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Anders Lund

Publications and source records attributed to Anders Lund.

At least 19 recordsLinked to original sources

Structures of the hexafluorocyclopropane, octafluorocyclobutane, and decafluorocyclopentane radical anions probed by experimental and computational studies of anisotropic electron spin resonance (ESR) spectra.

Anisotropic electron spin resonance (ESR) spectra are reported for the radical anions of hexafluorocyclopropane (c-C(3)F(6)(-)), octafluorocyclobutane (c-C(4)F(8)(-)), and decafluorocyclopentane (c-C(5)F(10)(-)) generated via gamma-irradiation in plastically crystalline tetramethylsilane (TMS) and rigid 2-methyltetrahydrofuran (MTHF) matrices. By combining the analysis of these experimental ESR spectra involving anisotropic hyperfine (hf) couplings with a series of quantum chemical computations, the geometrical and electronic structure of these unusual perfluorocycloalkane radical anions have been characterized more fully than in previous studies that considered only the isotropic couplings. Unrestricted Hartree-Fock (UHF) computations with the 6-311+G(d,p) basis set predict planar ring structures for all three radical anions, the ground electronic states being (2)A(2)(") for c-C(3)F(6)(-) (D(3h) symmetry), (2)A(2u) for c-C(4)F(8)(-) (D(4h)), and (2)A(2)(") for c-C(5)F(10)(-) (D(5h)), in which the respective six, eight, and ten 19F-atoms are equivalent by symmetry. A successful test of the theoretical computation is indicated by the fact that the isotropic 19F hf couplings computed by the B3LYP method with the 6-311+G(2df,p) basis set for the optimized geometries are in almost perfect agreement with the experimental values: viz., 19.8 mT (exp) vs 19.78 mT (calc) for c-C(3)F(6)(-); 14.85 mT (exp) vs 14.84 mT (calc) for c-C(4)F(8)(-); 11.6 mT (exp) vs 11.65 mT (calc) for c-C(5)F(10)(-). Consequently, the same computation method has been applied to calculate the almost axially symmetric anisotropic 19F hf couplings for the magnetically equivalent 19F atoms: (-4.90 mT, -4.84 mT, 9.75 mT) for c-C(3)F(6), (-3.54 mT, -3.48 mT, 7.02 mT) for c-C(4)F(8)(-), and (-2.62 mT, -2.56 mT, 5.18 mT) for c-C(5)F(10)(-). ESR spectral simulations performed using the computed principal values of the hf couplings and the spatial orientations of the 19F nuclei as input parameters reveal an excellent fit to the experimental anisotropic ESR spectra of c-C(3)F(6)(-), c-C(4)F(8)(-), and c-C(5)F(10)(-), thereby providing a convincing proof of the highly symmetric D(nh) structures that are predicted for these negative ions. Furthermore, using the computed 19F principal values and their orientations, the effective 19F anisotropic hf couplings along the molecular symmetry axes were evaluated for c-C(3)F(6)(-) and c-C(4)F(8)(-) and successfully correlated with the positions of the characteristic outermost features in both the experimental and calculated anisotropic spectra. In addition, the electronic excitation energies and oscillator strengths for the c-C(3)F(6)(-) , c-C(4)F(8)(-), and c-C(5)F(10)(-) radical anions were computed for the first time using time-dependent density functional theory (TD-DFT) methods.

Journal Article↗

EPR and DFT study on the stabilization of radiation-generated methyl radicals in dehydrated Na-A zeolite.

Electron paramagnetic resonance (EPR) spectroscopy was applied to study paramagnetic species stabilized in Na-A zeolite exposed to gaseous methane and gamma-irradiated at 77 K. Two types of EPR spectra were recorded during thermal annealing of zeolite up to room temperature. Owing to the results for the zeolite exposed to (13)CH(4) the multiplet observed at 110 K was assigned to a (.-)CH(3)...Na(+) complex. After decay of the multiplet, the isotropic quartet of methyl radical was recorded in the temperature range of 170-280 K. On the basis of the EPR parameters it is postulated that (.-)CH(3) radicals in this temperature region are able to freely rotate inside the zeolite cage. The structures of the (.-)CH(3)...Na(+) adsorption complex and respective hyperfine coupling constants were calculated by applying DFT quantum chemical methods. Two different models were applied to represent the zeolite framework: the 6T structure of one six-membered ring and the 3T cluster. The hyperfine coupling constants calculated for the (.-)CH(3)...Na(+) adsorption complex for both applied models show very good agreement with those obtained experimentally.

Computer Simulation↗

Structures of tetrafluorocyclopropene, hexafluorocyclobutene, octafluorocyclopentene and related perfluoroalkene radical anions revealed by electron spin resonance spectroscopic and computational studies.

Isotropic and anisotropic ESR spectra were observed for the radical anions of hexafluorocyclobutene (c-C(4)F(6)(-)), octafluorocyclopentene (c-C(5)F(8)(-)) and perfluoro-2-butene (CF(3)CF=CFCF(3)(-)) in gamma-irradiated plastically crystalline neopentane, tetramethylsilane (TMS) and TMS-d(12) matrices, or the rigid 2-methyltetrahydrofuran (MTHF) matrix. The isotropic spectra of c-C(4)F(6)(-) and c-C(5)F(8)(-) are characterized by three different sets of pairs of (19)F nuclei with the isotropic hyperfine (hf) splittings of 15.2 (2F), 6.5 (2F), 1.1 (2F) mT for c-C(4)F(6)(-) and 14.7 (2F), 7.4 (2F), 1.0 (2F) mT for c-C(5)F(8)(-). By comparison with the results of ab initio quantum chemical computations, the large triplet (19)F hf splittings of ca. 15 mT are assigned to the two fluorines attached to the C=C bond. The UHF, B3LYP and MP2 computations predict that the geometrical structures of the perfluoroalkenes are strongly distorted by one-electron reduction to form their radical anions; c-C(3)F(4)(-): C(2) symmetry ((2)A state) <-- C(2)(v) ((1)A(1)), c-C(4)F(6)(-): C(1) ((2)A) <-- C(2)(v) ((1)A(1)) and c-C(5)F(8)(-): C(1) ((2)A) <-- C(s) ((1)A'). The structural distortion arises from a mixing of the pi* and higher-lying sigma* orbitals at the C=C carbons similar to that previously found for CF(2)=CF(2)(-) with a C(2)(h) distortion. The isotropic (19)F hf splittings computed with the B3LYP method with 6-311+G(2df,p) basis set for the geometry optimized by the UHF and/or MP2 methods are within 6% error of the experimental values. The experimental anisotropic spectra of c-C(4)F(6)(-), c-C(5)F(8)(-) and CF(2)=CF(2)(-) were satisfactorily reproduced by the ESR spectral simulation method using the computed hf principal values and orientation of (19)F nuclei. In addition, the electronic excitation energies and oscillator strengths for the CF(2)=CF(2)(-), c-C(3)F(4)(-), c-C(4)F(6)(-) and c-C(5)F(8)(-) radical anions were computed for the first time by TD-DFT methods.

Journal Article↗

Automatic fitting to 'powder' EPR spectra of coupled paramagnetic species employing Feynman's theorem.

A previous automatic fitting procedure of EPR spectra has been extended with the purpose to characterise coupled paramagnetic complexes in powders and frozen solutions. The theoretical EPR spectra were obtained by matrix diagonalization of a general spin Hamiltonian. A least-squares fitting procedure using analytical derivatives of the calculated spectrum with respect to the spectroscopic, fine structure, nuclear quadrupole, electron-electron, and hyperfine coupling tensors was used to refine those parameters. The powder spectra of matrix isolated *CF3 and RCF2CF2* radicals, previously measured at low temperature, were reanalysed with this method. A theoretically modeled complex consisting of a Cu2+ ion, featuring an axially symmetric g-tensor and 63Cu hyperfine structure anisotropy, and a free radical located at different orientations, with respect to the symmetry axis of the Cu2+ ion, was examined in order to investigate the possibility to recover the magnetic parameters of the separate units and the magnetic couplings between them.

Copper↗

ESR and theoretical studies of trimer radical cations of coronene.

Highly resolved ESR spectra of monomer, dimer and trimer radical cations of coronene (C24H12) were observed at room temperature for a solution of 1,1,1,3,3,3-hexafluoro-2-propan-2-ol (HFP) containing thallium(III) trifluoroacetate as oxidant. The spectra consisting of multiple lines with isotropic 1H-hyperfine splitting (hfs) constants of 0.0766 mT (24H) and 0.013 mT (6H) were attributable to a mixture of the dimer with the trimer radical cations, (C24H12)2+ and (C24H12)3+. For (C24H12)2+, the 1H-hfs constant agreed well with the reported value, 0.077 mT. However, for (C24H12)3+, the values were significantly different from the reported ones, 0.117 mT (12H) and 0.020 mT (24H), by Ohya Nishiguchi et al. [H. Ohya-Nishiguchi, H. Ide, N. Hirota, Chem. Phys. Lett. 66 (1979) 581], but rather similar to those reported by Willigen et al. [H. van Willigen, E. De Boer, J.T. Cooper, W.F. Forbes, J. Chem . Phys. 49 (1968) 1190]. In conflict with Willigen's report, however, no ESR line broadening which has been ascribed to a low stationary concentration of (C24H12)3+ was detected. Based on ab initio MO calculations for benzene as a compact model of C24H12, the structure of (C24H12)3+ was investigated in terms of the observed 1H-hfs constants. A staggered sandwich C(2v) structure was suggested being at the "global" minimum for the benzene trimer cation. In the structure, the unpaired electron spin is predominantly localized to the central ring, which is qualitatively in agreement with the previous ESR results of (C24H12)3+ by Ohya-Nishiguchi et al. In addition, as a "local" minimum, the benzene trimer was indicated to have a slipped sandwich Cs structure, which is less stable by ca. 19 kJ mol(-1) than the "global" minimum. In this structure, the unpaired electron spin was nearly equally distributed on both the central and one of the two side C24H12 molecules. The observed 1H-hfs constants were possibly attributable to the (C24H12)3+ cation with the analogous slipped sandwich Cs structure.

Cations↗

Mr morphometry analysis of grey matter volume reduction in schizophrenia: association with hallucinations.

The authors used voxel-based morphometry (VBM) to study GM volume differences in the whole brain volume between a group of patients with schizophrenia and a healthy control group. There were 12 patients and 12 control subjects. The subjects were scanned in a 1.5 T MR scanner. The patients had all been evaluated by a senior psychiatrist on the brief psychiatric rating scale (BPRS). The VBM data was correlated with reports of rate and frequency of hallucinations based on their scores on the BPRS hallucination item. There were significant grey matter volume reductions in the schizophrenia patient group in the left superior (transverse) temporal gyrus, the left middle frontal gyrus, and in the right cuneus. Areas of grey matter volume reduction that correlated negatively with hallucinations were found in the left superior (transverse) temporal gyrus, left thalamus, and left and right cerebellum. This article proposes that significant reductions in grey matter volume may be instrumental in generating spontaneous neuronal activity that is associated with speech perception experiences in the absence of an external acoustic stimulus that may cause hallucinations.

Adult↗

Structure of radical cations of saturated heterocyclic compounds with two heteroatoms as studied by electron paramagnetic resonance, electron-nuclear double resonance, and density functional theory calculations.

The radical cations of piperazine, morpholine, thiomorpholine, and thioxane were investigated by electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) spectroscopy in a solid Freon matrix. Optimized geometry and magnetic parameters of the radical cations were calculated using a density functional theory (DFT)/Perdew-Burke-Ernzerhof (PBE) method. Both experimental and theoretical results suggest that all the studied species adopt chair (or distorted chair) conformations. No evidence for the boat conformers with intramolecular sigma-bonding between heteroatoms were obtained. In the cases of morpholine and thioxane, the oxygen atoms are characterized by relatively small spin populations, whereas a major part of spin density is located at N and S atoms, respectively. The thiomorpholine radical cation exhibits nearly equal spin population of N and S atoms. In most cases (except for thioxane), the calculated magnetic parameters agree with the experimental data reasonably well.

Journal Article↗

Density functional theory study of NO adsorbed in A-zeolite.

Density functional theory was employed to investigate the adsorption site and hyperfine interactions of nitric oxide adsorbed in Na-LTA (previous name NaA) zeolite. Three different cluster models of increasing complexity were used to represent the zeolite network: (1) a six-membered ring terminated by hydrogen atoms with one sodium ion above the ring, (2) as model 1 with the addition of three sodium ions located at the centers of three imagined four-membered rings adjacent to the six-membered ring, and (3) as model 2 with the addition of the three four-membered rings adjacent to the six-membered ring. Calculations on the largest system (model 3) showed very good agreement with measured electronic Zeeman interaction couplings, 14N hyperfine coupling tensors, and 23Na hyperfine and nuclear quadruple coupling tensors of the S = 1/2 Na+...N-O adsorption complex when the position of the sodium ion was relaxed. The optimized geometry of the complex agreed nicely with that estimated experimentally, except for the Na-N distance, where the present results indicate that the distance deduced from previous ENDOR experiments may be underestimated by as much as 0.5 angstroms.

Adsorption↗

Executive function improvement upon remission of recurrent unipolar depression.

The aim of the study was to investigate the improvement of executive function measures upon recovery from unipolar depression. Thirty patients who suffered from recurrent major unipolar depression were retested with regard to their executive function approximately two years after an initial baseline examination. At baseline, patients were depressed (average 17-item HAM-D score 21.8), at retesting they were partially or totally recovered (average HAM-D score 8.2). There was a significant positive association between improvement on the HAM-D and improvement of executive function. In those with complete recovery, overall executive function and most examined executive function measures were no longer different from the baseline performance of healthy controls (with the possible exception of semantic fluency and Stroop Colour-word). In conclusion, recovery from major unipolar depression was accompanied by a recovery of many aspects of executive function to a normal level. Our findings support previous studies that have shown that neuropsychological impairment associated with long-standing depressive symptomatology is reversible (i. e. state-related) in recurrent unipolar depression.

Adult↗

The association between depression, anxiety, and cognitive function in the elderly general population--the Hordaland Health Study.

OBJECTIVES: To examine the association between depression and/or anxiety and cognitive function in the elderly general population. SUBJECTS: Non-demented participants from the general population (n = 1,930) aged 72-74 years. METHODS: Symptoms and caseness of depression and anxiety disorder were assessed using the Hospital Anxiety and Depression Scale (HADS). Cognitive function was assessed by the Digit Symbol Test (modified version), the Kendrick Object Learning Test, and the 'S'-task from the Controlled Oral Word Association Test. RESULTS: There was a significant association between depression and reduced cognitive function. The inverse association between anxiety and reduced cognitive performance was explained by adjustment for co-morbid depression. The inverse association between depressive symptoms and cognitive function was found to be close to linear, and was also present in the sub-clinical symptom range. Males were more affected cognitively by depressive symptoms than females. CONCLUSION: The inverse association between depression and cognitive function is not only a finding restricted to severely ill patient samples, but it can also be found in the elderly general population.

Aged↗

Frequency and characteristics of recurrent major depressed patients with unimpaired executive functions.

Major depression is associated with impairment of cognitive functions, and especially higher-order cognitive processes referred to as executive functions (EF). Whether this is a general finding is unclear. Patients without EF impairment may have different treatment needs than patients with EF impairment, and will probably have a better everyday functioning. Thus, it is important to identify the prevalence and characteristics of depressed patients without EF impairment. Forty-three patients with recurrent major depressive disorder (19-51 years) and 50 healthy controls were included in the study. The subjects were assessed with neuropsychological tests selected to measure central areas of EF, and screened on clinical and demographic variables. Within the depressed group, a total of 56% were defined as EF unimpaired. These patients were characterised by higher intellectual abilities and fewer depression episodes than the subgroup of patients with EF impairment. The subgroups were similar in age at debut of illness, severity of depression, general psychopathology and global level of functioning. In conclusion, about half of patients with recurrent major depression have normal EF. Since cognitive impairment and depressive symptomatology seem to be distinct dimensions, a neuropsychological investigation could help to ensure optimal treatment in patients with recurrent major depression.

Adult↗

Validation of distinct amnesic and executive type memory deficit in a psychiatric sample based on retrieval performance.

Studies of localized brain dysfunctions have revealed connections between patterns of cognitive dysfunction and specific profiles of memory impairment. The amnesic type of memory impairment is defined by deficits in both free recall and recognition memory, whereas the dysexecutive memory impairment is characterized by retrieval deficits, i.e. a disproportional impairment in free recall relative to recognition memory. The present study tests whether classifications of psychiatric patients into recall impaired only (= RO group) and Recall and Recognition impaired (= RR group) correspond to the executive type and amnesic type of memory impairment. The alternative hypothesis is that the two groups merely differ in degree of neuropsychological and psychiatric disturbance. Forty-four subjects impaired on California Verbal Learning Test (CVLT) were selected from a larger database of 103 impaired and non-impaired subjects with schizophrenia or recurrent major depression. Subjects were classified into RO and RR groups and compared on measures of memory strategy (recency effect and interference on CVLT), overall neuropsychological function (Stroop Test and WAIS-R similarity) and psychiatric symptom load (positive and negative symptoms). Repeated measures ANOVA showed no effects of group, i.e. the RR group did not perform consistently below the RO group with regard to memory strategy, neuropsychological function or psychiatric symptom load. Two out of three analyses showed group x test interaction, supporting the dissociation of distinct executive and amnesic profiles among psychiatric patients. The RO group was more susceptible to interference but had better recency score than the RR group. The RO had higher negative symptoms while the RR group had higher positive symptoms.

Amnesia↗

Early visual information processing in schizophrenia compared to recurrent depression.

Patients with schizophrenia have repeatedly shown deficits in early visual processing using backward masking (VBM) tasks. Whether this represents a specific dysfunction in schizophrenia is an unsolved question. Patients with recurrent unipolar depression represent an interesting comparison group to examine the question of specificity, but have never previously been assessed on VBM. In addition to comparing VBM performance in patients with schizophrenia and patients with depression, we wanted to examine the relations between VBM and clinical symptoms. Fifty-one patients with schizophrenia were compared to 49 patients with recurrent unipolar depression and 47 healthy controls. All subjects were administered a two-digit identification task in a no-masking and four masking conditions. Patients with schizophrenia performed significantly worse than normal controls on four of the five conditions. No significant difference was found between depression patients and normal controls. The effect of masking stimuli had no differential effects on the three groups. VBM correlated strongly with positive symptoms in the schizophrenia group.

Adult↗

Nitric oxide adsorbed on zeolites: EPR studies.

CW-EPR studies of NO adsorbed on sodium ion-exchanged zeolites were focused on the geometrical structure of NO monoradical and (NO)2 biradical formed on zeolites. The EPR spectrum of NO monoradical adsorbed on zeolite can be characterized by the three different g-tensor components and the resolved y-component hyperfine coupling with the 14N nucleus. Among the g-tensor components, the value of g(zz) is very sensitive to the local environment of zeolite and becomes a measure of the electrostatic field in zeolite. The temperature dependence of the g-tensor demonstrated the presence of two states of the Na-NO adduct, in rigid and rotational states. The EPR spectra of NO adsorbed on alkaline metal ion-exchanged zeolite and their temperature dependency are essentially the same as that on sodium ion-exchanged zeolite. On the other hand, for NO adsorbed on copper ion-exchanged zeolite it is known that the magnetic interaction between NO molecule and paramagnetic copper ion are observable in the spectra recorded at low temperature. The signals assigned to (NO)2 biradical were detected for EPR spectrum of NO adsorbed on Na-LTA. CW-EPR spectra as well as their theoretical calculation suggested that the two NO molecules are aligned along their N-O bond axes. A new procedure for automatical EPR simulation is described which makes it possible to analyze EPR spectrum easily. In the last part of this paper, some instances when other nitrogen oxides were used as a probe molecule to characterize the zeolite structure, chemical properties of zeolites, and dynamics of small molecules were described on the basis of selected literature data reported recently.

Adsorption↗

Impairment across executive functions in recurrent major depression.

Depression is associated with impairment of cognitive functions, and especially executive functions (EFs). Despite the fact that most depressed patients experience recurrence of episodes, the pattern and the severity of executive impairment have not been well characterized in this group of depressed patients. We asked if and to what extent these patients were impaired on a range of neuropsychological tests measuring EFs, and also when confounding factors were adjusted for. Forty-five patients (aged 19-51 years) with moderate to severe (Hamilton score >18) recurrent major depressive disorder (DSM-IV) were compared to 50 healthy controls matched on age, education, gender and intellectual abilities. The subjects were administered a set of neuropsychological tests that assesses sub-components of EFs. The depressed patients were impaired compared to the control group on all selected tests, with a severity of impairment within -1 standard deviation from the control group mean. The group difference was statistically significant for eight of the 10 EFs that were assessed. These were measures of verbal fluency, inhibition, working memory, set-maintenance and set-shifting. The group difference was still significant for all sub-components except for set-shifting (Wisconsin Card Sorting Test) and planning (Tower of London), when additional medication and retarded psychomotor speed was adjusted for. In conclusion, the depressed subjects were mildly impaired across a wide range of EFs. This may have a negative impact on everyday functioning for this group of patients.

Adult↗

Brain activation measured with fMRI during a mental arithmetic task in schizophrenia and major depression.

OBJECTIVE: The authors used functional magnetic resonance imaging (fMRI) to investigate brain activation in patients with schizophrenia and major depression while they performed two tasks-a vigilance task and a mental arithmetic task-that differed in cognitive complexity. METHOD: In the vigilance task, the participants had to press a response button whenever a specific number was seen on a screen inside the MR scanner. In the mental arithmetic task, the participants had to add two consecutive numbers and press the response button whenever the sum was 10. fMRI was performed with a 1.5-T MR scanner. Twelve patients with recurrent nonpsychotic unipolar major depression, 12 patients with schizophrenia, and 12 healthy comparison subjects were included in the study. RESULTS: Performance data showed that the patients were impaired relative to the comparison subjects and showed no difference in performance between the patient groups. The patients with schizophrenia, but not those with major depression, had less activation in prefrontal brain regions, relative to the comparison participants. However, subtracting brain activation during the vigilance task from activation during the mental arithmetic task showed that the schizophrenia patients had activation in parietal areas. CONCLUSIONS: A double dissociation of parietal and frontal lobe activation was found for the schizophrenia patients and the depression patients. The greater parietal lobe activation in the patients with schizophrenia may reflect a compensatory strategy for the failure to recruit cognitive processes that involve frontal lobe areas when solving a mental arithmetic task.

Adult↗

Long-lasting cognitive impairment in unipolar major depression: a 6-month follow-up study.

The aim of the study was to investigate cognitive impairment in major depression both acutely and after 6 months. All patients were investigated within a neurocognitive experimental setting at two testing sessions: at inclusion and after 6 months. Automatic and effortful information processing was investigated with a visual search paradigm. Twenty-one patients with recurrent major depression according to DSM-IV and a Hamilton Depression Rating Scale score >18 were included in the study. Healthy subjects, matched for age and gender, were used as a control group. The results showed that the depressed patients performed equal to the control group on trials requiring automatic information processing at both sessions. However, the patients were impaired compared to the control group on trials requiring effortful information processing, also at both sessions. The depressed patients showed no improvement in cognitive performance from test 1 to test 2. The results indicate that the depressed patients had an impaired performance for effortful, but not automatic, visual search performance, and that the impairment remained after 6 months, despite significant improvement in their depression scores.

Adult↗

Attentional and executive dysfunctions in schizophrenia and depression: evidence from dichotic listening performance.

BACKGROUND: We compared performance on a dichotic listening (DL) task between schizophrenic, depressed, and healthy control subjects. A variant of the traditional DL paradigm was used in which the subjects were required to focus attention either on the left (forced-left condition) or right (forced-right condition) ear stimulus. METHODS: The subjects were 51 patients with a DSM-IV diagnosis of schizophrenia, 49 patients with recurrent unipolar major depression, and 49 healthy control subjects. They were tested with a consonant-vowel syllables dichotic listening task under three attentional instructions. RESULTS: There was a significant overall right ear advantage during the nonforced condition, which increased dramatically during the forced-right condition and was eliminated during the forced-left condition. The depressed patients showed no signs of impairments compared with the healthy control group. Thus, they showed a right ear advantage during the nonforced and forced-right conditions, which was shifted to a left ear advantage during the forced left condition. The schizophrenic patients, however, were impaired on the forced-left condition compared with the healthy control and depressed subjects. CONCLUSIONS: The results are discussed in terms of separating attentional and inhibitory executive impairments in schizophrenia and depression, taking into consideration illness duration and information-processing demands.

Attention↗