Application of capillary gas chromatography in the analysis of hydrocarbons in the environment

Summary Hydrocarbons are emitted into the environment in quantity and diversity. Some of these can be detrimental in low concentration, many can be active in photochemical smog production. For combatment there is also interest in the sources of hydrocarbons in the atmosphere. For source recognition fine-structured chromatographic fingerprints are essential. This also holds for oil pollution. A complicating factor in the determination of hydrocarbon pollutants may arise from the occurrence of recently biosynthesized hydrocarbons. For distinguishing between these two types the application of capillary gas chromatography is preferred to packed column gc. It will be clear that the application of capillary gc in the analysis of hydrocarbons in the environment is of great practical value. The modified Grob method used by us for the analysis of hydrocarbons in air is discussed. For the characterization and source recognition of oil pollution in water and soil application of capillary gc fingerprinting is essential; in this way valuable information can be gathered about weathering of oil pollution. Sources of oil pollution in water areas and harbour regions can be traced in certain cases. Also the possibility of measurement of residence time is present. Typical examples are given.Publication No. 601 of the TNO Research Institute for Environmental Hygiene.     

Unstable slit flow of a liquid crystalline polymer solution

A lyotopic solution of 27 wt% hydroxypropylcellulose [HPC] in m-cresol has been studied in pressure-driven slit flow. At high flow rates an instability leads to large wavelength disturbances in fluid structure. A combination of image analysis and time signal processing is used to determine the velocity at which the structural disturbances are convected downstream, which is shown to be equal to the independently measured and predicted centerline velocity. This implies that the disturbance structure is confined near the midplane of the slit flow. Upstream of the onset point of the wavy fluid structures, the fluid exhibits unusual optical properties when viewed between crossed polarizers that are rotated relative to the flow direction. Specifically, the optical properties indicate that there must be some variation in the macroscopic optical axis of the sample as light passes through the slit flow. A discrete optical model consisting of birefringent elements twisted away from and back to the flow direction as a function of depth in the sample is able to predict the essential optical characteristics; however, independent x-ray scattering measurements show that the macroscopic molecular alignment is along the flow direction. The wavy textures apparently emerge as a result of an inhomogeneous transition of orientation back to the flow direction, trapping thin bands of fluid in the twisted configuration.     

Molecular orientation, “Region I” shear thinning and the cholesteric phase in aqueous hydroxypropylcellulose under shear

Birefringence and flow visualization are used to study molecular orientation, texture, and the cholesteric nature of a 60 wt% aqueous hydroxypropylcellulose solution at low to moderate shear rates. There is a sharp transition in behavior at a shear rate near 0.5 s^–1. Below this rate, the sample shows “Region I” shear thinning, takes on a frosted appearance, has low flow-induced orientation, and exhibits faint optical diffraction characteristic of cholesteric liquid crystals. Upon flow cessation from low rates, a highly organized cholesteric phase showing bright optical diffraction is re-formed in around 5min. Above the critical shear rate, the sample exhibits much higher orientation and a striped texture which is readily apparent with or without polarized light illumination. Upon flow cessation, molecular orientation decays significantly for up to around 400 s; however, the striped textures established during shear persist. It is suggested that persistence of the cholesteric phase under shear is responsible for the occurrence of Region I shear thinning at low shear rates in this solution.     

Short-time dynamics through conical intersections in macrosystems. II. Applications

We present several numerical applications based upon the effective-mode formulation for the short-time dynamics through conical intersections in macrosystems, as detailed in the preceding paper and first proposed by Cederbaum et al. [Phys. Rev. Lett. 94, 113003 (2005)]. The macrosystem, containing a vast number of nuclear degrees of freedom (modes), is decomposed into a system part and an environment part. Only three effective environmental modes are needed-together with the system's modes-to accurately calculate the low resolution spectra and the short-time dynamics of the entire macrosystem. For the systems discussed here, results are compared to those of a full quantum wave-packet propagation. Some rules are extracted to provide general tendencies; these rules allow one to understand and predict the dynamical properties in more general situations where the exact quantum dynamics of the macrosystem is out of reach.     

Ab initio quantum dynamical study of photoinduced ring opening in furan

The nonadiabatic photoinduced ring opening occurring in the two lowest excited singlet states of furan is investigated theoretically, using wave-packet propagation techniques. The underlying multidimensional potential energy surfaces (PESs) are obtained from ab initio computations, using the equation-of-motion coupled cluster method restricted to single and double excitations (EOM-CCSD), reported in earlier recent work [E. V. Gromov, A. B. Trofimov, F. Gatti, and H. Ko?ppel, J. Chem. Phys. 133, 164309 (2010)]. Up to five nuclear degrees of freedom are considered in the quantum dynamical treatment. Four of them represent in-plane motion for which the electronic states in question (correlating with the valence (1)B(2)(V) and Rydberg (1)A(2)(3s) states at the C(2v) ground-state molecular configuration) have different symmetries, A(') and A('), respectively. The fifth mode, representing out-of-plane bending of the oxygen atom against the carbon-atom plane, leads to an interaction of these states, as is crucial for the photoreaction. The nonadiabatic coupling and conical intersection cause an electronic population transfer on the order of ～10 fs. Its main features, and that of the wave-packet motion, are interpreted in terms of properties of the PES. The lifetime due to the ring-opening process has been estimated to be around 2 ps. The dependence of this estimate on the nuclear degrees of freedom retained in the computations is discussed.     

Cationic polyfluorenes for intracellular delivery of proteins

Two cationic polyfluorene derivatives, quaternary amine 1 and guanidine 2 sheathed systems, were prepared as potential carriers to mediate import of proteins into cells without requiring covalent attachment to the protein. Neither polymer showed significant cytotoxicities (IC(50) 100 μM) when exposed to Clone 9 rat liver cells. Both polymers were shown to mediate import of a series of four proteins chosen because they have different pI values, sizes, and variable organic fluor attachments. Once inside the cells, the quaternary amine system 1 released more of its cargo into regions outside the lysosomes. In one exploratory experiment, pyrenebutyrate was shown to accelerate import of a protein system by polymer 1.     

Comparison of optical and mechanical measurements of second normal stress difference relaxation following step strain

Relaxation of the second normal stress difference (N ₂) following step strain of a concentrated monodisperse polystyrene solution has been studied using mechanical and optical rheometry. Measurements of normal thrust in a parallel plate geometry are corrected for strain inhomogeneity and combined with independent measurements of the first normal stress difference (N ₁) to determine N ₂. Optical experiments were performed using a novel configuration where flow birefringence data collected using multiple light paths within the shear plane are combined with the stress-optical law to determine all three independent stress components for shearing deformations. This technique eliminates end effects, and provides an opportunity to oversample the stress tensor and develop consistency checks of experimental data. N ₂ is found to be nonzero at all accessible times, and relaxes in roughly constant proportion to N ₁. This reflects nonaffine distribution of chain segments, even well within the regime of chain retraction at short times. Data collected with the two techniques are reasonably consistent with each other, and with results of previous studies, generally lying between the predictions of the Doi-Edwards model with and without the independent alignment approximation. The normal stress ratio –N ₂/N ₁ shows pronounced strain thinning in the nonlinear regime.