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PubMed2004

Improving neuron-to-electrode surface attachment via alkanethiol self-assembly: an alternating current impedance study.

In this work, the omega-amine alkanethiols, cysteamine (CA) and 11-amino-1-undecanethiol (11-AUT), were chemisorbed as self-assembled monolayers (SAMs) onto 250-microm gold microelectrodes that were microlithographically fabricated within eight-well cell culture plates and investigated as a means to improve neuron-to-electrode surface attachment (NESA). Dynamic contact angle (DCA) measurements showed similar advancing, theta(a) (69 degrees and 65 degrees ), but contrasting receding contact angles, theta(r) (9 and 30 degrees ) for CA- and 11-AUT-SAMs, respectively. The corresponding hysteresis (Deltatheta(ar) = 60 and 35 degrees, respectively) indicates the CA-SAM displays greater amphiphilic character than the 11-AUT-SAM. A portion of the greater Deltatheta(ar) for CA-SAMs may arise from surface heterogeneity, as compared to sputter-deposited gold and 11-AUT-SAMs. Tapping mode atomic force microscopy (AFM) confirmed a 6% increase (CA-SAM) and a 22% decrease (11-AUT-SAM) in surface roughness when compared to clean but unmodified, sputter-deposited gold. The extracellular matrix cell adhesion proteins, collagen, fibronectin, and laminin, were covalently coupled to the aminoalkanethiol-decorated gold electrodes via acid-amine heterobifunctional cross-linking. Using fluorescein isothiocyanate-tagged laminin, confocal fluorescence microscopy of both CA- and 11-AUT-SAM-modified and unmodified gold microelectrodes confirmed coupling of the protein to the electrode and was readily distinguishable from nonspecifically adsorbed protein. DCA measurements of laminin physisorbed directly onto gold or covalently immobilized via CA- or 11-AUT-SAM had similar advancing (ca. 63-65 degrees ) and receding (ca. 7-9 degrees ) contact angles. Tapping mode AFM of these protein-bearing surfaces likewise showed dimerized protein aggregates of similar surface roughness. PC-12 cells cultured to confluence on both unmodified and SAM-modified, protein-derivatized gold microelectrodes were examined by alternating current impedance (50 mV p-t-p at 4 kHz). CA- and 11-AUT-SAM-modified surfaces when serving as a foundation or covalently immobilized adhesion proteins produced highly stable and reproducible temporal impedance responses. On the basis of the magnitude and the reproducibility of the impedance responses, the CA-SAM-modified surfaces were identified as being best suited for optimal neuron-to-electrode contact with laminin. Laminin performed best when compared to collagen and fibronectin. Covalent immobilization of the adhesion-promoting proteins results in enhanced NESA by tightly anchoring cells to the electrode.

Adsorption↗
PubMed2004

An evanescent-field-driven self-assembled molecular photoswitch for macrocycle coordination and release.

Two self-assembled monolayer (SAM) films containing the photoswitchable 4-pyridylazophenoxy chromophore have been deposited onto a gold-coated glass substrate. One film contains the chromophore as a single component, 1 SAM, and the other is doped with a nonphotoactive component as a 1:1 mixture, 2 SAM. The reversible photoswitching performances of 1 SAM and 2 SAM via the evanescence field using light of appropriate wavelengths have been investigated by UV spectroscopic and electrochemical monitoring. In principle, the trans-form SAMs present a coordinating surface, the "on" state, that can be switched "off" in the cis form. This has been illustrated by immersing both the as-deposited (trans form) SAMs and the photoswitched (predominantly cis form) SAMs into solutions of cobalt and zinc tetraphenylporphyrin (CoTPP and ZnTPP, respectively) and an octaoctyl-substituted cobalt phthalocyanine. In a further phase of this study, the remote control of binding events at the surface of the SAMs has been demonstrated through evanescent-field-driven photoswitching of trans-form SAMs coordinated at the surfaces with examples of these metallomacrocycles. This photoswitching was undertaken with the constructs immersed in neat toluene, and the macrocycles were released from the surface into the solvent. The release was measured by spectroscopic monitoring of the material remaining on the constructs. The study was extended to develop an in situ release/coordination cycle. Thus, irradiation of a construct of ZnTPP bound to the surface of trans-form 2 SAM using waveguided light at 365 nm releases the macrocycle into a toluene solution of ZnTPP. Further irradiation of the SAM, now in its cis form, with waveguided 439 nm light regenerates the trans form, which recoordinates ZnTPP from the solution. The results demonstrate the potential for using waveguided light to control molecular events within and at the surfaces of SAM constructs.

Electrochemistry↗
PubMed2006

S-adenosylmethionine regulates cytoplasmic HuR via AMP-activated kinase.

BACKGROUND & AIMS: After liver injury, hepatic S-adenosylmethionine (SAM) content decreases, and the blockage this molecule imposes on hepatocyte proliferation is released, facilitating liver regeneration. This activity of SAM is important for normal liver function because mice deficient in hepatic SAM display abnormal liver regeneration and develop hepatocellular carcinoma. How SAM regulates hepatocyte growth is unclear, but because SAM blocks hepatocyte growth factor (HGF)-induced cyclin D1 expression and DNA synthesis without affecting HGF-induced extracellular signal-regulated kinase phosphorylation, the mitogen-activated protein kinase (MAPK) pathway is probably not the target. METHODS: The effects of SAM on AMPK, HuR localization were assessed in rat hepatocytes after HGF, AICAR, and SAM treatment. RESULTS: We show here that HGF and 5-aminoimidazole-4-carboxamide-riboside (AICAR), an activator of AMP-activated protein kinase (AMPK), induce the phosphorylation of AMPK in hepatocytes and that SAM blocks this process. We also show that HGF- and AICAR-induced AMPK activation stimulate the transport from nucleus to cytoplasm of HuR, an RNA-binding protein that increases the half-life of target mRNA such as cyclin A2, and that SAM blocks this process. We found that, in hepatocytes, AICAR increases HuR binding to cyclin A2 messenger RNA (mRNA) as well as the expression and stability of this mRNA and that SAM blocks these events. Consistently, we found that AICAR induces hepatocyte proliferation and that SAM blocks this effect. Finally, we found that liver AMPK phosphorylation, cytoplasmic HuR, and binding of HuR to HuR-target mRNA and the steady-state levels of these mRNA are increased in knockout mice deficient in hepatic SAM. CONCLUSIONS: Our results yield novel insights about the mechanism by which SAM inhibits cell-cycle progression in the liver.

AMP-Activated Protein Kinases↗
PubMed1999

Efficacy on climacteric symptoms of a new estradiol transdermal patch with active matrix in comparison with a reference reservoir patch. Two long-term randomized multicenter parallel-group studies.

METHODS: Two randomized prospective multicentre parallel group studies were performed (one in Germany and the other in Italy) in symptomatic postmenopausal women. The goal was to assess the efficacy on climacteric symptoms and the safety of a new estradiol (CAS 50-28-2) transdermal patch with solid active matrix (SAM) in comparison to a conventional liquid reservoir (LR) type estradiol transdermal patch. Both patches released 50 micrograms/day estradiol. One group of patients received the SAM patch and the other the LR patch in 4-week cycles, with a twice-weekly application of the patches for 3 weeks, followed by one week without patches. Progestin opposition was achieved with medroxyprogesterone acetate 5 mg/day orally in the last 11 days of patch application in the German study and with 10 mg/day in the last 12 days of patch application in the Italian study. Both studies were divided into two Parts: Part 1 with three 4-week cycles for a total of 12 weeks and Part 2 for other ten 4-weeks cycles in which the patches could be applied also continuously. The total duration of the study was therefore 52 weeks. RESULTS: Germany study. 133 patients resulted randomized to the SAM group and 129 to the LR group. Both estradiol patches quickly relieved climacteric symptoms already during the first 3 weeks of patch application, as shown by the rapid decrease of the Kupperman Index. At the end of Part 1, in the SAM group 91% and in the LR group 96% of patients reported relief from climacteric symptoms. At the end of Part 2 the percentages were 98% and 95%, respectively. The two patches were therapeutically equivalent with a power greater than 99.7%. Both patches were systemically fairly well tolerated. Only 4.5% of patients in the SAM group and 3.9% in the LR group discontinued prematurely for possible adverse reactions related to estradiol. There was no significant difference between the two patches with regard to systemic tolerability. Conversely, with regard to local skin reactions, the SAM patch was significantly (p < 0.01) better tolerated than the LR patch. The adhesion to the skin of the SAM patches was better than that of the LR patches. RESULTS. Italian study. 139 patients resulted randomized to the SAM patch and 128 to the LR patch. Also in this study both types of patches relieved the climacteric symptoms already during the first 3 weeks of patch application, as shown by the rapid decrease of the visual analogue scale (VAS) recordings of severity of hot flushes and of sweats. At the end of Part 1 both patches relieved 95% of patients from climacteric symptoms. At the end of Part 2, i.e. after 52 weeks, 100% of patients were relieved from climacteric symptoms. Of these, 72% in the SAM group and 78% in the LR group reported complete disappearance of symptoms. Also in the Italian study, therefore, the two patches were found therapeutically equivalent. Both patches stopped or even reversed bone mineral loss in L2-L4 and had some favorable effects on lipid metabolism. Both patches were systemically equally fairly well tolerated with premature discontinuations for systemic adverse drug reactions in only 5.0% of patients in the SAM group and 3.9% in the LR group. Conversely, as in the German study, the SAM patches were significantly better tolerated by the skin (p < 0.0001). CONCLUSIONS: The two types of estradiol transdermal patches were equivalent in providing an effective and rapid relief from climacteric symptoms. Systemically both patches were fairly well tolerated. The SAM patches were significantly better tolerated by the skin. The better local tolerability combined with better adhesion and cosmetic properties render the SAM patches very patient friendly and improve the compliance in the long term estrogen replacement therapy required to reduce osteoporosis and cardiovascular risks.

Adhesiveness↗
PubMed1995

A three-dimensional computational investigation of intraventricular fluid dynamics: examination into the initiation of systolic anterior motion of the mitral valve leaflets.

Systolic anterior motion of the mitral valve leaflets (SAM) is a disease of the left ventricle which results from an abnormal force balance on the mitral valve. The mechanism by which is initiated is poorly understood, and a complete understanding of this mechanism is required for effective treatment of SAM. There are currently two theories for the initiation mechanism of SAM, the Venturi hypothesis and the altered papillary muscle-mitral valve geometry theory (PM-MV). The Venturi hypothesis states that abnormally high ejection velocities create Venturi forces which initiate SAM. The PM-MV theory asserts that SAM is the result of abnormally distributed chordal forces which are incapable of preventing SAM. To investigate the initiation mechanism of SAM, a computer model of early systolic flow in an anatomically-correct human left ventricle was developed using Peskin's immersed boundary algorithm. The computer model was used to determine the effect of chordal force distribution and septal thickness of the intraventricular flow field. The results show that the degree of SAM is inversely proportional to the amount of chordal restraint applied to the central portion of the leaflets. Also, the results support the PM-MV theory and indicate the following: (i) fluid forces capable of initiating SAM as always present in a normal human ventricle; (ii) SAM does not occur normally because of the presence of chordal forces on the central portion of the mitral leaflet; (iii) SAM will occur when these central chordal forces are sufficiently low; (iv) the extent of SAM is inversely proportional to these central chordal forces; and (v) Venturi forces alone can not cause SAM.

Algorithms↗
PubMed1984

Muscular subaortic stenosis: the quantitative relationship between systolic anterior motion and the pressure gradient.

We performed simultaneous echocardiographic and hemodynamic studies in 11 patients with muscular subaortic stenosis to determine whether systolic anterior motion (SAM) of the anterior mitral leaflet and the pressure gradient are related quantitatively. SAM without septal contact was associated with either no gradient or a small impulse gradient of less than 10 mm Hg. SAM with septal contact was always associated with a pressure gradient of more than 10 mm Hg. The size of the pressure gradient correlated inversely with the time periods: (1) onset of SAM-septal contact (r = .79, p less than .001) and (2) onset of aortic ejection to onset of SAM-septal contact (r = -.89, p less than .001). Size also correlated directly with the time period: (3) duration of SAM-septal contact (r = .80, p less than .001). Thus when the time from the onset of SAM to the onset of SAM-septal contact was long, SAM-septal contact developed late in systole, the duration of SAM-septal contact was brief and the pressure gradient was low. When SAM-septal contact developed in early systole, the duration of SAM-septal contact was long and the pressure gradient was high. With the index of time period (3) divided by time period (1), a regression equation was devised to predict the size of the pressure gradient (pressure gradient [mm Hg] = 25 [ratio] + 25; r = .90, p less than .001; SE +/- 15 mm Hg). The echocardiographic time period index was validated prospectively in nine other patients and the significant correlation with the hemodynamically determined gradient persisted (r = .89, p less than .01). We conclude that SAM and the pressure gradient are related quantitatively in muscular subaortic stenosis. These observations have implications regarding the mechanism and significance of the pressure gradient in muscular subaortic stenosis.

Adult↗
PubMed1976

Early events during substrate adhesion of normal and virus-transformed mouse fibroblasts.

The relationship between attachment of Balb/c3T3 cells and their SV40 transformants to glass or plastic substrates and deposition of substrate-attached material (SAM-proteoglycans implicated in substrate adhesion) has been examined very early after inoculation of cells subcultured with ethylenebis (oxyethylenenitrilo) tetra-acetic acid (EGTA). The metabolic inhibitors cycloheximide and colchicine minimally affected the kinetics or short-term stability of attachment of cells or deposition of SAM. SAM deposition on to the substrate began immediately after inoculation of cells and was maximal prior to the highest cell attachment level (30-40 min after inoculation). At 4 degrees C, there was no attachment of cells to the substrate and no deposition of leucine- or glucosamine-radiolabelled SAM on to the substrate. 3T3 cells deposited SAM to a maximal level earlier during the attachment process than SV40-transformed cells. SVT2 cells deposited much smaller amounts of SAM (measured on a per-cell basis) to 3T3 SAM-coated substrates during attachment processes, whereas 3T3 cells and concanavalin A (con A) revertant variants of SVT2 cells, which have regained density-dependent inhibition of growth, deposited identical amounts of SAM (per-cell) on untreated or SAM-coated substrates. Serial attachment experiments with SVT2 cells indicated that all SVT2 cells reduced their deposition amounts on SAM-coated substrates, rather than there being an ability of a small proportion of cells to attach preferentially to SAM-coated substrates while being unable to deposit SAM themselves. The data are consistent with the presence of a sizeable pool of SAM-like proteoglycans being present on the surface of EGTA-removed cells whose deposition may be a requirement for, but may not necessarily be sufficient for, stable adhesion of cells to the substrate.

Cell Adhesion↗
PubMed2001

Echocardiographic correlates of left ventricular outflow obstruction and systolic anterior motion following mitral valve repair.

BACKGROUND AND AIM OF THE STUDY: Systolic anterior motion (SAM) of the mitral valve resulting in left ventricular outflow obstruction is a well-recognized complication of repair of the degenerative myxomatous mitral valve. A precise mechanism is unknown. A current approach consists of sliding annuloplasty of the posterior leaflet. It was postulated that excess tissue of the anterior mitral leaflet (AML) was as equally (or more) important as the excess posterior mitral leaflet (PML) tissue in the development of SAM subsequent to valve repair. METHODS: Thirty-two patients without post-repair SAM (No-SAM group) were compared with eight patients with SAM (SAM group). The AML and PML heights and the mitral annulus diameter were measured by TEE using mid-esophageal four-chamber and long-axis planes. RESULTS: Pre-repair TEE showed the AML height to be greater in the SAM group (p = 0.04), and that of the posterior leaflet tended to be greater (p = 0.08), whilst the annular dimensions were similar in both groups. In the post-repair status, the AML height was markedly greater (p = 0.005) and the annulus markedly smaller (p = 0.001) in the SAM group. Post-repair assessment showed the relative difference between AML height and annular dimension (AML - Ann) as well as the difference between combined leaflet heights and annular dimension (AML + PML - Ann) to be strikingly greater in the SAM group as compared with the No-SAM group (p = 0.001). CONCLUSION: A disparity between dimension of the annulus following mitral valve repair and combined heights of the two leaflets explains post-repair SAM. The AML height is a more important factor in the development of SAM. Thus, surgical techniques to reduce AML heights should be considered in patients with disproportionately large anterior leaflets in order to prevent SAM. Selection of size of the annuloplasty ring should take into consideration the height of the AML.

Echocardiography, Transesophageal↗
PubMed1982

Effects of hypophysectomy and dexamethasone administration on central and peripheral S-adenosylmethionine levels.

The effects of hypophysectomy and dexamethasone administration on S-adenosylmethionine (SAM) levels in the adrenal, liver, pineal, and various brain regions were examined to determine the central and peripheral relationships between SAM and glucocorticoids in vivo. A simple and sensitive radioenzymatic assay was developed to measure tissue SAM concentrations following removal of its demethylated metabolite, S-adenosylhomocysteine (SAH), whose presence precludes accurate SAM determinations. Three patterns of SAM control emerged. In the adrenal, pineal, striatum, and midbrain, SAM levels fell after hypophysectomy and were restored by dexamethasone administration. In the thalamus, hypothalamus, hippocampus, and cerebellum, SAM levels increased after hypophysectomy and were not altered further by dexamethasone administration. In the liver, cortex, septum, and pons-medulla, SAM levels were not affected by either hypophysectomy or dexamethasone administration. These results suggest that multiple controls regulate SAM levels in vivo. The control factors are both highly tissue and region specific. While glucocorticoids are an important regulatory factor of SAM in some peripheral and CNS tissues, they are not the sole regulatory factor. In CNS regions where hypophysectomy increases SAM levels but glucocorticoid administration does not reverse the effects, other hypothalamic hormones, pituitary hormones, or neural factors may be involved in SAM regulation. Likewise, in regions where neither hypophysectomy nor glucocorticoid administration affects SAM levels, hypothalamic or neural factors may be involved even though pituitary factors do not appear to be important.

Adrenal Glands↗
PubMed1976

Sodium salicylamide: relative bioavailability and subjective effects.

The bioavailability of sodium salicylamide (NaSAM) in solution of salicylamide (SAM) tablets was compared in 6 healthy human volunteers. Bioavailability was assessed by plasma level determinations of nonmetabolized salicylamide (free SAM) and salicylamide plus conjugated metabolites (total SAM) for 3 hr following oral doses of 0.65, 1.30, 1.95, and 2.60 gm of salicylamide. The availability of NaSAM was found to be superior to SAM and dose-dependent. Mean peak levels of free SAM and total SAM were higher and were reached earlier after NaSAM liquid than after SAM tablets. Significantly higher mean levels of free SAM were found at the 1.95 and 2.60 gm dose levels after NaSAM administration than after SAM. Mean total SAM concentration was significantly higher after NaSAM at all dosage levels. The sedative effects of salicylamide were assessed with a self-scoring questionnaire. Sedation seemed to increase with increasing dose of both NaSAM and SAM. The sedative response occurred earlier after NaSAM than after SAM. Side effects were minor and transient in nature, occurred at the higher dosage levels, and were predominantly lightheadedness and dizziness. Because NaSAM produces higher drug levels and has a more rapid onset of subjective effects, we conclude that it represents a potentially superior dosage form.

Biological Availability↗
PubMed1979

Fibronectin and proteoglycans as determinants of cell-substratum adhesion.

When normal or SV40-transformed Balb/c 3T3 cells are treated with the Ca++-specific chelator EGTA, they round up and pull away from their footpad adhesion sites to the serum-coated tissue culture substrate, as shown by scanning electron microscope studies. Elastic membranous retraction fibers break upon culture agitation, leaving adhesion sites as substrate-attached material (SAM) (Cells leave "footprints" of substrate adhesion sites during movement by a very similar process.) SAM contains 1-2% of the cell's total protein and phospholipid content and 5-10% of its glucosamine-radiolabeled polysaccharide, most of which is glycosaminoglycan (GAG). By one- and two-dimensional sodium dodecyl sulfate-polyacrylamide gel electrophoresis, there is considerable enrichment in SAM for specific GAGs; for the glycoprotein fibronectin; and for the cytoskeletal proteins actin, myosin, and the subunit protein of the 10 nm-diameter filaments. Fibrillar fibronectin of cellular origin and substratum-bound fibronectin of serum origin (cold-insoluble globulin, CIg) have been visualized by immunofluorescence microscopy. The GAG composition in SAM has been examined under different cellular growth and attachment conditions. Heparan sulfate content correlates with glycopeptide content (derived from glycoprotein). Newly attaching cells deposit SAM with principally heparan sulfate and fibronectin and little of the other GAGs. Hyaluronate and chrondroitin proteoglycans are coordinately deposited in SAM as cells begin spreading and movement over the substrate. Cells attaching to serum-coated or CIg-coated substrates deposited SAM with identical compositions. The proteoglycan nature of the GAGs in SAM has been examined, as well as the ability of proteoglycans to form two classes of reversibly dissociable "supramolecular complexes" - one class with heparan sulfate and glycopeptide-containing material and the second with hyaluronate-chondroitin complexes. Enzymatic digestion of "intact" SAM with trypsin or testicular hyaluronidase indicates that (1) only a small portion of long-term radiolabeled fibronectin and cyto-skeletal protein is bound to the substrate via hyaluronate or chondroitin classes of GAG; (2) most of the fibronectin, cytoskeletal protein and heparan sulfate coordinately resist solubilization; and (3) newly synthesized fibronectin, which is metabolically labile in SAM, is linked to SAM by hyaluronate- and/or chondroitin-dependent binding. All of our studies indicate that heparan sulfate is a direct mediator of adhesion of cells to the substrate, possibly by binding to both cell-surface fibronectin and substrate-bound CIg in the serum coating; hyaluronate-chondroitin complexes in SAM appear to be most important in motility of cells by binding and labilizing fibronectin at the periphery of footpad adhesions, with subsequent cytoskeletal disorganization.

Animals↗
PubMed2005

Significance of systolic anterior motion of the mitral valve during dobutamine stress echocardiography.

Left ventricular outflow tract obstruction related to systolic anterior motion of the mitral valve (SAM) induced during dobutamine stress echocardiography (DSE) is not unusual but its significance is not established. A total of 100 consecutive patients (mean age 62 +/- 12 years; 67% male) without previous transmural myocardial infarction, valvular disease, or hypertrophic cardiomyopathy, undergoing DSE to assess the presence of myocardial ischemia, were prospectively evaluated. A SAM with DSE was searched and correlated with clinical and baseline echocardiographic findings. Patients who demonstrated SAM with DSE were selected for exercise echocardiographic Doppler study with bicycle, within 6 months of the DSE. The development of an intraventricular gradient with DSE or exercise was defined as a new gradient of > or =36 mm Hg. In all, 23 patients developed SAM during DSE with a mean gradient of 79 +/- 33 mm Hg (range: 39-144 mm Hg) and mitral regurgitation related to SAM. Compared with patients without SAM, patients who developed SAM with DSE were characterized at rest by a smaller mitroaortic angle and septoaortic angle, a higher posterior mitral leaflet length, and a smaller left ventricular cavity. Neither ischemic nor hypotensive response during DSE were correlated to SAM. In the group of patients with SAM, of the 9 patients who were referred for unexplained chest pain or dyspnea, 5 reproduced symptoms with DSE, compared with 2 of 17 patients in the group without SAM (P = .005). Despite these findings, only 3 of the 16 patients who underwent exercise echocardiography Doppler study developed SAM (two with symptoms), with a wide range of achieved heart rate, compared with DSE. Although patients with SAM with DSE exhibit predisposing echocardiographic findings, the clinical impact of this phenomenon is real in only a minority of patients, particularly those who experienced unexplained dyspnea or chest pain.

Aged↗
PubMed2002

Surface potential contrasts between silicon surfaces covered and uncovered with an organosilane self-assembled monolayer.

Surface potentials of Si substrates covered with a organosilane self-assembled monolayers (SAMs) were measured with reference to the substrate uncovered with the SAM using Kelvin probe force microscopy. Based on a photolithographic technique, the reference surface was prepared in a micrometer scale on each of the samples. SAMs were prepared from n-octadecyltrimethoxysilane [ODS: CH3(CH2)17Si(OCH3)3], 3,3,3-trifluoropropyltrimethoxysilane [FAS3: CF3(CH2)2Si(OCH3)3], heptadecafluoro-1,1,2,2-tetahydro-decyl-1-trimethoxysilane [FAS17: CF3(CF2)7(CH2)2Si(OCH3)3] or n-(6-aminohexyl) aminopropyltrimethoxysilane [AHAPS: H2N(CH2)6NH(CH2)3Si(OCH3)3) by chemical vapor deposition. Potentials of the surfaces covered with ODS-, FAS3- and FAS17-SAMs became more negative than the uncovered Si substrate, while the surface covered with AHAPS-SAM showed a more positive surface potential than the reference. The potential contrasts of these SAMs to the reference were -25, -170, -225 and +50 mV for ODS-, FAS3-, FAS17- and AHAPS-SAMs, respectively. These results almost agreed with potentials expected from the dipole moments of the corresponding precursor molecules estimated by ab initio molecular orbital calculation, except for FAS3-SAM. Despite FAS3 molecule having a larger dipole moment than FAS17 molecule, the surface potential contrast of FAS3-SAM was smaller than that of FAS17-SAM, since surface coverage of FAS3-SAM was relatively incomplete compared with the other SAMs.

Journal Article↗
PubMed2001

Reversed-phase high-performance liquid chromatography procedure for the simultaneous determination of S-adenosyl-L-methionine and S-adenosyl-L-homocysteine in mouse liver and the effect of methionine on their concentrations.

An improved reversed-phase high-performance liquid chromatography (HPLC) procedure with ultraviolet detection is described for the simultaneous determination of S-adenosyl-L-methionine (SAM) and S-adenosyl-L-homocysteine (SAH) in mouse tissue. The method provides rapid resolution of both compounds in a 25-microl perchloric acid extract of the tissue. The limits of detection in 25-microl injection volumes were 22 and 20 pmol for SAM and SAH, respectively. The limits of quantitation in 25-microl injection volumes were 55 and 50 pmol for SAM and SAH, respectively, with recovery consistently >98%. The assay was validated over linear ranges of 55-11000 pmol for SAM and 50-10000 pmol for SAH. The intra-day precision and accuracy were < or =6.4% relative standard deviation (RSD) and 99.9-100.0% for SAH and < or =6.7% RSD and 100.0-100.1% for SAM. The inter-day precision and accuracy were < or =5.9% RSD and 99.9-100.6% for SAH and < or =7.0% RSD and 99.5-100.1% for SAM. Compared to earlier procedures, the HPLC method demonstrated significantly better separation, detection limit and linear range for SAM and SAH determination. The assay demonstrated applicability to monitoring in mice the time-course of the effect of methionine on SAM and SAH levels in the liver. Administering methionine to mice increased by 10-fold the liver concentration of SAM and SAH within 2 h, which then rapidly decreased to the control levels by 8 h. This indicated that methionine was promptly converted to SAM and then rapidly catabolized into SAH. Thus, the metabolism of methionine to SAM should be considered in the supplementation of methionine to maintain SAM levels in the body.

Animals↗
PubMed2006

Cofactor dependence of reduction potentials for [4Fe-4S]2+/1+ in lysine 2,3-aminomutase.

Lysine 2,3-aminomutase (LAM) catalyzes the interconversion of l-lysine and l-beta-lysine by a free radical mechanism. The 5'-deoxyadenosyl radical derived from the reductive cleavage of S-adenosyl-l-methionine (SAM) initiates substrate-radical formation. The [4Fe-4S](1+) cluster in LAM is the one-electron source in the reductive cleavage of SAM, which is directly ligated to the unique iron site in the cluster. We here report the midpoint reduction potentials of the [4Fe-4S](2+/1+) couple in the presence of SAM, S-adenosyl-l-homocysteine (SAH), or 5'-{N-[(3S)-3-aminocarboxypropyl]-N-methylamino}-5'-deoxyadenosine (azaSAM) as measured by spectroelectrochemistry. The reduction potentials are -430 +/- 2 mV in the presence of SAM, -460 +/- 3 mV in the presence of SAH, and -497 +/- 10 mV in the presence of azaSAM. In the absence of SAM or an analogue and the presence of dithiothreitol, dihydrolipoate, or cysteine as ligands to the unique iron, the midpoint potentials are -479 +/- 5, -516 +/- 5, and -484 +/- 3 mV, respectively. LAM is a member of the radical SAM superfamily of enzymes, in which the CxxxCxxC motif donates three thiolate ligands to iron in the [4Fe-4S] cluster and SAM donates the alpha-amino and alpha-carboxylate groups of the methionyl moiety as ligands to the fourth iron. The results show the reduction potentials in the midrange for ferredoxin-like [4Fe-4S] clusters. They show that SAM elevates the reduction potential by 86 mV relative to that of dihydrolipoate as the cluster ligand. This difference accounts for the SAM-dependent reduction of the [4Fe-4S](2+) cluster by dithionite reported earlier. Analogues of SAM have a weakened capacity to raise the potential. We conclude that the midpoint reduction potential of the cluster ligated to SAM is 1.2 V less negative than the half-wave potential for the one-electron reductive cleavage of simple alkylsulfonium ions in aqueous solution. The energetic barrier in the reductive cleavage of SAM may be overcome through the use of binding energy.

Clostridium↗
PubMed2004

Characterization of self-assembled monolayers of porphyrins bearing multiple thiol-derivatized rigid-rod tethers.

A series of multithiol-functionalized zinc porphyrins has been prepared and characterized as self-assembled monolayers (SAMs) on Au. The molecules, designated ZnPS(n) (n = 1-4), contain from one to four [(S-acetylthio)methyl]phenylethynylphenyl groups appended to the meso-position of the porphyrin; the other meso-substituents are phenyl groups. For the dithiol-functionalized molecules, both the cis- and the trans-appended structures were examined. The ZnPS(n) SAMs were investigated using X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and various electrochemical methods. The studies reveal the following characteristics of the ZnPS(n) SAMs. (1) The ZnPS(n) molecules bind to the Au surface via a single thiol regardless of the number of thiol appendages that are available per molecular unit. (2) The porphyrins in the ZnPS(3) and ZnPS(4) SAMs bind to the surface in a more upright orientation than the porphyrins in the ZnPS(1), cis-ZnPS(2), and trans-ZnPS(2) SAMs. The porphyrins in the ZnPS(3) and ZnPS(4) SAMs are also more densely packed than those in the cis-ZnPS(2) and trans-ZnPS(2) SAMs. The packing density of the ZnPS(3) and ZnPS(4) SAMs is similar to that of the ZnPS(1) SAMs, despite the larger size of the molecules in the former SAMs. (3) The thermodynamics and kinetics of electron transfer are generally similar for all of the ZnPS(n) SAMs. The general similarities in the electron-transfer characteristics for all of the SAMs are attributed to the similar binding motif.

Journal Article↗
PubMed2004

Giant shoot apical meristems in cacti have ordinary leaf primordia but altered phyllotaxy and shoot diameter.

BACKGROUND AND AIMS: Shoot apical meristems (SAMs) in most seed plants are quite uniform in size and zonation, and molecular genetic studies of Arabidopsis and other model plants are revealing details of SAM morphogenesis. Some cacti have SAMs much larger than those of A. thaliana and other seed plants. This study examined how SAM size affects leaf primordium (LP) size, phyllotaxy and shoot diameter. METHODS: Apices from 183 species of cacti were fixed, microtomed and studied by light microscopy. KEY RESULTS: Cactus SAM diameter varies from 93 to 2565 microm, the latter being 36 times wider than SAMs of A. thaliana and having a volume 45 thousand times larger. Phyllotaxy ranges from distichous to having 56 rows of leaves and is not restricted to Fibonacci numbers. Leaf primordium diameter ranges from 44 to 402 microm, each encompassing many more cells than do LP of other plants. Species with high phyllotaxy have smaller LP, although the correlation is weak. There is almost no correlation between SAM diameter and LP size, but SAM diameter is strongly correlated with shoot diameter, with shoots being about 189.5 times wider than SAMs. CONCLUSIONS: Presumably, genes such as SHOOT-MERISTEMLESS, WUSCHEL and CLAVATA must control much larger volumes of SAM tissue in cacti than they do in A. thaliana, and genes such as PERIANTHIA might establish much more extensive fields of inhibition around LP. These giant SAMs should make it possible to more accurately map gene expression patterns relative to SAM zonation and LP sites.

Arabidopsis↗
PubMedDate not supplied

Levodopa intake increases plasma levels of S-adenosylmethionine in treated patients with Parkinson disease.

Metabolism of levodopa via the enzyme catechol-O-methyltransferase requires S-adenosylmethionine (SAM) as a methyl donor. SAM caused Parkinson disease (PD)-like symptoms in rodents. Therefore, SAM could contribute to a decreased efficacy of levodopa in the long term. SAM levels were significantly reduced in levodopa-treated PD patients, but they showed increased enzyme methionine adenosyl transferase (MAT) activity, which induces SAM synthesis from methionine (MET). This may result from a rebound increase of SAM production. The objective of the study was to demonstrate an effect of acute levodopa intake on SAM synthesis in the plasma of treated PD patients. The authors measured SAM, MET, and levodopa plasma concentrations in 13 levodopa-treated PD patients before and after application of 125 mg levodopa/benserazide. Plasma levels of SAM and levodopa significantly increased, but MET concentrations did not significantly decrease. The SAM increase after levodopa intake may exert both a certain antidepressant and cognitive function improving effect. This is often observed in untreated PD patients who receive levodopa for the first time, or in more advanced, fluctuating PD patients, when they turn from the OFF to the ON phase. Because SAM in higher dosages may also counteract the antiparkinsonian efficacy of levodopa according to animal trials, this SAM increase may hypothetically contribute to the onset of wearing-off phenomena and other clinical signs of limited efficacy of levodopa during long-term treatment with levodopa in PD patients.

Administration, Oral↗