observed, which confirms the red shift of emission spectra of Ti:sapphire. This work offers a quantitative understanding of the optical properties and crystal-field theory of Ti-doped sapphire. The first-principles calculation framework developed here can also be followed to predict the optical properties and study the electron-vibration coupling in other doped materials.

Physicochemical Investigation of 2,4,5-Trimethoxybenzylidene Propanedinitrile (TMPN) Dye as Fluorescence off-on Probe for Critical Micelle Concentration (CMC) of SDS and CTAB.

2,4,5-trimethoxybenzylidene propanedinitrile (TMPN) was synthesized by Knoevenagel condensation. Structure of the TMPN was conformed by the elemental analysis and EI-MS, FT-IR, (1)H-NMR, (13)C-NMR spectroscopy. Absorbance and emission spectrum of the TMPN was studied in different solvent provide that TMPN is good absorbent and emission red shift in absorbance and emission spectra as polarity of the solvents increase. Photophysical properties including, oscillator strength, extinction coefficient, transition dipole moment, stokes shift and fluorescence quantum yield were investigated in order to investigate the physicochemical behaviors of TMPN. Dye undergoes solubilization in different micelles and may be used as a probe to determine the critical micelle concentration (CMC) of SDS and CTAB.

Directional solidification, thermo-mechanical and optical properties of (Mg(x)Ca(1-x))(3)Al(2)Si(3)O(12) glasses doped with Nd(3+) ions.

In this work glass rods of (Mg(x)Ca(1-x))(3)Al(2)Si(3)O(12) (x = 0, 0.5 and 1) doped with 1 wt% Nd(2)O(3) were produced by the laser floating zone technique. Thermo-mechanical and spectroscopic properties have been evaluated. The three glass samples present good thermo-mechanical properties, with similar hardness, toughness and glass transition temperatures. The spectroscopic characterization shows spectral shifts in absorption and emission spectra. These spectral shifts together with Judd-Ofelt intensity parameters and ionic packing ratio have been used to investigate the local structure surrounding the Nd(3+) ions and the covalency of the Nd-O bond. All obtained results agree and confirm the higher covalency of the Nd-O bond in the Ca(3)Al(2)Si(3)O(12) glass.