Interaction and energy transfer studies between bovine serum albumin and CdTe quantum dots conjugates: CdTe QDs as energy acceptor probes.

In this paper, a systematic investigation of the interaction of bovine serum albumin (BSA) with water-soluble CdTe quantum dots (QDs) of two different sizes capped with carboxylic thiols is presented based on steady-state and time-resolved fluorescence measurements. Efficient Förster resonance energy transfer (FRET) was observed to occur from BSA donor to CdTe acceptor as noted from reduction in the fluorescence of BSA and enhanced fluorescence from CdTe QDs. FRET parameters such as Förster distance, spectral overlap integral, FRET rate constant and efficiency were determined. The quenching of BSA fluorescence in aqueous solution observed in the presence of CdTe QDs infers that fluorescence resonance energy transfer is primarily responsible for the quenching phenomenon. Bimolecular quenching constant (kq ) determined at different temperatures and the time-resolved fluorescence data provide additional evidence for this. The binding stoichiometry and various thermodynamic parameters are evaluated by using the van 't Hoff equation. The analysis of the results suggests that the interaction between BSA and CdTe QDs is entropy driven and hydrophobic forces play a key role in the interaction. Binding of QDs significantly shortened the fluorescence lifetime of BSA which is one of the hallmarks of FRET. The effect of size of the QDs on the FRET parameters are discussed in the light of FRET parameters obtained.

Spectroscopic investigation of water-soluble alloyed QDs with bovine serum albumin.

We present here a systematic investigation on the interaction between a water-soluble alloyed semiconductor quantum dot and bovine serum albumin using various spectroscopic techniques i.e. fluorescence quenching, resonance light scattering and synchronous fluorescence spectroscopy. The analysis of fluorescence spectrum and fluorescence intensity indicates that the intrinsic fluorescence of bovine serum albumin (BSA) gets quenched by both static and dynamic quenching mechanism. The Stern-Volmer quenching constants, energy transfer efficiency parameters, binding parameters and corresponding thermodynamic parameters (ΔH0 , ΔS0 and ΔG0 ) have been evaluated by using van 't Hoff equation at different temperatures. A positive entropy change with a positive enthalpy change was observed suggesting that the binding process was an entropy-driven, endothermic process associated with the hydrophobic effect. The intermolecular distance (r) between donor (BSA) and acceptor (CdSeS/ZnS quantum dots) was estimated according to Förster's theory of non-radiative energy transfer. The synchronous fluorescence spectra revealed a blue shift in the emission maxima of tryptophan which is indicative of increasing hydrophobicity. Negative ΔG0 values implied that the binding process was spontaneous. It was found that hydrophobic forces played a role in the quenching process. Copyright © 2016 John Wiley & Sons, Ltd.

Electronic state spectroscopy of diiodomethane (CH2I2): experimental and computational studies in the 30,000-95,000 cm⁻¹ region.

The electronic absorption spectrum of diiodomethane in the 30,000-95,000 cm(-1) region is investigated using synchrotron radiation; the spectrum in the 50,000-66,500 cm(-1) region is reported for the first time. The absorption bands in the 30,000-50,000 cm(-1) region are attributed to valence transitions, while the vacuum ultraviolet (VUV) spectrum (50,000-95,000 cm(-1)) is dominated by several Rydberg series converging to the first four ionization potentials of CH2I2 at 9.46, 9.76, 10.21, and 10.56 eV corresponding to the removal of an electron from the outermost 3b2, 2b1, 1a2, and 4a1 non-bonding orbitals, respectively. Rydberg series of ns, np, and nd type converging to each of the four ionization potentials are assigned based on a quantum defect analysis. Time dependent density functional theory calculations of excited states support the analysis and help in interpretation of the Rydberg and valence nature of observed transitions. Density functional theory calculations of the neutral and ionic ground state geometries and vibrational frequencies are used to assign the observed vibronic structure. Vibronic features accompanying the Rydberg series are mainly due to excitation of the C-I symmetric stretch (ν3) and CH2 wag (ν8) modes, with smaller contributions from the C-H symmetric stretch (ν1). UV absorption bands are assigned to low lying valence states 1(1)B2, 1(1)B1, 2(1)A1, 3(1)A1, 2(1)B1, and 2(1)B2 and the unusually high underlying intensity in parts of the VUV spectrum is attributed to valence states with high oscillator strength. This is the first report of a comprehensive Rydberg series and vibronic analysis of the VUV absorption spectrum of CH2I2 in the 50,000-85,000 cm(-1) region. The VUV absorption spectrum of CD2I2 which serves to verify and consolidate spectral assignments is also reported here for the first time.

On the effects of permanent molecular dipoles in the simultaneous absorption of two photons: full generalized rotating wave approximation versus analytical results.

The effects of permanent dipoles, and the relative effects of the direct permanent dipole and the virtual state excitation mechanisms, are discussed for excitations involving the simultaneous absorption of two identical photons. Two molecular models for two-photon excitation, one dominated by the direct permanent dipole mechanism and the other having significant contributions from both excitation mechanisms, are used for this purpose. Resonance profiles, as a function of laser intensity, are evaluated for both models by employing the full Generalized Rotating Wave Approximation method and the recently developed Analytic Generalized Rotating Wave Approximation (AGRWA). The profiles are used to assess (1) the nature of the effects of permanent molecular dipoles, (2) the relative contributions of the two excitation mechanisms, and (3) the validity of the AGRWA for two-photon excitations. The AGRWA is a very useful interpretive∕predictive tool even for higher laser intensities where its validity becomes questionable. It can be used to suggest how to exploit the effects of molecular permanent dipoles to enhance two photon excitations using both excitation mechanisms.

Excited states of aniline by photoabsorption spectroscopy in the 30,000-90,000 cm(-1) region using synchrotron radiation.

The photoabsorption spectrum of aniline (C6H5NH2) in gas phase in the 30,000-90,000 cm(-1) (3.7-11.2 eV) region is recorded at resolution limit of 0.008 eV using synchrotron radiation source for the first time to comprehend the nature of the excited valence and Rydberg states. The first half of the energy interval constitutes the richly structured valence transitions from the ground to excited states up to the first ionization potential (IP) at 8.02 eV. The spectrum in the second half consists of vibrational features up to second IP (9.12 eV) and structureless broad continuum up to the third IP (10.78 eV). The electronic states are assigned mainly to the singlets belonging to π → π* transitions. A few weak initial members of Rydberg states arising from π → 4s, np or nd transitions are also identified. Observed vibrational features are assigned to transitions from the ground state A' to the excited states 1A", 3A', 5A", 6A', and 10A" in C(s) symmetry. Time dependent density functional theory (TDDFT) calculations at B3LYP level of theory are employed to obtain the vertical excitation energies and the symmetries of the excited states in equilibrium configuration. The computed values of the transition energies agree fairly well with the experimental data. Further the calculated oscillator strengths are used to substantiate the assignments of the bands. The work provides a comprehensive picture of the vacuum ultraviolet photoabsorption spectrum of aniline up to its third ionization limit.

Electromagnetically induced transparency in a Λ-type molecular system with permanent dipole moments revisited.

Electromagnetically induced transparency (EIT) in a molecular three-level Λ system with permanent dipole moments and undergoing m- and n-photon transitions by pump and probe lasers is investigated. Analytical expressions are derived for probe absorption spectrum and dispersion for a medium of stationary as well as thermal molecules. Contrary to the earlier study by Zhou et al. [J. Chem. Phys. 131, 034105 (2009)], we observe no amplification in 2 + 2 photon process when the sign of the difference of the permanent moments of the excited and the ground levels is reversed. Reasons for these contrasting observations are discussed. Our study shows that the permanent moments essentially damp the laser-molecule Rabi frequency to result in narrower EIT line width and larger group velocity index. These effects are further enhanced when the order of the multi-photon process is increased. The importance of the virtual mechanism is discussed by considering the special case of 2 + 1 photon EIT.

Measurement of temperature of laser cooled atoms by one-dimensional expansion in a magneto-optical trap.

We discuss a simple time of flight technique for measurement of temperature of a cold cloud in a magneto-optical trap (MOT). The technique is based on spatiotemporal fluorescence imaging of the cloud that is allowed to undergo one-dimensional expansion in the presence of the orthogonal two-dimensional configuration of laser beams by temporal modulation of a pair of counterpropagating trapping beams in the MOT. We show that, in the time scale 0< or =t<5 ms, the expansion of the cloud is ballistic and the temperature can be extracted from the time variation of the rms size of the cloud in the expansion direction. The reliability of the technique has been established by comparing the results with release and recapture method, and also by fitting them to the known temperature scaling law.

Absorption behavior of neutral uranium atoms in a pulsed hollow cathode discharge.

The temporal behavior of uranium neutrals in the postdischarge conditions in a pulsed hollow cathode discharge has been investigated by monitoring the time dependent absorption of the output radiation of a single-axial-mode dye laser by uranium atoms. Studies of the kinetics of the absorption suggest that electron ion recombination followed by deactivation, Penning ionization, and diffusion to the cathode wall are the dominant mechanisms in the postdischarge conditions.