Selective inhibition of paraffin deposition under high flow rate as a function of the crude oil paraffin type and content by fluorescence depolarization: polypropylene and high-density polyethylene

High-density polyethylene (HDPE) and polypropylene (PP) were studied to identify tailor-made materials for walls of pipelines and ducts for crude paraffinic oil that inhibit paraffin depositions. The interfacial interaction was investigated from 50 to 70 degrees C and as a function of the n-C(36)H(74) paraffin concentration added to the paraffinic crude oil. The static and the dynamic interfacial tensions were observed, respectively, by traditional contact angle measurements and by fluorescence depolarization of the natural fluorescent probes of the crude oil, flowing at a high rate. The static interaction showed a low dependence on the n-paraffin content for both surfaces. For PP, it decreased slightly as the n-paraffin concentration increased, evidencing an increase in the liquid-liquid interaction. The dynamic interfacial tension with PP clearly decreased as temperature and n-paraffin concentration increased, the latter effect being attributed to the PP methyl groups hindering the interaction between the n-paraffin and the PP main chain. For the flow on HDPE, the interaction proved to be highly dependent on the n-paraffin concentration and temperature. It increased as n-paraffin was added and temperature decreased. The former effect is attributed to the alignment of the n-paraffin chains within the high rate flowing liquid and the similar molecular geometry of the n-paraffin and the linear polymer surface (almost without branches), which increases the number of sites available for interaction. PP proved to be more suitable for transportation of crude oil rich in paraffins with more than 36 carbon atoms, while HDPE was more suitable for those with smaller paraffinic chains.     

Protein immobilization on epoxy-activated thin polymer films: effect of surface wettability and enzyme loading

A series of epoxy-activated polymer films composed of poly(glycidyl methacrylate/butyl methacrylate/hydroxyethyl methacrylate) were prepared. Variation in comonomer composition allowed exploration of relationships between surface wettability and Candida antartica lipase B (CALB) binding to surfaces. By changing solvents and polymer concentrations, suitable conditions were developed for preparation by spin-coating of uniform thin films. Film roughness determined by AFM after incubation in PBS buffer for 2 days was less than 1 nm. The occurrence of single CALB molecules and CALB aggregates at surfaces was determined by AFM imaging and measurements of volume. Absolute numbers of protein monomers and multimers at surfaces were used to determine values of CALB specific activity. Increased film wettability, as the water contact angle of films increased from 420 to 550, resulted in a decreased total number of immobilized CALB molecules. With further increases in the water contact angle of films from 55 degrees to 63 degrees, there was an increased tendency of CALB molecules to form aggregates on surfaces. On all flat surfaces, two height populations, differing by more than 30%, were observed from height distribution curves. They are attributed to changes in protein conformation and/or orientation caused by protein-surface and protein-protein interactions. The fraction of molecules in these populations changed as a function of film water contact angle. The enzyme activity of immobilized films was determined by measuring CALB-catalyzed hydrolysis of p-nitrophenyl butyrate. Total enzyme specific activity decreased by decreasing film hydrophobicity.     

Stereoregulation of thermoresponsive polymer brushes by surface-initiated living radical polymerization and the effect of tacticity on surface wettability

In this study, stereocontrolled poly(N-isopropylacrylamide) (PIPAAm) brushes were grafted from surfaces by atom transfer radical polymerization (ATRP) in the presence of a Lewis acid, and the effect of PIPAAm brush tacticity on the thermoresponsive wettabiliy was investigated. PIPAAm grafted by ATRP in the presence of Y(OTf)(3) showed high isotacticity, while the control brush polymerized in the absence of Y(OTf)(3) was clearly atactic. The isotacticity and molecular weight of PIPAAm brushes were controlled by polymerization conditions. The wettability of isotactic PIPAAm-grafted surfaces decreased slightly below 10 °C, although the phase transition temperature of atactic surface was 30 °C, and the bulk isotactic polymer was water-insoluble between 5 and 45 °C.     

External electric field effects on fluorescence of pyrene butyric acid in a polymer film: concentration dependence and temperature dependence

Fluorescence spectra and electrofluorescence spectra (plots of the electric field-induced change in fluorescence intensity as a function of wavelength) have been measured at different temperatures for pyrene butyric acid (PBA) in a PMMA film at different concentrations. At a low concentration of 0.5 mol % where fluorescence emitted from the locally excited state of PBA (LE fluorescence) is dominant, LE fluorescence spectra show only the Stark shift in the presence of an electric field (F), which results from the difference in molecular polarizability between the ground and emitting states. At a high concentration of 10 mol % where the so-called sandwich-type excimer fluorescence (EX(1)) is dominant, both EX(1) and LE fluorescence are quenched by F. Another fluorescence assigned to a partially overlapped excimer (EX(2)) also exists at room temperature, and this emission is enhanced by F. As the temperature decreases, three fluorescence emissions whose electric field effects are different from each other become clear besides EX(1) and LE fluorescence, indicating that at least five fluorescence components exist at high concentrations at low temperatures. At a medium concentration of 5 mol % where EX(1) is comparable in intensity to the LE fluorescence, the intensity of EX(1) is not affected by F at any temperature, but LE fluorescence and EX(2) are markedly influenced by F at room temperature, and four fluorescence emissions are confirmed at low temperatures.     

The effect of surface wettability on induction and growth of neurites from the PC-12 cell on a polymer surface

Surface properties of polymeric devices that are used to regenerate nervous damage are a point to be considered for axon regeneration in nerve system. In our previous studies, we prepared a wettability gradient on polyethylene (PE) surfaces using a corona discharge treatment from a knife-type electrode whose power increases gradually along the sample length. The PE surfaces were oxidized gradually with increasing power. The effect of surface wettability on the different types of cells has an important role for cell adhesion and proliferation. The purpose of this study is to investigate neurite formation on polymer surfaces with different wettability. Induction and growth of neurites from the rat pheochromocytoma (PC-12) cells attached on the polymer surfaces with different hydrophilicity were investigated using the wettability gradient PE surfaces prepared by a corona discharge treatment. Neurites were investigated for number and length of neurites in terms of surface wettability. It was observed that neurite formation of PC-12 cells was increased more onto the positions with moderate hydrophilicity of the wettability gradient surface than onto the more hydrophobic or hydrophilic positions. From those results, it could be assumed that initial adhesion of PC-12 cells was caused by more calf serum (CS) protein than nerve growth factor (NGF), whereas the neurite formation of PC-12 cells was caused by more NGF than CS protein. It follows from what has been said thus far that PC-12 cells are a differentiated neuronal phenotype with a long neurite at around the position 2.5 cm (water contact angle of about 55 deg). In conclusion, surface wettability plays an important role for neurite formation on the polymer surfaces for axon regeneration.     

Coverage dependence of oxygen decomposition and surface diffusion on rhodium 111: a DFT study

A systematic study of oxygen adsorption, decomposition and diffusion on Rh111 and its dependence on coadsorbed oxygen molecules has been performed using density functional theory calculations. First, the bonding strength between metal surface and adsorbed oxygen molecules has been studied as a function of initial oxygen coverage. The bonding strength decreases with increasing oxygen coverage, which points towards a self-inhibition of the adsorption process. The potential energy hypersurface (PES) for the dissociation of oxygen molecules adsorbed on a threefold fcc position perpendicular to the surface was calculated using a combined linear/quadratic synchronous transit method with conjugate gradient refinements. The results indicate that a minor amount of oxygen on the surface enhances the decomposition of further oxygen molecules, while this process is inhibited at higher coverage. Moreover, PES calculations of a single site jump of atomic oxygen on rhodium 111 indicate that the activation energy increases as well with increasing oxygen coverage. All results are discussed with respect to a rhodium based catalytic NOx reduction/decomposition system proposed by Nakatsuji, which decomposes nitrogen oxides in oxygen excess.     

煤尘表面碳、氧基团随变质增加的演化规律及其对润湿性的影响

为探究煤自身结构差异对润湿性造成的影响,针对煤尘中碳、氧两大主要元素展开研究。通过NMR以及XPS实验分别获得六种不同变质程度煤尘表面碳(氧)基团的分布特征,利用距离分析得到碳(氧)基团的演化规律,发现随变质程度加深,一种基团的增减会伴随着其他基团的变化,是聚类变化的过程。碳基团中的芳烃碳(Ar-C,H)与羧基碳(-COOH)、次甲基碳(CH2)、醚基碳(Ar-O、R-O)演化规律接近,氧基团中的羟基氧(-OH)和醚基氧(C-O-C)的演化规律接近。利用因子分析研究碳、氧基团演化对润湿性的影响,发现芳香基团(Ar-C,H)作为解释碳基团对煤尘润湿性(接触角)影响程度的公因子,贡献95.366%的因素,是碳基团的主要影响因子,羟基(-OH)作为解释氧基团对煤尘润湿性(接触角)影响程度的公因子,贡献94.818%的因素,是氧基团的主要影响因子。     

Effect of oxygen plasma treatment on surface charge and wettability of PVC blood bag—In vitro assay

Wettability and zeta potential studies were performed to characterize the hydrophobicity and surface charge of PVC blood bag samples and evaluate the effect of these properties on fibroblast cells growth. The surface properties of PVC and plasma treated PVC were compared by water drop contact angle and zeta potential measurement. Light microscopy was used to study the behavior of cell attachment and growth on these surfaces. Water drop contact angle measurement shows that the plasma treated PVC becomes more hydrophilic and wettability increased. Zeta potential and in vitro cell culture measurements noticed that the plasma treated PVC surface is more negatively charge and consequently attachment of the L929 fibroblast cells decreased on this surface.     

Comparison of effects of sodium carboxymethylcellulose and superabsorbent polymer on coal dust wettability by surfactants

The interactions of sodium carboxymethylcellulose (SCMC) and a superabsorbent polymer (SA) with aqueous solutions of active surfactants such as sodium dodecylbenzenesulfonate (SDBS) and alkyl polyglycoside were investigated in terms of surface tension, sink time, and foam liquid fraction. An SA is a more suitable surfactant than SCMC for wetting coal dust, and SDBS and an SA additive in an SA:SDBS weight ratio of 1:4 is the best coal dust suppressant.     

Observation of intramolecular singlet and triplet excimers of tethered naphthalene moieties under the geometric constraints imposed by the host framework of zeolites

This paper describes the emission spectroscopic investigation of singlet and triplet excimers of tethered bisnaphthalene species at room temperature. 1,1'-Dinaphthylethane (DNE) and 1,1'-dinaphthylpropane (DNP) were incorporated into a 3-D network of a 1.3 nm diameter pseudo-spherical supercage of zeolites Y (with an entry aperture of 0.74 nm), and a 1-D channel of zeolite L with a 0.71 nm aperture. In the straight channel of zeolite L, DNP adopts a parallel-sandwich conformation as suggested by the observation of entirely excimeric fluorescence, while DNE can only enter the channel in an open form. As a result, incorporation of DNP into zeolite L exchanged with Tl(+) ions, which induce enhanced intersystem-crossing, allowed the observation of a broad and featureless phosphorescence spectrum that is ascribable to the triplet excimer of DNP. In contrast, an entirely monomeric phosphorescence is observed for DNE. Furthermore, we observed a monomeric phosphorescence spectrum for DNP in Tl(+)-exchanged zeolite Y, in which DNP was shown to assume its open conformation. Thus the parallel-sandwich structure is responsible for the triplet excimer of the bisnaphthalene species as well as for the singlet counterpart. The parallel-sandwich conformation of the triplet excimer of DNP immobilized by the host framework is significantly different from the previously proposed L-shaped configuration in solution. However, it is very similar to that of the triplet excimer of triple-tethered carbazolophane, as revealed quite recently by Ohkita's group (J. Phys. Chem. B, 2007, 111, 10905). Thus the present study helps tackle the long-term issue of triplet excimer through the use of zeolites.     

pH-Sensitive Wettability Induced by Topologicaland Chemical Transition on the Self AssembledSurface of Block Copolymer简

pH-sensitive wettability of polystyrene-b-poly（4-vinylpyridine） （PS-b-P4VP） self assembled films, exhibiting superoleophobicity under water and hydrophilicity at low pH value, and oleophobicity under water and hydrophobicity at neutral condition, has been realized. The wettability properties resulted from the surface topological and chemical transition, which were confirmed by in situ AFM measurements under water at different pH. At low pH, P4VP chains, which were confined in the hexagonal-packed nanodomains, got protonated into a swollen state, while at high pH, P4VP chains were deprotonated into a collapsed state. The reversible protonation/deprotonation procedure on the molecular scale leads to surface topological and chemical transition, thereby pH-sensitive wettability.     

Probing the interplay between chain diffusion and polymer crystal growth under nanoscale confinement: a study by single molecule fluorescence microscopy

Motions of single poly(ε-caprolactone) (PCL) molecules during the formation of the dendrite crystals in ultrathin films are captured by single molecule fluorescence microscopy. The relationship of single molecule diffusion coefficient with the crystal growth rate, together with radius curvature, side-branch spacing of dendrite crystal and morphology are examined. The results support Mullins-Sekerka (MS) instability as the origin of lamellar branching induced by a diffusion field generated by a gradient of polymer segment density ahead of the crystal. Further analysis of the molecular trajectories has recognized different types of motions, depending on the distance to the crystal front: Fickian diffusion in regions far away from the crystal, sub-diffusion in regions adjacent to the crystal, and directed motion between these two regions. Anti-correlation of successive steps is discovered accompanying the sub-diffusion, providing a clear signature of macromolecule crowding at the crystal growth front. This anomalous diffusion process in polymer ultrathin films presents a new insight into the understanding of the retarded dynamics of interfacial mass transport towards the crystal front. It is considered to play a decisive role in controlling the crystal growth and evolution of crystal morphology.     

Single particle confocal fluorescence spectroscopy in microchannels: dependence of burst width and burst area distributions on particle size and flow rate.

This article presents a non-invasive, optical technique for measuring particulate flow within microfluidic channels. Confocal fluorescence detection is used to probe single fluorescently labeled microspheres (200-930 nm diameter) passing through a focused laser beam at a variety of flow rates (100 - 1000 nL/min). Simple statistical methods are subsequently used to investigate the resulting fluorescence bursts and generate single-particle burst width and burst area distributions. Analysis of such distributions demonstrates that the average burst width and burst area decrease as particle size increases. In addition, both burst width and burst area (for a given particle size) are observed to decrease as volumetric flow rate is increased. The dependence of such distributions on particle size is proposed as a potential route to sizing single particles and molecules in microfluidic systems.     

Dendron-containing tetraphenylethylene compounds: dependence of fluorescence and photocyclization reactivity on the dendron generation

The synthesis and characterization of four dendron-containing tetraphenylethylenes (TPEs), 1(1)-1(4), were synthesized, along with a TPE compound that contained four OCH(2) Ph groups (referred to as 1(0)) for comparison. Photophysical studies revealed that the TPE core became emissive after linking dendrons onto its periphery. Moreover, the fluorescence intensity was significantly enhanced when high-generation dendrons were linked onto the TPE core; the fluorescence intensity increased in the following order: 1(1)<1(2)<1(3)<1(4). This phenomenon was tentatively attributed to an enhancement in the energy barrier for internal rotation and torsion of the TPE core to which four dendrons were connected. In addition, the photocyclization of the TPE core into the respective 9,10-diphenylphenanthrene was facilitated when high-generation dendrons were linked to the TPE core. Again, the photocycliztion reactivity increased in the following order: 1(1)<1(2)<1(3)<1(4). We found that the fluorescence and photocyclization reactivity of TPE could be modulated by covalent interactions with dendrons, and such modulation was strongly dependent on the dendron-generation.     

Elemental analysis of human amniotic fluid and placenta by total-reflection X-ray fluorescence and energy-dispersive X-ray fluorescence: child weight and maternal age dependence

This work is an attempt to evaluate the possible influence of the mother's age in trace element concentrations in human amniotic fluid and placenta and whether these concentrations are correlated to the weight of the newborn infants. Total-reflection X-ray fluorescence (TXRF) was used to analyze 16 amniotic fluid samples, and the placenta samples were analyzed by energy dispersive X-ray fluorescence (EDXRF). The whole samples were collected during delivery from healthy mothers and healthy infants and full-term pregnancies. According to the age of the mother, three different groups were considered: 20–25, 25–30 and 30–40 years old. Only two mothers were aged more than 35 years. The weight of the infants ranged from 2.56 to 4.05 kg and three groups were also considered: 2.5–3, 3–3.5 and 3.5–4 kg. The organic matrix of the amniotic fluid samples was removed by treatment with HNO₃ followed by oxygen plasma ashing. Yttrium was used as the internal standard for TXRF analysis. Placenta samples were lyophilized and analyzed by EDXRF without any chemical treatment. Very low levels of Ni and Sr were found in the amniotic fluid samples, and were independent of the age of the mother and weight of the child. Cr, Mn, Se and Pb were at the level of the detection limit. Zn, considered one of the key elements in neonatal health, was not significantly different in the samples analyzed; however, it was weakly related to birth weigh. The concentrations obtained ranged from 0.11 to 0.92 mg/l and 30 to 65 μg/g in amniotic fluid and placenta, respectively. The only two elements which seemed to be significantly correlated with mother's age and newborn weight were Ca and Fe for both types of sample: Ca levels were increased in heavier children and older mothers; however, Fe increased with increasing maternal age, but decreased for heavier babies. The same conclusions were obtained for placenta and amniotic fluid samples. Cu is closely associated with Fe in its function in the organism and has a similar behavior to this element, but not as pronounced.     

TNT及RDX蒸气对基于芘氧敏感膜荧光猝灭的研究

制备了以芘为敏感材料,聚苯乙烯(PS)以及聚氯乙烯(PVC)粉末为支持体系的两种荧光猝灭氧敏感膜.PS以及PVC氧敏感膜的最大激发波长分别为349 nm和355 nm,最大发射波长分别为399 nm和398 nm.分子氧对PS以及PVC氧敏感膜的荧光均有猝灭作用.同时,实验发现2,4,6-三硝基甲苯(TNT)和环三亚甲基三硝基胺(RDX)对这两种氧敏感膜的荧光也有一定的猝灭.     

Acyloin condensation by polymer supported thiazolium salt: Relation between the catalytic activity and the degree of quarternization

Thiazolium salt polymers were synthesized by the quarternization of thiazole polymers by alkyl halides. It was found that these polymers had high catalytic activities for the acyloin condensation of furfural. The catalytic activities of thiazolium salt polymers increased as the degree of quarternization decreased. This tendency was observed both in the polar solvents such as MeOH and in the nonpolar solvents such as dioxane. From the results of the acyloin condensation catalyzed by more hydrophobic polymer catalyst PTS⁺–St (which had styrene unit instead of free thiazole unit) and CnPTS⁺ (which had a long alkyl chain around the active site), it became clear that the hydrophobicity and the steric hindrance around the active site greatly affected the catalytic activity.     

The action of oxygen on chlorophyll fluorescence quenching and absorption spectra in pea thylakoid membranes under the steady-state conditions

The effect of oxygen concentration on both absorption and chlorophyll fluorescence spectra was investigated in isolated pea thylakoids at weak actinic light under the steady-state conditions. Upon the rise of oxygen concentration from anaerobiosis up to 412 microM a gradual absorbance increase around both 437 and 670 nm was observed, suggesting the disaggregation of LHCII and destacking of thylakoids. Simultaneously, an increase in oxygen concentration resulted in a decline in the Chl fluorescence at 680 nm to about 60% of the initial value. The plot of normalized Chl fluorescence quenching, F(-O(2))/F(+O(2)), showed discontinuity above 275 microM O(2), revealing two phases of quenching, at both lower and higher oxygen concentrations. The inhibition of photosystem II by DCMU or atrazine as well as that of cyt b(6)f by myxothiazol attenuated the oxygen-induced quenching events observed above 275 microM O(2), but did not modify the first phase of oxygen action. These data imply that the oxygen mediated Chl fluorescence quenching is partially independent on non-cyclic electron flow. The second phase of oxygen-induced decline in Chl fluorescence is diminished in thylakoids with poisoned PSII and cyt b(6)f activities and treated with rotenone or N-ethylmaleimide to inhibit NAD(P)H-plastoquinone dehydrogenase. The data suggest that under weak light and high oxygen concentration the Chl fluorescence quenching results from interactions between oxygen and PSI, cyt b(6)f and Ndh. On the contrary, inhibition of non-cyclic electron flow by antimycin A or uncoupling of thylakoids by carbonyl cyanide m-chlorophenyl hydrazone did not modify the steady-state oxygen effect on Chl fluorescence quenching. The addition of NADH protected thylakoids against oxygen-induced Chl fluorescence quenching, whereas in the presence of exogenic duroquinone the decrease in Chl fluorescence to one half of the initial level did not result from the oxygen effect, probably due to oxygen action as a weak electron acceptor from PQ pool and an insufficient non-photochemical quencher. The data indicate that mechanism of oxygen-induced Chl fluorescence quenching depends significantly on oxygen concentration and is related to both structural rearrangement of thylakoids and the direct oxygen reduction by photosynthetic complexes.