Photoluminescence spectroscopy and lifetime measurements from self-assembled semiconductor-metal nanoparticle hybrid arrays

We present results of photoluminescence spectroscopy and lifetime measurements on thin film hybrid arrays of semiconductor quantum dots and metal nanoparticles embedded in a block copolymer template. The intensity of emission as well as the measured lifetime would be controlled by varying the volume fraction and location of gold nanoparticles in the matrix. We demonstrate the ability to both enhance and quench the luminescence in the hybrids as compared to the quantum dot array films while simultaneously engineering large reduction in luminescence lifetime with incorporation of gold nanoparticles. (C) 2010 American Institute of Physics. [doi:10.1063/1.3483162].

Influence of phosphate ligands in abolishing the conformational difference between ribonuclease A and its acid-denatured derivative

The initial structural alteration of RNAase A due to acid denaturation (0.5 N HCl, 30 degrees C) that accompanies deamidation (without altering enzymic activity) has been dectected by spectrophotometric titration, fluorescence and ORD/CD measurements. It is shown that acid treated RNAase A has an altered conformation at neutral pH, 25 degrees C. This is characterized by the increased accessibility of buried tyrosine residue(s) towards the solvent. The most altered conformation of RNAase A is found in the 10 h acid-treated derivative. This has about 1.5 additional exposed tyrosine residues and a lesser amount of secondary structure than RNAase A. All three methods (titration, fluorescence and CD) established that the structural transition of RNAase A is biphasic. The first phase occurs within 1 h and the resulting subtle conformational change is constant up to 7 h. Following this, after the release of 0.55 mol of ammonia, the major conformational change begins. The altered conformation of the acid-denatured RNAase A could be reversed completely to the native state through a conformational change induced by substrate analogs like 2'- or 3'-CMP. Thus the monodeamidated derivative isolated from the acid-denatured RNAase A by phosphate is very similar to RNAase A in over-all conformation. The results suggest the possibility of flexibility in the RNAase A molecule that does not affect its catalytic activity, as probed through the tyrosine residues.

XPS evidence for molecular charge-transfer doping of graphene

By employing X-ray photoelectron spectroscopy (XPS), we have been able to establish the occurrence of charge-transfer doping in few-layer graphene covered with electron acceptor (TCNE) and donor (TTF) molecules. We have performed quantitative estimates of the extent of charge transfer in these complexes and elucidated the origin of unusual shifts of their Raman G-bands and explained the differences in the dependence of conductivity on n- and p-doping. The study unravels the cause of the apparent difference between the charge-transfer doping and electrochemical doping. (C) 2010 Elsevier B.V. All rights reserved.

Structure, stoichiometry and spectroscopy of oxide superconductors

In the new oxide superconductors, structure and oxygen stoichiometry play the most crucial role. Thus, all the high-temperature oxide superconductors are orthorhombic perovskites with low-dimensional features. Oxygen stoichiometry in YBa2Cu3O7-δ has an important bearing on the structure as well as superconductivity. This is equally true in the La3-xBa3+xCu 6O14+δ system of which only the 123 oxide (x = 1) with the orthorhombic structure shows high Tc. Orthorhombicity though not essential, is generally found ; it is necessary for the formation of twins. The nature of oxygen and copper in the cuprates has been examined by electron spectroscopy. Copper in these cuprates is only in 1 + and 2 + states. It seems likely that oxygen holes are responsible for superconductivity of the cuprates as well as Ba(Bi, Pb)O3. High Tc superconductivity is also found in oxides of the Bi-(Ca, Sr)-Cu-O and related oxides possessing Cu-O sheets.

System effects in double‐channel gated‐integrator‐based deep‐level transient spectroscopy

The effects of the two sampling gate positions, and their widths and the integrator response times on the position, height, and shape of the peaks obtained in a double‐channel gated‐integrator‐based deep‐level transient spectroscopy (DLTS) system are evaluated. The best compromise between the sensitivity and the resolution of the DLTS system is shown to be obtained when the ratio of the two sampling gate positions is about 20. An integrator response time of about 100 ms is shown to be suitable for practical values of emission time constants and heating rates generally used.

Two-dimensional NMR spectroscopy of connected transitions by linear combination of flip angle dependent cosy: An alternative scheme for E.COSY

An alternative pulse scheme which simplifies and improves the recently proposed P.E.COSY experiment is suggested for the retention of connected or unconnected transitions in a coupled spin system. An important feature of the proposed pulse scheme is the improved phase characteristics of the diagonal peaks. A comparison of various experiments designed for this purpose, namely COSY-45, E.COSY, P.E.COSY and the present scheme (A.E.COSY), is also presented. The suppression of unconnected transitions and the measurement of scalar coupling constants and their relative signs are illustrated from A.E.COSY spectra of 2,3-dibromopropionic acid and 2-(2-thienyl)pyridine.

Improved retrieval of aerosol size-resolved properties from moderate resolution imaging spectroradiometer over India: Role of aerosol model and surface reflectance

We have compared the total as well as fine mode aerosol optical depth (tau and tau(fine)) retrieved by Moderate Resolution Imaging Spectroradiometer (MODIS) onboard Terra and Aqua (2001-2005) with the equivalent parameters derived by Aerosol Robotic Network (AERONET) at Kanpur (26.45 degrees N, 80.35 degrees E), northern India. MODIS Collection 005 (C005)-derived tau(0.55) was found to be in good agreement with the AERONET measurements. The tau(fine) and eta (tau(fine)/tau) were, however, biased low significantly in most matched cases. A new set of retrieval with the use of absorbing aerosol model (SSA similar to 0.87) with increased visible surface reflectance provided improved tau and tau(fine) at Kanpur. The new derivation of eta also compares well qualitatively with an independent set of in situ measurements of accumulation mass fraction over much of the southern India. This suggests that though MODIS land algorithm has limited information to derive size properties of aerosols over land, more accurate parameterization of aerosol and surface properties within the existing C005 algorithm may improve the accuracy of size-resolved aerosol optical properties. The results presented in this paper indicate that there is a need to reconsider the surface parameterization and assumed aerosol properties in MODIS C005 algorithm over the Indian region in order to retrieve more accurate aerosol optical and size properties, which are essential to quantify the impact of human-made aerosols on climate.

Cystine peptides. Disulfide conformations in fourteen membered loops investigated by Raman spectroscopy and circular dichroism

NHCH3 (X = Gly 1, Ala 2, Aib 3, Leu 4 and D-Ala 5), have been investigated by Raman and circular dichroism (CD) spectroscopy. Solid state Raman spectra are consistent with β-turn conformations in all five peptides. These peptides exhibit similar conformations of the disulfide segment in the solid state with a characteristic disulfide stretching frequency at 519 ± 3 cm-1, indicative of a trans-gauche-gauche arrangement about the Cα—Cβ—S—S—Cβ—Cα bonds. The results correlate well with the solid state conformations determined by X-ray diffraction for peptides 3 and 4. CD studies in chloroform and dimethylsulfoxide establish solvent dependent conformational changes for peptides 1, 3 and 5. Disulfide chirality has been derived using the quadrant rule. CD results together with previously reported nuclear magnetic resonance (n.m.r.) data suggest a conformational coupling between the peptide backbone and the disulfide segment

Conformations of dehydrophenylalanyl containing peptides. Nuclear Overhauser effect study of two acyclic

Two isomeric, acyclic tetrapeptides containing a Z-dehydrophenylalanine residue (Δz-Phe) at position 2 or 3, Boc-Leu-Ala-Δz-Phe-Leu-OMe (1) and Boc-Leu-Δz-Phe-Ala-Leu-OMe (2), have been synthesized and their solution conformations investigated by 270MHz 1H n.m.r. spectroscopy. In peptide 1 the Leu(4) NH group appears to be partially shielded from solvent, while in peptide 2 both Ala(3) and Leu(4) NH groups show limited solvent accessibility. Extensive difference nuclear Overhauser effect (n.O.e.) studies establish the occurrence of several diagnostic inter-residue n.O.e.s (CαjH ⇆ Ni+1H and NiH ⇆ Ni+1H) between backbone protons. The simultaneous observation of “mutually exclusive” n.O.e.s suggests the presence of multiple solution conformations for both peptides. In peptide 1 the n.O.e. data are consistent with a dynamic equilibrium between an -Ala-Δz-Phe- Type II β-turn structure and a second species with Δz-Phe adopting a partially extended conformation with Ψ values of ± 100° to ± 150°. In peptide 2 the results are compatible with an equilibrium between a highly folded consecutive β-turn structure for the -Leu-Δz-Phe-Ala- segment and an almost completely extended conformation.

Photobleaching reduced fluorescence correlation spectroscopy

A dual beam excitation-depletion pulse technique is proposed for photobleaching reduced fluorescence correlation spectroscopy (FCS). Excitation pulse promote the molecules to the excited singlet state (S-1), a fraction of that population goes to energetically favorable metastable triplet state (T-1) due to strong intersystem crossing. The depletion pulse followed by excitation pulse instantaneously depletes the triplet states thereby recycling the bleached molecules back to the ground state (S-0). FCS study on diffusing Fluorescein and Rh6G molecules show more than 95% reduction in triplet state population and the associated photobleaching. (c) 2010 American Institute of Physics.

Terahertz Time Domain Spectroscopy to Detect Low-Frequency Vibrations of Double-Walled Carbon Nanotubes

We have measured the frequency-dependent real index of refraction and extinction coefficient (and hence the complex dielectric function) of a free-standing double-walled carbon nanotube film of thickness 200 nm by using terahertz time domain spectroscopy in the frequency range 0.1 to 2.5 THz. The real index of refraction and extinction coefficient have very high values of approximately 52 and 35, respectively, at 0.1 THz, which decrease at higher frequencies. Two low-frequency phonon modes of the carbon nanotubes at 0.45 and 0.75 THz were clearly observed for the first time in the real and imaginary parts of the complex dielectric function along with a broad resonance centred at around 1.45 THz, the latter being similar to that in single-walled carbon nanotubes assigned to electronic excitations. Our experiments bring out a possible application of double-walled carbon nanotube films as a neutral density filter in the THz range.