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31.
Desorption atmospheric pressure photoionization high‐resolution mass spectrometry: a complementary approach for the chemical analysis of atmospheric aerosols
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32.
Limantara L Koehler P Wilhelm B Porra RJ Scheer H 《Photochemistry and photobiology》2006,82(3):770-780
The photostabilities of bacteriochlorophyll a and several of its derivatives, which are of interest as potential sensitizers in photodynamic tumor therapy, were investigated. The pigments were irradiated with light >630 nm in organic solvents (acetone, tetrahydrofuran, pyridine, methanol, ethanol, n-propanol, 2-propanol and toluene) and in aqueous detergent solutions (cetyl-trimethyl-ammonium bromide [CTAB], lauryldimethyl-aminoxide [LDAO] or sodium dodecyl-sulfate [SDS] and Triton X-100 [TX100]). Their stabilities in these different solvents were determined in the presence and absence of an external sensitizer (pyromethyl-pheophorbide a), oxygen, sodium ascorbate and inert gas (Ar) or vacuum. The photodegradation products of bacteriochlorophyll a in acetone solution were isolated, purified by HPLC and analyzed by their absorption spectra and mass spectroscopy. Besides the well-known dehydrogenation products, such as [3-acetyl]-chlorophyll a, which were obtained as by-products, the major products had low absorption in the visible-near infrared spectral range. The spectral signature of the major component of these products was characteristic of linear open-chain tetrapyrroles, but they lacked the characteristic protonation-deprotonation behavior and reactivity of bilins with Zn(++). 相似文献
33.
Mirja Andersson Sirkka Liisa Maunu 《Journal of Polymer Science.Polymer Physics》2006,44(23):3305-3314
Thermoresponsive colloidal microgels were prepared by polymerization of N‐isopropylacrylamide (NIPAM) in the presence of a crosslinking monomer, N,N‐methylenebisacrylamide, in water with varying concentrations (<CMC) of an anionic surfactant, sodium dodecylsulphate (SDS). Volume phase transitions of the prepared microgels were studied in D2O by 1H NMR spectroscopy including the measurements of spin–lattice (T1) and spin–spin (T2) relaxation times for the protons of poly(N‐isopropylacrylamide) (PNIPAM) at temperature range 22–50 °C. In addition, microcalorimetry, turbidometry, dynamic light scattering, and electrophoretic mobility measurements were used to characterize the aqueous microgels. As expected, increasing SDS concentration in the polymerization batch decreased the hydrodynamic size of an aqueous microgel. Structures with high mobilities at temperatures above the LCST of PNIPAM were observed in the microgels prepared with small amount of SDS, as indicated by the relaxation times of different PNIPAM protons. It was concluded that the high mobility at high temperatures is in connection to a mobile surface layer with polyelectrolyte nature and with high local LCST. High SDS concentration in the synthesis was observed to prevent the formation of permanent, solid PNIPAM particles. The results from different characterization methods indicated that PNIPAM microgels prepared in high SDS concentrations appear to be more homogeneously structured than their correspondences prepared in low SDS concentration. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3305–3314, 2006 相似文献
34.
N-methylmorpholine N-oxide (NMMO) is a known cellulose solvent used in industrial scale (LyoCel process). We have studied interactions between pretreated softwood pulp fibers and aqueous NMMO using nuclear magnetic resonance (NMR) spectroscopic methods, including solid state cross polarisation magic angle spinning (CP-MAS) 13C and 15N spectroscopies, and 1H high resolution MAS NMR spectroscopy. Changes in both cellulose morphology and in accessibility of solvents were observed after the pulp samples that were exposed to solvent species were treated at elevated temperature. Evidence about interactions between cellulose and solvent components was observed already after a heat treatment of 15 min. The crystalline structure of cellulose was seen to remain intact for the first 30 min of heat treatment, at the same time there was a re-distribution of solvent species taking place. After a 90 min heat treatment the crystalline structure of cellulose had experienced major changes, and potential signs of regeneration into cellulose II were observed. 相似文献
35.
Miia Hiltunen Simon Riihelä Sirkka Liisa Maunu 《Journal of Polymer Science.Polymer Physics》2009,47(19):1869-1879
The syntheses and rheological behavior of ethyl hydroxyethyl cellulose (EHEC)‐based graft‐copolymers were studied. Copolymers were prepared by grafting EHEC with acrylamide (Aam) via reversible addition fragmentation chain transfer (RAFT) polymerization. Hydroxyl groups of EHEC were esterified with a carboxylic acid functional chain transfer agent (CTA) to prepare EHEC‐macroCTAs with different degrees of substitution. EHEC‐macroCTAs were characterized by ATR‐FTIR, 13C NMR, and SEC, and elemental analysis was used to quantify the degree of CTA substitution. EHEC‐macroCTAs with different degrees of substitution were copolymerized with acrylamide by “grafting from” technique. Formation of new cellulose‐based copolymers was comprehensively confirmed by 1H NMR, ATR‐FTIR, and SEC measurements. Further, the associations of EHEC‐g‐PAam copolymers in water were studied at various concentrations and temperatures by means of UV–vis spectroscopy, fluorescence spectroscopy, and rheological measurements. The results indicate that copolymers have both intra and intermolecular association in water depending on the amount of grafts. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1869–1879, 2009 相似文献
36.
Pirita Uschanov Leena-Sisko Johansson Sirkka Liisa Maunu Janne Laine 《Cellulose (London, England)》2011,18(2):393-404
Heterogeneous modification of various types of cellulose (microcrystalline cellulose, cellulose whiskers and regenerated cellulose)
was performed with long-chain fatty acids by an esterification reaction. The differences in reactivity between the celluloses
were studied as well as the influences of the chain length and double bond content of the fatty acids. The success of the
modification reaction and the structure of modified samples were studied with diverse characterization methods. Surface modification
changed the thermal stability of cellulose by decreasing the degradation temperature but also made the pyrolysis curve two-stepped
due to the double bonds in the fatty acid chain. It was observed that the nature of the fatty acid affected the degree of
substitution (DS). The longer the fatty acid chain was, the lower was the DS. Fatty acids with increased double bond content
gave decreased DS. Regenerated cellulose seemed to have the highest surface reactivity due to the distinct morphological structure,
which also led to a much lower quantity of fatty acids attached to the structure than for other modified cellulose particles.
The mixture of tall oil fatty acids behaved in the same manner as the commercial fatty acids, proving to be an excellent “green”
choice for this kind of application. 相似文献
37.
Miia Hiltunen Joonas Siirilä Vladimir Aseyev Sirkka Liisa Maunu 《European Polymer Journal》2012,48(1):136-145
Water-soluble cellulose-graft-PDMAam copolymers were prepared by single-electron-transfer living radical polymerization (SET-LRP). Cellulose based macroinitiator for SET-LRP with a degree of substitution DS ≈ 2 was synthesized from softwood dissolving pulp in a homogeneous LiCl/DMAc solution. The macroinitiator was then grafted using N,N-dimethyl acrylamide (DMAam) in DMSO. Formation of cellulose-g-DMAam copolymers were confirmed by ATR–FTIR, 1H and 13C NMR spectroscopy and SEC analyses. Light scattering and steady–shear viscosity measurements revealed that the studied chain length of grafts (DPgraft) had only minor effects on the solution properties of cellulose-g-PDMAam copolymers. SLS studies suggested a loose, solvent-draining architecture of the cellulose-g-PDMAam copolymer particles in H2O. 相似文献
38.
Kris Krug Liisa Porra Paola Coan Arie Wallert Joris Dik Andrea Coerdt Alberto Bravin Muthaffar Elyyan Péter Reischig Lukas Helfen Tilo Baumbach 《Journal of synchrotron radiation》2008,15(1):55-61
X‐ray radiography is a common tool in the study of old master paintings. Transmission imaging can visualize hidden paint layers as well as the structure of the panel or canvas. In some medieval altarpieces, relics seem to have been imbedded in the wooden carrier of paintings. These are most probably thin organic fibrous materials such as paper or textile, which in traditional radiography are shadowed by the more absorbing surrounding material. This paper studies the application potential of synchrotron‐based tomographic and laminographic imaging complemented with phase‐contrast imaging for detection of such relics. The techniques are applied to a dummy painting. The results demonstrate that by using these imaging methods it is possible to three‐dimensionally visualize hidden cavities in panels and detect thin fibrous low‐Z materials sandwiched between a high‐Z paint layer and a thick wooden panel. 相似文献
39.
Jaakko Paasivirta Jarmo Simanainen Raili Vesterinen Liisa Virkki 《Magnetic resonance in chemistry : MRC》1977,9(12):708-711
Proton, phosphorus and carbon magnetic resonance spectra of dimethoate, dimethoxon, des-N-methyldimethoate, ω-hydroxydimethoate, trimethyldithiophosphate and O,O-dimethyldithiophosphate in different solvents have been measured. Most of the n.m.r. parameters were characteristic of the structural environment of the corresponding nucleus and solvent-independent. However, in the amide structures dimethoate, dimethoxon, des-N-methyldimethoate and ω-hydroxydimethoate the 31P? S? C? 1H vicinal coupling showed an unusually large solvent effect of a 2.3 to 6.5 Hz decrease when CDCI3 was replaced by acetone-d6 or DMSO-d6. 相似文献
40.
Jaakko Paasivirta Raili Versterinen Liisa Virkki Pekka Pyykk 《Magnetic resonance in chemistry : MRC》1977,10(1):265-266
Proton and carbon magnetic resonance spectra of Lewisite or dichloro(trans-2-chlorovinyl)arsine have been measured and the results are compared with the n.m.r. spectral parameters of other trans-1,2-substituted ethylenes. The coupling constants can be rationalized by substituent electronegativity. The chemical shifts show an unusually large paramagnetic effect from the AsCl2 group. 相似文献