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41.
The gas-phase proton affinities of 4,4'-di(R)-2,2'-bipyridines (R: H, Br, Cl, NO(2), Me) were determined by mass spectrometric measurements and by ab initio calculations at the HF/6-31G and MP2/6-31G levels of theory. The energy barriers for rotation about the central C-C bond were also studied computationally. Two minima were found for both unprotonated and protonated species, the global minima being at the trans planar and cis planar conformations, respectively. Local minima for the unprotonated compounds were at the cis nonplanar conformation and for the protonated compounds at the trans nonplanar. Two different proton affinity values were calculated for each compound by employing different conformations for the protonated species. The computational values were in good agreement with the experimental proton affinities. Substituents affect the proton affinity according to their ability to withdraw or to donate electrons, halogen and nitro-substituted bipyridines having a lower proton affinity and methyl-substituted bipyridine having a higher proton affinity than 2,2'-bipyridine itself. 相似文献
42.
Karoliina Joutsiniemi Markku Ahlgrn Pirjo Vainiotalo Olaf Morgenstem Mario Meusel 《Journal of heterocyclic chemistry》1995,32(1):283-290
The mass spectra of ten 1,3-dithioxo[1,2,4]triazolo[1,2,-b]phthalazines, five 3-iminosubstituted 1-thioxo-[1,3,4]thiadiazolo[3,4-b]phthalazines, three 3-iminosubstituted-1-thioxo[1,2,4]triazolo[1,2-b]phthalazines, and 1,3-dithioxo-5,10-dihydro[1,3,4]thiadiazolo[3,4-b]phthalazine were recorded under electron ionization. The fragmentation pathways were elucidated by metastable ion analysis and exact mass measurements. The changes in the ring-system had little effect on the fragmentation mechanism, but the effect on peak intensities was considerable. The most important fragmentations began with the opening of the triazole ring. Substituents at nitrogen atoms also had a marked effect on the mass spectral behavior. The aryl substituents prompted a whole new fragmentation. The X-ray crystal structure was determined for a few compounds. Two of the three structures of the 1,3-dithioxo[1,2,4]triazolo[1,2-b]phthalazines that were studied proved to be relatively planar, whereas the structure of 1,3-dithioxo-5,10-dihydro[1,3,4]thiadiazolo[3,4-b]phthalazine was considerably bent similarly to the 2-(4-chlorophenyl)-1,3-dithioxo-2,3,5,10-tetrahydro[1,2,4]triazolo[1,2-b]-phthalazine. The triazole and the thiadiazole rings had a strong double bond nature. 相似文献
43.
Stress Tolerance of the Endemic Antarctic Brown Alga Desmarestia anceps to UV Radiation and Temperature is Mediated by High Concentrations of Phlorotannins
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María Rosa Flores‐Molina Ralf Rautenberger Pamela Muñoz Pirjo Huovinen Iván Gómez 《Photochemistry and photobiology》2016,92(3):455-466
The endemic Antarctic brown macroalga Desmarestia anceps is strongly shade‐adapted, but shows also a high capacity to cope with different environmental stressors, e.g. UV radiation and temperature. Therefore, this species colonizes wide depth gradients, which are characterized by changing environmental conditions. In this study, we examine whether the different physiological abilities allowing D. anceps to grow across a wide depth range is determined by high levels of phlorotannins. Photosynthesis, measured by PAM‐fluorometry, the contents of soluble phlorotannins, antioxidant capacities of field grown were analyzed in response to different conditions of radiation (PAR and PAR + UV) and temperature (2, 7 and 12°C). The results show that maximal quantum of fluorescence (Fv/Fm) decreased with increasing doses of UV radiation, but remained unaffected by temperature. High levels of soluble phlorotannins were detected and confirmed by microscopic observation revealing the abundance of large physodes. Exposure to UV radiation and elevated temperature showed that phlorotannins were not inducible by UV but increased at 12°C. ROS scavenging capacity was positively correlated with the contents of phlorotannins. In general, highest contents of phlorotannins were correlated with the lowest inhibition of Fv/Fm in all experimental treatments, highlighting the UV‐protective role of these compounds in D. anceps. 相似文献
44.
Reetaleena Rissanen Ilpo Niskanen Jukka Räty Pirjo Kyyrönen Asta Leinonen Risto Myllylä Kai-Erik Peiponen 《Optical Review》2014,21(3):395-400
We have built a novel optical multi-sensor apparatus (MSA) for the measurement of light absorption, scattering and fluorescence either separately or simultaneous from a liquid. From the measured data it is possible to calculate different optical properties of liquid samples, such as absorbance and turbidity. The MSA is a portable device which is an advantage considering different field applications. The MSA was tested in laboratory conditions using well-known reference liquids. Data obtained with the MSA were compared with data obtained with a commercial spectrophotometer, fluorometer and a nephelometer, respectively. Relatively good correlations between the data of MSA and the three commercial devices were found. It is proposed that MSA is a potential device for monitoring changes of process liquids and liquid products in industry. 相似文献
45.
Jaana M. H. Pakarinen Pirjo Vainiotalo 《Rapid communications in mass spectrometry : RCM》2009,23(12):1767-1775
Metal complex formation was investigated for di‐exo‐, di‐endo‐ and trans‐2,3‐ and 2,5‐disubstituted trinorbornanediols, and di‐exo‐ and di‐endo‐ 2,3‐disubstituted camphanediols using different divalent transition metals (Co2+, Ni2+, Cu2+) and electrospray ionization quadrupole ion trap mass spectrometry. Many metal‐coordinated complex ions were formed for cobalt and nickel: [2M+Met]2+, [3M+Met]2+, [M–H+Met]+, [2M–H+Met]+, [M+MetX]+, [2M+MetX]+ and [3M–H+Co]+, where M is the diol, Met is the metal used and X is the counter ion (acetate, chloride, nitrate). Copper showed the weakest formation of metal complexes with di‐exo‐2,3‐disubstituted trinorbornanediol yielding only the minor singly charged ions [M–H+Cu]+, [2M–H+Cu]+ and [2M+CuX]+. No clear differences were noted for cobalt complex formation, especially for cis‐2,3‐disubstituted isomers. However, 2,5‐disubstituted trinorbornanediols showed moderate diastereomeric differentiation because of the unidentate nature of the sterically more hindered exo‐isomer. trans‐Isomers gave rise to abundant [3M–H+Co]+ ion products, which may be considered a characteristic ion for bicyclo[221]heptane trans‐2,3‐ and trans‐2,5‐diols. To differentiate cis‐2,3‐isomers, the collision‐induced dissociation (CID) products for [3M+Co]2+, [M+CoOAc]+, [2M–H+Co]+ and [2M+CoOAc]+ cobalt complexes were investigated. The results of the CID of the monomeric and dimeric metal adduct complexes [M+CoOAc]+ and [2M–H+Co]+ were stereochemically controlled and could be used for stereochemical differentiation of the compounds investigated. In addition, the structures and relative energies of some complex ions were studied using hybrid density functional theory calculations. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
46.
47.
Anni Karppinen Arja-Helena Vesterinen Tapio Saarinen Pirjo Pietikäinen Jukka Seppälä 《Cellulose (London, England)》2011,18(6):1381-1390
Using two cationic methacrylate polymers: poly([2-(methacryloyloxy)ethyl] trimethyl ammonium iodide) (PDMQ) and poly[(stearyl
methacrylate)-stat-([2-(methacryloyloxy)ethyl] trimethyl ammonium iodide)] (PSMA13Q), we modified microfibrillated cellulose (MFC) water suspensions.
The aim was to affect the flocculation and rheological behavior of the MFC suspension. PDMQ is a strongly cationic polymer
while PSMA13Q, also a cationic polymer, contains hydrophobic segments. We studied the MFC/polymer suspension rheological properties
with a rotational rheometer in oscillatory and flow measurements. To observe structural changes in suspensions at different
shear rates, we measured flow curves with transparent outer geometry and photographed the sample with a digital camera. The
oscillatory measurements showed that a small amount of the cationic PDMQ in the MFC suspension strengthened the gel, whereas
a small amount of amphiphilic PSMA13Q weakened it. Increased amounts of either polymer increased the gel strength. PSMA13Q
also changed the rheological character of the MFC suspension turning it more fluid-like. When we photographed the flow curve
measurement, we saw a clear change in the floc structure. This floc structure rupture coincided with a transient region in
the flow curve. 相似文献
48.
Ventola E Hyyryläinen A Vainiotalo P 《Rapid communications in mass spectrometry : RCM》2006,20(8):1218-1224
Noncovalent complex formation between a tetramesityl sulfonated tetramethyl resorcarene and primary, secondary, and tertiary alkylammonium ions was investigated by electrospray ionization (ESI) Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Competition measurements, collision-induced dissociation, and gas-phase hydrogen/deuterium (H/D)-exchange reactions were employed to elucidate the interactions involved in complexation, the stability of the complexes, and the position of the guest with relation to the resorcarene. The complex formation ability of tetramesityl sulfonated resorcarene and the stability of the compexes were compared with the corresponding properties of tetratosylium tetraethyl resorcarene, which has been studied previously. Complex formation and the properties of the complexes were most strongly determined by the steric properties of the guests and their ability to form hydrogen bonds. Comparison of the two host molecules revealed the impact of steric hindrance in tetramesityl sulfonated tetramethyl resorcarene. 相似文献
49.
Teresa CzuryszkiewiczJarno Ahvenlammi Pirjo KortesuoManja Ahola Freddy KleitzMika Jokinen Mika Lindén J.B. Rosenholm 《Journal of Non》2002,306(1):1-10
Sol-gel derived biodegradable SiO2 gel fibers have been prepared and characterized by Raman spectroscopy, SEM, 29Si MAS NMR and TG-MS, respectively. An active component, dexmedetomidine hydrochloride, was incorporated in situ into the fiber structure, by adding it to the sol used for fiber spinning. The subsequent release of the active component was studied in vitro and shown to be determined by differences in the fiber structure, for which clear but indirect evidence was obtained from the different characterization methods used. 相似文献
50.
In the course of mass spectrometric measurements a self-assembled hydrogen bonded resorcinarene dimer was observed, the formation of which was driven by the binding of triethylammonium ion as a guest and as an ionic label. 相似文献