Search

The chromatographic properties of reversed-phase high-performance liquid chromatographic (RP-HPLC) packings with chemically bonded C 18 groups of controlled coverage were characterized by correlation of the capacity factor and the composition of the mobile phase, taking physico-chemical properties of the packings into account. On the basis of a cylindrical model of pores and the dependence of retention on density and homogeneity of the surface coverage with alkylsilyl ligands, an attempt was made to describe the retention mechanism in the RP-HPLC system. It was found that packings with a coverage density higher than 3.8 μmol/m 2 were dense, homogeneous and shielded the unblocked surface silanol groups sufficiently.

Previous studies on neuronal activation correlates of panic attacks were mostly based on challenge tests, sensory-related stimulation or fear conditioning in healthy subjects. In the present study, we report on a female patient with panic disorder experiencing a spontaneous panic attack under an auditory habituation paradigm in the last stimulation block with sine tones captured with fMRI at 3T. The panic attack was associated with a significantly increased activity in the right amygdala. This is the first report on neuronal activation correlates of a spontaneous panic attack in a patient with panic disorder as measured by fMRI, which lends further support to a pivotal role of the amygdala in the pathogenesis of the disease.

Fibromyalgia syndrome (FMS) is characterized by widespread pain. Studies with functional neuroimaging support the hypothesis of central pain augmentation in FMS. We tested this in our study with a novel paradigm of tonic pain induced by a single stimulus. Tonic pain, in contrast to phasic pain, seems to be a more appropriate experimental approach to study adaptive mechanisms of pain processing in FMS. We hypothesized that brain areas related to the "medial" pain system and the amygdalae will present different activation in patients compared to healthy subjects. An fMRI-block design before, during and after an incision was made in patients with FMS and in healthy controls. Acute pain caused by the incision was measured during the course of the experiment. A 2 factorial model of BOLD-signal changes was designed to explore significant differences of brain activation between both groups during the pain stimulus. Additionally the first Eigenvariates in those areas which show an interaction between both factors were determined over the time course of pain stimulation. Differences of activation in the fronto-cingulate cortex, the supplemental motor areas, and the thalamus were found between both groups with distinct differences in BOLD-signals changes over the time course of pain stimulation, even during anticipation of pain. Our results support the hypothesis that central mechanisms of pain processing in the medial pain system, favourable cognitive/affective factors even during the anticipation of pain, may play an important role for pain processing in patients with FMS.

Metabolites within the left dorsolateral prefrontal cortex (DLPFC) of six inpatients with bipolar II rapid cycling (RC) during various mood states (depressed, hypomanic, and euthymic), six depressed inpatients with non-RC bipolar disorder (BIPD), and six healthy controls (HC) were assessed by proton magnetic resonance spectroscopy (MRS). We hypothesized that glutamate/glutamine levels should be altered in RC compared with HC. Patients with RC in contrast to BIPD and HC exhibited elevated levels of N-acetylaspartate (NAA), choline (Cho), creatine (Cr), and glutamate/glutamine (Glx) during all mood states. The Glx levels of BIPD compared with HC did not differ significantly; the other metabolites were increased, though less than in RC patients. Our findings of elevated metabolites in patients with RC, especially Glx as a possible marker of cortical activity, indicate that increased neuronal activity may constitute an important neurobiological feature of RC.

Structural alterations of the basal ganglia occur in patients with Huntington’s disease (HD). The aim of this exploratory study was to assess auditory processing mechanisms by functional MRI (fMRI) in patients with premanifest (pHD) and manifest HD to gain more insight in possible alterations in basal ganglia–thalamic circuits. Sixteen HD and 18 pHD as well as corresponding age- and gender-matched controls were included. The pHD group was divided into two subgroups close (cpHD; 10 years), according to their estimated age of disease onset (eAO). Tone perception and processing were visualized by 3 T fMRI by employing repeated tone stimulation through digitally generated pulsed (ν = 5 Hz) 800-Hz sine tones. We found altered activation in basal ganglia–thalamic circuits in HD and/or pHD compared to controls. (i) The cpHD group presented predominantly down-regulated processes compared to fpHD and HD. (ii) HD presented stronger bilateral activation of the putamen and (iii) fpHD presented stronger bilateral activation of the thalamus and also right caudatum. (iv) Depending on the progress of the disease, a shift towards the activation of more right hemispherical areas can be observed. Our findings seem to reflect an altered activation pattern to auditory stimulation depending on the progression of neuronal dysfunction in HD and pHD. They also stress the involvement of the basal ganglia–thalamic circuits in the processing of sensory auditory stimuli. © 2007 Elsevier Ltd. All rights reserved.

Although neuroimaging research has made substantial progress in identifying the large-scale neural substrate of anxiety disorders, its value for clinical application lags behind expectations. Machine-learning approaches have predictive potential for individual-patient prognostic purposes and might thus aid translational efforts in psychiatric research.To predict treatment response to cognitive behavioral therapy (CBT) on an individual-patient level based on functional magnetic resonance imaging data in patients with panic disorder with agoraphobia (PD/AG).We included 49 patients free of medication for at least 4 weeks and with a primary diagnosis of PD/AG in a longitudinal study performed at 8 clinical research institutes and outpatient centers across Germany. The functional magnetic resonance imaging study was conducted between July 2007 and March 2010.Twelve CBT sessions conducted 2 times a week focusing on behavioral exposure.Treatment response was defined as exceeding a 50% reduction in Hamilton Anxiety Rating Scale scores. Blood oxygenation level-dependent signal was measured during a differential fear-conditioning task. Regional and whole-brain gaussian process classifiers using a nested leave-one-out cross-validation were used to predict the treatment response from data acquired before CBT.Although no single brain region was predictive of treatment response, integrating regional classifiers based on data from the acquisition and the extinction phases of the fear-conditioning task for the whole brain yielded good predictive performance (accuracy, 82%; sensitivity, 92%; specificity, 72%; P .001). Data from the acquisition phase enabled 73% correct individual-patient classifications (sensitivity, 80%; specificity, 67%; P .001), whereas data from the extinction phase led to an accuracy of 74% (sensitivity, 64%; specificity, 83%; P .001). Conservative reanalyses under consideration of potential confounders yielded nominally lower but comparable accuracy rates (acquisition phase, 70%; extinction phase, 71%; combined, 79%).Predicting treatment response to CBT based on functional neuroimaging data in PD/AG is possible with high accuracy on an individual-patient level. This novel machine-learning approach brings personalized medicine within reach, directly supporting clinical decisions for the selection of treatment options, thus helping to improve response rates.

Objectives: Depression is accompanied by disturbed implicit (unconscious) and explicit (conscious) memory functions. The aim was the assessment of immediate and delayed verbal and visual memory functions, concentration/attention during the course of electroconvulsive therapy (ECT) treatment. Methods: Twenty severely depressed, drug-treatment resistant, elderly patients were assessed with the Wechsler Memory Scale-Revised (WMS-R) before and at the end of the ECT series. Results: Patients revealed deficits in acquisition (immediate verbal and visual memory), attention/concentration, and retrieval of information (delayed memory) before ECT. After ECT, significant improvements were observed in immediate memory but not in delayed memory. Although higher total stimulation levels (millicoulombs) (P = 0.015) were associated with improvements in immediate visual memory, we found that longer duration of convulsions (P = 0.016) as well as lower levels of stimulation at last ECT (P = 0.036) were associated with improvements in immediate verbal memory. Moreover, we found that stimulation energy (millicoulombs) in total and at last ECT was the best predictor among several clinical and ECT parameters of improved visual memory and concentration and decreased verbal and general memory. Conclusions: Prefrontal cortex-related memory processes, especially immediate memory encoding, improved after ECT, whereas long-term memory remained impaired, indicating that severely depressed patients remain cognitively inferior to normal subjects despite clinically successful treatment. This study may yield a better understanding of the time course of memory alterations in severely depressed patients receiving ECT. Improvement of immediate memory may be essential for establishing normal daily activities of life in the recovery phase of depression.

Post-mortem and in-vivo studies support the hypothesis that astrocytes might be involved in the pathogenesis of schizophrenia. To further substantiate this hypothesis two markers of astroglial activation (myo-inositol, S100B) acquired with independent methods ((1)H-MRS, quantitative immunoassay) were concomitantly measured in schizophrenic patients. Patients with increased S100B levels showed elevated myo-inositol concentrations. This pilot study demonstrates a concomitant elevation of two markers indicating astrocyte activation in a subgroup of schizophrenic patients.

Background A combination of magnetoencephalography and proton magnetic resonance spectroscopy was used to correlate the electrophysiology of rapid auditory processing and the neurochemistry of the auditory cortex in 15 healthy adults. To assess rapid auditory processing in the left auditory cortex, the amplitude and decrement of the N1m peak, the major component of the late auditory evoked response, were measured during rapidly successive presentation of acoustic stimuli. We tested the hypothesis that: (i) the amplitude of the N1m response and (ii) its decrement during rapid stimulation are associated with the cortical neurochemistry as determined by proton magnetic resonance spectroscopy. Results Our results demonstrated a significant association between the concentrations of N-acetylaspartate, a marker of neuronal integrity, and the amplitudes of individual N1m responses. In addition, the concentrations of choline-containing compounds, representing the functional integrity of membranes, were significantly associated with N1m amplitudes. No significant association was found between the concentrations of the glutamate/glutamine pool and the amplitudes of the first N1m. No significant associations were seen between the decrement of the N1m (the relative amplitude of the second N1m peak) and the concentrations of N-acetylaspartate, choline-containing compounds, or the glutamate/glutamine pool. However, there was a trend for higher glutamate/glutamine concentrations in individuals with higher relative N1m amplitude. Conclusion These results suggest that neuronal and membrane functions are important for rapid auditory processing. This investigation provides a first link between the electrophysiology, as recorded by magnetoencephalography, and the neurochemistry, as assessed by proton magnetic resonance spectroscopy, of the auditory cortex.

Background Alterations in brain metabolism as well as in brain function in different brain areas can be observed in severely depressed patients. Methods The present study combined proton magnetic resonance spectroscopy ( 1 H MRS, n = 16; healthy controls n = 27) and magnetoencephalography (MEG, n = 17, controls n = 18) of the left auditory cortex in severely depressed inpatients pre- and postsuccessful antidepressive therapy. For MEG recordings, patients were stimulated with trains of 4 successive vowels or 4 sine tones, respectively. For each of the 4 stimuli, the amplitude and latency of the N1m was calculated. As a measure of habituation the decrease of the individual amplitudes of the second, third and fourth N1m compared to the first N1m was calculated. Results Prior to therapy, a subset of patients presented clearly disturbed auditory processing to stimuli (missing of distinct N1m1 and subsequent habituation; 5 of 17 patients (vowels) and 9/17 (tones, respectively)). After treatment, compared to controls, a normalized habituation pattern was observed in all patients for vowels, but not for tones. In contrast, MRS revealed no significant differences between the metabolite concentrations of patients and healthy controls in both measurements. Conclusion Depression may be accompanied by impaired auditory processing, which seems to improve with reduction in depressive symptoms. Auditory cortical dysfunction probably reflects only a part from more widespread aberrations of brain function occurring with severe mood disorder.

Objective. 31 P magnetic resonance spectroscopy (MRS) is useful for evaluating metabolic disturbances in dermatomyositis (DM). However, short-term alterations of metabolic parameters such as Pi/PCr (inorganic phosphate/phosphocreatine) have not been assessed in detail, although they may reveal insights into the origin of the known long-term changes. We therefore performed real-time functional 31 P MRS to find out if there are characteristic short-term alterations of metabolic dynamics during muscular exercise and if they are of diagnostic relevance. Methods. MRS measurements were performed on lower calf muscles of 10 DM patients and 18 healthy subjects throughout five short (1 min) cycles of submaximal exercise (50% maximum voluntary contraction). Results. Pi/PCr ratios during exercise increased in patients and controls. They rapidly returned to baseline values in the controls, but both Pi and PCr remained above baseline values in patients and resulted in irregular Pi/PCr ratios. This was true for each individual patient, but resulted in broad variation in individual Pi/PCr values. To compare groups with limited patient numbers, it was therefore more appropriate to use a recovery index, i.e. the quotient of the Pi/PCr ratio during and after exercise, which was independent of individual parameters, such as age and the work/energy cost ratio. Conclusion. Evaluation of short-term changes by real-time functional 31 P MRS provides insight into alterations of Pi/PCr ratios and could improve diagnostic parameters in DM.

The left frontal cortex plays an important role in executive function and complex language processing inclusive of spoken language. The purpose of this work was to assess metabolite levels in the left and right prefrontal cortex and left anterior cingulum by proton magnetic resonance spectroscopy and relate results to verbal intelligence (Wechsler Adult Intelligence Scale revised) in a sample of college-educated healthy volunteers (dorsolateral prefrontal cortex [DLPFC]: n=52, 23 females, and left anterior cingulum: n=62, 22 females; age range: 20-75 years). In women only, N-acetylaspartate in the DLPFC and in the left anterior cingulate cortex was positively correlated with vocabulary scores. Our data support the hypothesis of existing gender differences regarding the involvement of the left frontal cortex in verbal processing as reflected in different correlations of specific metabolites with verbal scores.

The aim of this study was to measure and quantify habituation effects to auditory stimulation within the auditory cortex of 11 depressed patients with major depressive disorder compared to 11 healthy subjects. Habituation was visualized by functional magnetic resonance imaging (fMRI) employing a block design (repeated stimulation with sine tones). A subgroup of patients (n = 5) presented the following abnormal habituation fMRI pattern: significantly lower activation after the first stimulation block (p = 0.05), missing characteristic signal decay to repeated acoustic stimulation and a marked undershoot after each stimulation block. This abnormal pattern may indicate functional deficits in auditory processing occurring with depression, but our results need be confirmed in a larger, more homogeneous patient group. This paradigm may be a useful tool for assessing cortical dysfunction in mood disorders.

Background. The dorsolateral prefrontal cortex (DLPFC) is involved in the pathophysiology of major depression. In particular, metabolic (functional hypometabolism) and structural alterations have been described. In this study metabolic changes within the DLPFC of severely depressed patients before and after electroconvulsive therapy (ECT) were evaluated by proton STEAM spectroscopy (1H-MRS).Method. Twelve severely depressed patients with a diagnosis of major depressive episode, unipolar with melancholic features (DSM-IV), were enrolled, and the left dorsolateral prefrontal cortex (DLPFC) was investigated before and after unilateral ECT by 1H-MRS. Three of the four non-responding patients were remeasured a third time after a combined ECT/antidepressant pharmacotherapy. The results were compared with 12 age- and gender-matched controls.Results. In depressed patients reduced glutamate/glutamine (Glx) levels were measured pre-ECT; Glx concentrations correlated negatively with severity of depression. After successful treatment, Glx increased significantly and levels no longer differed from those of age-matched controls.Conclusions. Our results indicate that major depressive disorder is accompanied by state-dependent metabolic alterations, especially in glutamate/glutamine metabolism, which can be reversed by successful ECT.

Cortical glutamate/glutamine (Glx) metabolism seems to be affected by a major depressive disorder. Recently, a Glx deficit was detected by proton magnetic resonance spectroscopy (1H-MRS) in the bilateral anterior cingulum of depressives. The aim of this study was to assess the effect of successful electroconvulsive therapy (ECT) on Glx levels in the anterior cingulum. The left anterior cingulum of 17 severely depressed unipolar patients was measured by 1H STEAM spectroscopy before and after ECT, and the results were compared with those for 17 age- and gender-matched controls. We observed significantly reduced Glx levels in the patients' left cingulum compared to healthy controls. In ECT responders, in contrast to non-responders, Glx levels normalized (P=0.04) and then did not differ statistically from controls. Severe depression seems to be associated with a Glx deficit and increasing Glx may be an important mechanism of ECT action.

The dorsolateral prefrontal cortex (DLPFC) participates in the pathophysiology of mania. In particular, left-sided structural and metabolic abnormalities have been described. Clinical symptoms may be due to hyperactivity of cortical glutamatergic neurons, resulting in increased excitatory neurotransmitter flux and thus enhanced Glx levels. Glutamate/glutamine (Glx) levels were assessed by proton magnetic resonance spectroscopy (1H-MRS) in eight acute manic patients compared with age- and gender-matched controls. Manic patients had significantly elevated Glx levels (t-test; t=–3.1, P=0.008) within the left DLPFC. Our results indicate that the prefrontal cortical glutamatergic system is involved in the pathophysiology of acute mania. This may have implications for the treatment of mania.

Silicone [poly(dimethylsiloxane)] gel used in breast implants has been known to migrate through intact silicone elastomer shells, resulting in the clinically observable "gel bleed" on the implant surface. Although silicon concentrations in capsular tissues of women with silicone prostheses have been measured with element-specific silicon analyses, no silicone-specific investigation of these tissues has been performed as yet.A combination of element-specific inductively coupled plasma high-resolution isotope dilution mass spectrometry (ICP-HR-IDMS) and species-specific gas chromatography coupled mass spectrometry (GC-MS) was used to analyze silicon, platinum, and siloxanes in prosthesis capsule, muscle, and fat tissues of women (n=3) who had silicone gel-filled breast implants and in breast tissue of non-augmented women (n=3) as controls.In all tissues of augmented women, siloxanes, in particular octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) were identified. Depending on the siloxane species and type of tissue analyzed, siloxane levels in the range of about 10-1,400 ng g(-1) were detected; total silicon was found in all tissue samples in the range of about 8,900-85,000 ng g(-1). Higher platinum levels ranging from 25-90 ng g(-1 )were detected in fibrin layer and fat tissue of two patients with prostheses. No siloxanes were detected in control breast tissue samples. This investigation of human tissues by a combination of element-specific and species-specific analytical techniques clearly demonstrates for the first time that platinum and siloxanes leak from prostheses and accumulate in their surrounding tissues.

Studies using magnetic resonance spectroscopy in human volunteers to evaluate their livers in vivo and to analyze their blood in vitro suggest that there are measurable amounts of silicon compounds in the blood of some women with implants and that there is migration of silicone to other organs such as the liver.

A sensitive, one-step sample preparation method for detection of volatile, low molecular weight (LMW) cyclic silicones hexamethylcyclotrisiloxane (D3), octamethyl-cyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in plasma and blood using gas chromatography coupled with mass spectrometry (GC/MS, SIM mode) is presented. In spiked experiments, extraction efficiencies for these siloxanes (100-20 000 ng/mL) were approximately 90% for plasma and approximately 80% for blood; only in the case of D3 was the recovery very low. Plasma and blood of women who are or were exposed to silicone gel-filled implants and of control subjects were analyzed for low molecular weight silicones. D3-D6 were not detectable in control plasma or blood. Although the investigated numbers of patients samples are very limited, and thus, no statistical analysis is possible, our data clearly show a general increase in the amount of LMW cyclic siloxanes in the bodies of women with silicone implants. In particular, several years after ruptured silicone implants were removed, siloxanes could still be found in blood samples from several women. Siloxane compound D3 varied between 6 and 12 ng/mL (plasma) and between 20 and 28 ng/mL (blood), whereas the concentration range of D4 was 14-50 ng/mL (plasma) and 79-92 ng/mL (blood). D5 and D6, with one exception, could not be detected.

This letter to the editor examines how gender seems to affect the course of bipolar disorder especially regarding the development of rapid cycling which occurs more frequently in women. It reports on a young woman who experienced rapid cycling after cessation of oral contraceptive medication as the onset of bipolar II disorder indicating an influence of sex hormones on the course of bipolar disorder.

Linear and cyclic polysiloxanes and extracts (free polymer) from a silicone gel-filled implant are used to investigate the reactivity of silicones in vivo. Aqueous emulsions of polysiloxanes and controls (without polysiloxanes) are injected once (day 0, approximately 10% w/v) or six times (starting at day 0, every 14 days, approximately 3% w/v) in the right thigh of rats and the popliteal and lumbar lymph nodes are harvested (3 rats per time point and compound investigated) at 2, 16, 30, 44, 58 and 72 days after the injection. 29Si NMR spectroscopy is used to detect and evaluate the presence of polysiloxanes and their metabolites in the lymph nodes. In addition to the resonance associated with the polysiloxane injected (approximately -20 ppm), the NMR spectra of lymph nodes show new resonances that are attributed to partially hydrolyzed polysiloxanes (-5 to -15 ppm) and silica (-90 to - 120 ppm). These resonances are not present in polysiloxanes emulsions before injection or in the lymph nodes of controls. Our results demonstrate that all polysiloxanes and extracts from silicone gel-filled implants are biotransformed in the lymph nodes, but high molecular weight polymer degrades at a slower rate than oligomers.

To evaluate, at hydrogen-1 magnetic resonance (MR) spectroscopy, the effect of implantation time, implant status, and implant removal on the amount of silicone in the liver in women with silicone gel-filled breast prostheses.The study population included 55 women (39 patients with silicone gel-filled prostheses and seven from whom implants had been removed, and nine control subjects [eight with no implant and one with saline-filled implants]). Stimulated-echo acquisition mode, or STEAM, H-1 MR spectroscopy was performed to determine the concentration of silicone in the liver. Implant status at the time of spectroscopy was diagnosed at MR imaging.Twenty of 39 (51%) women with implants had ruptured prostheses. Resonances associated with the presence of silicone and partially hydrolyzed silicone (0.3 to -0.8 ppm with respect to water at 4.7 ppm) and other resonances that are not yet assigned (-2 to -5 ppm) were detected in 27 (69%) of the 39 women (17 with ruptured implants). Relative signal intensities of the silicone species detected in the liver in these women were found to vary substantially and were not correlated with the status of the implants (P.70). Silicone resonances were not detected in the livers in the nine control subjects. After implant removal, no resonances between 0.3 and -0.8 ppm were observed in six of seven women, but silicone-related peaks were still detectable in the region of -2 to -5 ppm.Proton MR spectra obtained in the liver of women with silicone gel-filled breast implants helped measure silicone exposure.

Silicones, generic name of synthetic polymers with a backbone of SiO bonds and organic side groups (aliphatic and/or aromatic), are among the most widely used materials for biomedical purposes [1]. In particular, it is estimated that about 1.5 million silicone gel-filled breast prosthesis are presently implanted in the U.S. for the purpose of reconstruction and augmentation mammaplasty. Although silicones have been assumed to be stable, their benign nature has been questioned recently, and in April 1992 the Food and Drug Administration (FDA) severely restricted the use of silicone gel-filled prostheses for breast augmentation arguing that the risks have not been adequately defined [2].

Diabetic lens glucose metabolism in vivo can be altered by a number of exogenous substrates. We have chosen two, one a glucose epimer (mannose) and the other a glycolytic intermediate (pyruvate), to demonstrate the possibility of this approach. d (+)-Mannose is a d (+)-glucose epimer but in lenses incubated in 35·5 m m mannose, no mannitol (the sorbitol equivalent) was detected, while both lactate production and 31 P profile appeared normal. Mannose therefore is a good glucose substitute causing no polyol formation. Mannose metabolism in the rat lens in vivo was then examined. Diabetic rats fed mannose-enriched diet over a period of 14 days showed retardation of changes in 31 P metabolites, specifically the levels of phosphorylcholine and glycerophosphorylcholine, suggesting a protective effect. Rat lenses incubated in 35·5 m m glucose in the presence of 5 m m pyruvate (pyr) showed 50% lower sorbitol than without pyr. With 5 m m pyr in the drinking water, i.e. pretreatment in vivo during a 3-day diabetes induction period, the diabetic rat lens accumulated acetate and alanine when incubated in the presence of pyr. The decrease in sorbitol was most likely due to a lower glucose flux rather than an increased polyol dehydrogenase activity. Increasing glucose concentration from 5·5 to 35·5 m m or provision of exogenous pyr both caused an intermediate increase in O 2 consumption in the normal lens; a maximal activity was reached with both 35·5 m m glucose and 5 m m pyruvate in the incubating medium. In the diabetic lens. O 2 consumption could reach the intermediate but not the maximal level. Dietary pyr pre-treatment also prevented normal and diabetic lenses from maximal pyr-stimulated O 2 consumption. The NMR and O 2 consumption data together indicated activation of alanine dehydrogenase and saturation of Krebs cycle. It appears that dietary supplement of mannose can preserve 31 P membrane metabolites in the diabetic lens. Mannose can be used in conjunction with hypoglycemic therapy for the management of diabetic cataract. In addition, pyruvate may be effective in enhancing lens energy metabolism and lower sorbitol production.

Multinuclear nuclear magnetic resonance (NMR) spectroscopy (29Si, 13C, 1H) is used to characterize the aging process of silicone rubber-based biomaterials in a rat model. 1H NMR relaxation measurements (spin-lattice, T1, and spinspin, T2, relaxation times) were performed to better understand the molecular dynamics of polysiloxane chains in implants. After 1 year of implantation in animals, changes in the 1H T2 relaxation times and the NMR spectra were observed in polydimethylsiloxane, Silastic® sheets and chin implants, while these measurements remain unchanged in finger joints. Very small amounts of fat were detected in all types of silicone rubber implants at the end of the implantation period. This work shows that free silicone migrates from the implants to adjacent tissues and distant sites, such as spleen or liver, and is chemically modified. © 1995 John Wiley & Sons, Inc.

Background: There is increasing evidence for functional interactions of the auditory and the motor system in music perception. Based on that we hypothesized that altered music perception in patients with a movement disorder, here Huntington's disease (HD), compared to controls should be present. Additionally, there should be also a relation between areas associated with the assessment of musical rhythms and measures of movement deterioration in patients.Methods: Manifest (HD) and premanifest HD (pHD), as well as healthy controls underwent an examination with auditory functional MRI (fMRI) with presentation of music and syllables as stimuli. Additionally, motor performance was assessed in tasks with different complexity and related to fMRI-data.Results: There was a significant interaction of type of stimuli (music, syllables) and group (HD, phD, controls). During music processing when compared to blocks with syllables only, HDs revealed hyperactivations, especially in cerebellar structures,. In contrast, these structures were stronger activated during syllable presentation in pHD´s and controls, when compared to HD and music processing. Increased cerebellar activations during music processing in HDs were related to more severe voluntary and involuntary movement dysfunction. No correlations were observed with activations after syllable presentation. Generally, no relations were found in pHDs.Conclusion: The results suggest modulation of auditory music processing in a movement disorder, which seems to relate to severity of movement deterioration. Language: en

1H NMR localized spectroscopy (STEAM) can assess unambiguously the presence of free chemically unchanged silicone in animal tissue after injection of silicone oil. Although the signal-to-noise ratio obtained in 1H imaging is sufficient to detect the distribution of relatively large amounts of silicone in vivo, the specificity of silicone detection can be improved by using 1H localized spectroscopy techniques. The sensitivity of the STEAM experiments is sufficient to detect silicone at a concentration of 0.5% in a voxel of 27 mm3. Preliminary results from rats with silicone gel-filled implants show no detectable amounts of silicone in sites such as lymph nodes, the liver or the spleen, 3 or 6 months after implantation.

29Si nuclear magnetic resonance (NMR) spectroscopy is applied to study the degradation of polysiloxanes (silicones) in vivo. Our results with animal models show that silicone migrates from the implant to the liver (29Si resonance at -20 ppm) and new silicon containing compounds form after the silicones are introduced into the rats. The new 29Si resonances in the chemical shift range of -40 to -85 ppm are related to hydrolyzed silicone, those at -90 to -115 ppm are indicative of the presence of silica (SiO2), and the peaks observed at -120 to -150 are related to high coordinated silicon complexes. These resonances are not present in the 29Si spectra of the silicones before implantation. Our findings demonstrate that silicones are not metabolically inert.

We have developed an echo-planar (EP) proton chemical shift imaging (CSI) MR technique that allow us to discriminate the polydimethylsiloxane (PDMS, silicone) proton MR signal from that of the fat and water protons found in tissues, in order to map the distribution of PDMA in humans who have silicone gel prostheses. Silicone gel-filled prosthetic implants induce histologic changes in the surrounding tissue which are attributed to the leakage of free PDMS from the prosthesis. The T2 relaxation measurements of three silicone gels show that there are two components in them, each with a different degree of molecular mobility. The presence of free silicone is confirmed by chloroform extraction, which removed 14-28% of the material. This free polymer present in the gel can pass through the intact or ruptured membrane of the implant into the surrounding tissue. Our preliminary imaging results indicate that EP-CSI MR might be useful as a diagnostic technique for implant malfunction.

Silicone based biomaterials are characterized with NMR. Bulk spin-lattice (T1) and spin-spin (T2) relaxation times are measured in polydimethylsiloxane (PDMS) model networks and various types of implants. The T2 results seem to indicate that crosslink densities of these biomaterials are lower than those of the PDMS model networks studied. 1H chemical shift NMR imaging techniques are developed to investigate the aging (e.g., migration of free polymer, rupture due to mechanical stress, etc.) of biomaterials in vivo.

Fe 3+ ions in iron(III) chloride-modified silica gels have previously been reported to be bound exclusively to silanediol groups on the surface. A silica gel (Nucleosil) was modified with various amounts of iron(III) and this masking had an influence on the retention of bases. As the iron(III) load increased, the capacity k ′factors decreased and the number of plates increased. At a certain iron(III) content saturation occurred and thereafter the k ′ value remained constant. Only about 40% of the total silanediol groups of Nucleosil influenced retention, which can be explained by the presence of silanediols with different reactivities. Electron paramagnetic resonance measurements of the modified silica gels revealed that Fe 3+ ions are bound to the silanediol groups as a chelate complex.