Time-resolved spectroscopy of long-path fluorescence and scattering for measuring total absorption of fluids

Optical methods are appropriate tools to detect organic micro-pollutants in fluids. A new technique is introduced which uses the decay of interaction processes like fluorescence and elastically scattered radiation by a fluid. Principally two different parameters are determined:

1. (i) the decay-time of the conventional interaction τ_C, which occurs at relatively short path-lengths of the incidence beam in the fluid, and

2. (ii) the decay-time τ_MP of the multi-path-saturation interaction originating at long path-lengths, e.g. in multi-path-reflection cuvettes, where the incidence beam is fully absorbed by the fluid.

A relation between the decay-time and the absorption coefficient of a fluid is theoretically derived. A simple preliminary experiment is performed considering distilled water polluted with non-fluorescent azobenzene and fluorescent quinine-sulphate. A nitrogen laser has been used to generate the fluorescence and scattering signals. The reciprocal value of the difference between the decay-time of the multi-path and conventional signals, 1/(τ_MP − τ_C), yields the total absorption coefficient directly. In comparison to the conventional absorption technique the decay-time method is characterized by a higher sensitivity.     

Distance-dependent fluorescence quenching ofN-acetyl-l-tryptophanamide by acrylamide

We examined the time-dependent intensity decays ofN-acetyl-l-tryptophanamide (NATA) when collisionally quenched by acrylamide in propylene glycol over a range of temperatures. The intensity decays of NATA became increasingly heterogeneous in the presence of acrylamide. The NATA intensity decays were not consistent with the Collins-Kimball radiation boundary condition (RBC) model for quenching. The steady-state Stern-Volmer plots show significant upward curvature, and quenching of NATA by acrylamide was observed even in vitrified propylene glycol, where translational diffusion cannot occur during the lifetime of the excited state. These frequencydomain and steady-state data indicate a through-space quenching interaction between NATA and acrylamide, and the results are consistent with a rate constant for quenching that depends exponentially on the fluorophore-quencher separation distance. The exponential distance-dependent rate of quenching also explains the upward curvature of the Stern-Volmer plot, and the steady-state data aid in determining the interaction distance between NATA and acrylamide. These results suggest that the distance-dependent quenching rates need to be considered in the interpretation of acrylamide quenching of proteins.     

Microenvironmental differences amongst micelles of various shapes and structures

Micelles of different amphiphiles adopt different shapes and internal packing arrangements in water, depending on their chemical structures and the conditions of the medium. Two microenvironmental features, namely the polarity and the microviscosity that the aggregate offers to a solubilized molecule, have been monitored using extrinsic fluorescence probes. While the differences between micelles of spherical and rod-like shapes are not always distinct, stacked micelles and peptide micelles offer distinctly lower polarity and higher microviscosity to solubilizates than the others.     

Positron annihilation studies of poly(N‐isopropyl acrylamide) gel in mixed solvents

Positron annihilation lifetime spectroscopy was used to characterize the reentrant volume‐phase‐transition behavior of poly(N‐isopropyl acrylamide) hydrogel in an ethanol/water mixed solvent. The polymer gel was synthesized with γ irradiation. The ortho‐positronium lifetime (τ₃) in the gel slowly increased with an increase in the ethanol content in the mixed solvent. τ₃ was not influenced by the volume phase transition. The ortho‐positronium intensity decreased with the collapse of the gel in an approximately 10% ethanol/water mixture. When swelled in pure ethanol, τ₃ initially increased with the solvent amount in the gel, showing the destruction of intramolecular hydrogen bonding and the relaxation of polymer chains. The lower critical solution temperature of the gel in the 10% ethanol/water mixture was lower than that in pure water, and τ₃ for various solvent contents showed behavior similar to that seen in pure solvent. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1028–1036, 2002     

From a point-like to an arbitrarily shaped sample: A survey of equations for electron paramagnetic resonance signal intensity calculations

A set of original, analytical equations useful for theoretical calculation of the electron paramagnetic resonance (EPR) signal intensity are presented for the multitude of sample shapes, which range from point-like, line-like, planar, rectangular, cubical, circular, cylindrical, spherical to an irregularly shaped sample. The samples can be situated at any available position within the prescribed part of the microwave cavity (a central cylinder of diameter 11 mm and length 23.5 mm, in either a Bruker single TE₁₀₂ or double TE₁₀₄ rectangular cavity, with the modulation coils situated in the left and right side cavity walls, which is connected to a X-band, field-modulated CW Bruker EPR spectrometer). The theoretical computations of EPR signal intensity can be used in the computer simulations in which: (i) the EPR signal intensity profiles are constructed; (ii) the optimal sample positions in the cavity to give a maximum value of signal intensity are found; (iii) the errors associated with sample positioning within the cavity when compared to a second sample of a different size, shape or position are studied.     

交联聚丙烯酰胺吸水凝胶的强度

高吸水材料是一类新型的功能高分子材料,已有广泛开发和应用。本文讨论了含大量无机填料膨润土的阴离子型交联聚丙烯酰胺(JSWAM)吸水凝胶的强度及其形态结构。 吸水材料JSWAM的制备:将填料搅拌分散于丙烯酰胺水溶液中,同时加入规定量的甲叉基双丙烯酰胺、过硫酸铵、碱,而后聚合并水解。将聚合物胶块造粒、烘干、粉碎。凝胶强度     

DFT study and vibrational spectra of the phoshorus-containing G0 generation dendrimer

The Raman (10–3500 cm⁻¹) and infrared (150–3500 cm⁻¹) spectra have been recorded for tris(4-oxibenzaldehyde)thiophosphate. This compound includes structural parts of elementoorganic dendrimers: a core and terminal aldehyde groups. The structural optimization and normal mode analysis are performed for elementoorganic dendrimer on the basis of the ab initio density functional theory. It is found that the dendrimer exist in a single stable conformation with planar C₆H₄CHO fragments. Our calculations show that conformer with one trans and two gauche 4-oxibenzaldehyde groups is realized. All these observations suggest that steric congestion does not disturb the construction of dendrimers even for the highest generations, and that terminal groups are readily available for further reactions. Relying on DFT calculations a complete vibrational assignment is proposed for different parts of the studied dendrimers.     

Atom-surface elastic scattering in the presence of laser radiation

A qualitative discussion on atom-surface elastic scattering taking place in the presence of laser radiation is given. It is suggested that appreciable effects of laser radiation on diffraction patterns may be expected if the laser radiation is capable of inducing electronic transitions in atoms with a large probability.Research sponsored by the Air Force Office of Scientific Research (AFSC), United States Air Force, under Contract No. F49620-78-C-0005, and the National Science Foundation under Grant No. CHE77-27826. The United States Government is authorized to reproduce and distribute reprints for governmental purposes notwithstanding any copyright notation hereon.Alfred P. Sloan Research Fellow, 1976–1980; Camille and Henry Dreyfus Teacher-Scholar, 1975–1980.     

8,10-二炔廿五碳酸LB膜的周期结构

合成了8,10-二炔廿五碳酸,在玻璃片、石英片和镀金片上沉积了它的LB膜,X-射线衍射研究了LB膜的周期结构和聚合对它的影响。在2θ=1°—15°范围内观察到了多达7个布拉格衍射峰。由此计算了等同周期和分子在基片上的倾斜角。用分子模型计算了衍射峰强度,得到了与实验结果相符合的衍射峰强度奇偶起伏现象。     

SCATTERING FUNCTION OF POLYMER BLENDS

For a system of flexible polymer molecules, the concepts of two concentrations, namely the segmental and the molecular concentrations, have been proposed in this paper. The former is equivalent to the volume fraction. The latter can be defined as the number of the gravity centers of macromolecules in a unit volume. The two concentrations should be correlated with each other by the conformational function of the polymer chain and should be discussed in different thermodynamic equations. On the basis of these concepts it has been proved that the Flory-Huggins entropy of mixing should be the result of the mixing “ideal gases of the gravity centers of macromolecules“. The general correlation between the free energy of mixing and the scattering function (structural factor) of polymer blends has been studied based on the general fluctuation theory. When the Flory-Huggins free energy of mixing is adopted, the de Gennes scattering function of a polymer blend can be derived.