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51.
Schlesinger J Rajander J Ihalainen JA Ramesh D Eklund P Fagerholm V Nuutila P Solin O 《Inorganic chemistry》2011,50(10):4260-4271
The model complex [(64)Cu((S)-p-NH(2)-Bn-NOTA)](-) ([(64)Cu]1) was used to study the isomerism of [(64)Cu-NOTA-Bn]-labeled radiotracers. Two complex isomers [(64)Cu]1a and [(64)Cu]1b, which were formed at a ratio of 1:9 during the complexation of [(64)Cu]Cu(2+) with (S)-p-NH(2)-Bn-NOTA, were separated using ion pair chromatography. To study the interconversion, the nonradioactive complex isomers Cu1a and Cu1b were separated and thermally treated at 90 °C in both ammonium acetate solution and deionized water. A faster interconversion rate was observed for both isomers with lower concentrations of ammonium ions. At the end of reaction, the thermodynamic Cu1a to Cu1b equilibrium ratio was 6:94. The particular energy barriers of the interconversion for Cu1a and Cu1b were 130 kJ mol(-1) and 140 kJ mol(-1). Spectrophotometric measurements with Cu1a and Cu1b revealed two isomers adopting different geometrical configurations. 相似文献
52.
Phlorotannins of brown algae are multifunctional compounds with putative roles in herbivore deterrence, antioxidation and as primary cell wall components. Due to their peripheral localization and absorption at short wavelengths, a photoprotective role is suggested. We examined the induction of phlorotannins by artificial UV radiation in the intertidal kelp Lessonia nigrescens and whether they attenuate the inhibition of photosynthesis and DNA damage, two major detrimental effects of UV. The soluble and cell wall-bound fractions of phlorotannins were quantified in blades collected in summer and winter. Major findings were that (1) the synthesis of phlorotannins (both forms) was induced by UV only in summer; (2) the induction was fast (within 3 days); and (3) there was a positive relationship between of the contents of insoluble phlorotannins and the suppression of photoinhibition and DNA damage, measured as formation of cyclobutane pyrimidine dimers and 6-4 photoproducts. Overall, the photoprotective role of phlorotannins appears to respond to an interplay between the external UV stimulus, seasonal acclimation and intrinsic morpho-functional processes. In summer, when algae are naturally exposed to high UV irradiances, soluble phlorotannins are induced, while their transition to insoluble phlorotannins could be related with the growth requirements, as active blade elongation occurs during this season. 相似文献
53.
Gas-phase ring-chain tautomeric equilibria with eight 2-phenyl-substituted perhydro-1,3-oxazines and six 2-aryl-substituted l,2-dihydro-4H-3,1-benzoxazines were studied by recording their mass spectra Finder different conditions. Their fragmentation behaviour was also studied using metastable ion analysis and exact mass measurement. For the monocyclic compounds the existence of tautomerism was apparent and it resembled that found in non-polar solvents. In contrast, benzoxazines gave little evidence for the presence of the open-chain forms. 相似文献
54.
A toxicological analysis was developed and validated for simultaneous screening and quantification of methadone (METH) and its primary metabolite 2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine (EDDP). The method employs microscale liquid-liquid extraction (microLLE) and direct injection of a separated aliquot of the organic layer into a gas chromatography/mass spectrometric (GC/MS) system without any other pre-treatment stages. A fast GC/MS runtime (total 5.8 min; METH, Rt = 3.55 min; EDDP, Rt = 3.40 min) combined with rapid sample preparation allowed cost-efficient and routinely applicable performance with a low amount of manual work. The validated parameters included: linearity (25-1000 ng mL(-1) both; R(METH)2 = 0.998 and R(EDDP)2 = 0.997), accuracy (Bias(METH): from -0.05 to 11.3%, Bias(EDDP): from 1.11 to 4.37%); intra and inter-assay precision (RSD(METH): from 2.4 to 3.9%, from 4.89 to 10.3%; RSD(EDDP): from 4.50 to 6.20%, from 4.57 to 15.2%), extraction efficiency (METH = 95.5%; EDDP = 90.6%), LOQ(Meth,EDDP) = 25 ng mL(-1). Samples were stable for at least 25 h and no selectivity problems or baseline interference were observed. The method should be applicable for identifying and quantitative confirmation of possible misuse and/or illegal use of METH in toxicological cases. 相似文献
55.
Ostman P Pakarinen JM Vainiotalo P Franssila S Kostiainen R Kotiaho T 《Rapid communications in mass spectrometry : RCM》2006,20(24):3669-3673
We performed a systematic study using a set of compounds with different proton affinities (PAs) on the ionization in atmospheric pressure desorption/ionization on silicon mass spectrometry (AP-DIOS-MS). The compounds studied included various aromatic molecules of different sizes. The PAs of these compounds were calculated using ab initio and hybrid density functional theory calculations at the B3LYP/6-31G(d) level of theory. We observed that only compounds with relatively high PAs above a threshold value of 920-950 kJ/mol were efficiently ionized as protonated molecules under AP-DIOS conditions and produced very clean mass spectra. 相似文献
56.
Ventola E Vainiotalo P Suman M Dalcanale E 《Journal of the American Society for Mass Spectrometry》2006,17(2):213-221
Alcohol complexation properties of eight mono- and diphenyl phosphonate-bridged cavitands were studied by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR) and theoretical calculations. The cavitands varied in number and position of phenyl phosphonate bridges and their orientation with respect to the cavity, length of the lower rim alkyl chains, and substituents at apical positions of the resorcarene skeleton. The specificities of the different cavitands toward primary, secondary, and tertiary alcohols varying long of the alkyl chain were investigated, together with the stabilities of the formed complexes. The number, position, and orientation of the P = O moieties affected the complex formation of the cavitands and stability of the complexes dramatically. Methyl groups at apical positions of the resorcarene skeleton also affected the complexation properties. Although length and branching of the alkyl chain of the alcohol influenced the complex formation, the effect on stability of the complexes was negligible. 相似文献
57.
Hyyryläinen AR Pakarinen JM Fülöp F Vainiotalo P 《Journal of the American Society for Mass Spectrometry》2009,20(1):34-41
Stereochemical differentiation of five diastereomeric pairs of β-amino acids, di-endo- and di-exo-2,3-disubstituted norbornane and norbornene amino acids, cis- and trans-2-aminocyclohexane-, 2-amino-4-cyclohexene-, and 2-aminocyclopentanecarboxylic acids, was investigated via the kinetic method
with metal-bound trimeric complexes. This is the first time that diastereomers (di-endo/di-exo and cis/trans) have been differentiated with metal-bound trimeric complexes and the kinetic method. Moreover, determination of diastereochemical
excess by the kinetic method was applied to norbornane β-amino acids and cyclopentane β-amino acids. Experiments showed that a remarkable differentiation of the studied diastereomers was achieved. It was observed
that better selectivity values correlated to more rigid structures. The reference compounds for the studied β-amino acids varied from α-amino acids to some β-amino acids. In addition, variation of the metal ion (Cu2+ and Ni2+) had some role in the selectivity values obtained. Ab initio and hybrid density functional theory calculations were performed
to clarify the results obtained by mass spectrometry. 相似文献
58.
Anna R. M. Hyyryläinen Jaana M. H. Pakarinen Enikő Forró Ferenc Fülöp Pirjo Vainiotalo 《Journal of the American Society for Mass Spectrometry》2009,20(7):1235-1241
Chiral differentiation of four enantiomeric pairs of β-amino acids, cis-(1R,2S)-, cis-(1S,2R)-, trans-(1R,2R)-, and trans-(1S,2S)-2-aminocyclopentanecarboxylic acids (cyclopentane β-amino acids), and cis-(1R,2S)-, cis-(1S,2R)-, trans-(1R,2R)-, and trans-(1S,2S)-2-aminocyclohexanecarboxylic acids (cyclohexane β-amino acids) was performed successfully by using host-guest complexes and ion/molecule reactions. The experiments were conducted
by using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. The effect of a chiral host
molecule was tested by using three different host compounds; (+)-(18-Crown-6)-2,3,11,12-tetracarboxylic acid, (−)-(18-Crown-6)-2,3,11,12-tetracarboxylic
acid, and β-cyclodextrin. This is the first time that small enantiomeric pairs with two chiral centers have been differentiated using
ion/molecule reactions and host-guest complexes. 相似文献
59.
Elina Virtanen Jari Tamminen Juha Linnanto Pia Mätttäri Pirjo Vainiotalo Erkki Kolehmainen 《Journal of inclusion phenomena and macrocyclic chemistry》2002,43(3-4):319-327
The synthesis, structural characterization, and cation/anion binding properties ofa new bile acid-amino acid conjugate, N-deoxycholyl-l-tryptophan, aredescribed. The structures of the ligand and its cadmium adduct at different pHconditions and various cadmium perchlorate concentrations were determined bymodern multinuclear magnetic resonance spectroscopic as well as ESI-TOF MStechniques. Also semiempirical PM3 and ab initio/HF molecular modellingstudies were performed. Based on 1H,1H NOESY measurementsN-deoxycholyl-l-tryptophan in alkaline conditions was found to appearin a bent conformation which was clearly different from the conformations in neutraland acidic solutions. According to molecular modelling in its minimum energy structurethe tryptophan backbone of the ligand was folded close to the deoxycholic acid skeletonand the structure was stabilized by an intramolecular hydrogen bond. The multinuclearmagnetic resonance experiments indicated that Cd2+-cation was bound with theligand in neutral and alkaline conditions while in acidic conditions protons block thebinding site. ESI-TOF MS revealed clearly a competition between sodium and cadmiumions, the ligand having a stronger affinity for sodium. Cadmium binding occurred onlywhen excess of cadmium was used. Further, ESI-TOF MS spectra showed that variouschlorine oxyanions originated from perchlorate anion formed together with cationsdifferent adducts with the ligand. 相似文献
60.
The mass spectral behaviour of nine 1,3-dioxolanes, seven 1,3-dithiolanes and seven 1,3-oxathiolanes was studied under chemical ionization conditions with ammonia, isobutane, methane, acetone, acetone-d6 or pentan-3-one as reagent gas. The proton affinity of the first members in each series was not large enough for ammonia to protonate them; instead, the ionization took place through unstable [M + NH4]+ ions. Isobutane, which gave rise to abundant [M + H]+ ions in all cases, was the best reagent gas for the determination of the molecular mass. Methane chemical ionization caused extensive fragmentations either through ring cleavage or through the elimination of the largest substituent from ring positions 2 as a neutral hydrocarbon. The ketones used as reagent gas reacted to form adduct ions. In the case of dioxolanes and oxathiolanes, the [M + RCO]+ adduct ion decomposed through ring opening and then, as a consequence of intramolecular nucleophilic substitution, through the elimination of a neutral carbonyl compound. Resonance-stabilized dioxolanylium and oxathiolanylium ions were obtained for dioxolanes and oxathiolanes, respectively. This reaction was almost non-existent for the dithiolanes. 相似文献