Roentgen and the "new light"--Roentgen's moment of discovery. Part 3: The genealogy of Roentgen's barium platinocyanide screen.
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History, 19th Century↗
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Anion exchange in the channels of a robust alkaline earth sulfonate coordination network.
The barium sulfonate network presented herein, [[Ba2(L)(H2O)5]Cl]infinity (1), represents the first metal sulfonate compound to possess a cationic framework. The network is layered with channels between pillaring ligands in which chloride ions reside. Compound 1 contracts slightly upon dehydration but retains its overall structural motif to 420 degrees C. Significantly, the chloride ions of the structure can be exchanged in 80% yield for fluoride ions in a facile manner. This exchange is quantified by elemental analyses, gravimetric determination, and 19F NMR spectroscopy. Confirmation of retention of structure is provided by standardized powder X-ray diffraction experiments. This last point is notable as the F-analogue of the structure is not attainable by a direct synthesis. These results illustrate one of the hallmark features of supramolecular chemistry, that a robust and functional framework can result through cooperative interactions between more weakly interacting units.
Journal Article↗
Synthesis, spectral characterization, and structural studies of 2-aminobenzoate complexes of divalent alkaline earth metal ions: X-ray crystal structures of [Ca(2-aba)2(OH2)3]infinity, [[Sr(2-aba)2(OH2)2].H2O]infinity, and [Ba(2-aba)2(OH2)]infinity (2-abaH = 2-NH2C6H4COOH).
Reactions of alkaline earth metal chlorides with 2-aminobenzoic acid (2-abaH) have been investigated. The treatment of MCl2.nH2O (M = Mg, Ca, Sr or Ba) with 2-abaH in a 1:2 ratio in a MeOH/H2O/NH3 mixture leads to the formation of anthranilate complexes [Mg(2-aba)2] (1), [Ca(2-aba)2(OH2)3]infinity (2), [[Sr(2-aba)2(OH2)2].H2O)]infinity (3), and [Ba(2-aba)2(OH2)]infinity (4) respectively. Alternatively, these products can also be obtained starting from the corresponding metal acetates. Anthranilate complexes 1-4 have been characterized with the aid of elemental analysis, pH measurements, thermal analysis, and infrared, ultraviolet, and NMR (1H and 13C) spectroscopic studies. All the products are found to be thermally very stable and do not melt on heating to 250 degrees C. Thermal studies of complexes 2-4, however, indicate the loss of coordinated and lattice water molecules below 200 degrees C. In the case of the magnesium complex, the analytical and thermogravimetric studies indicate the absence of any coordinated or uncoordinated water molecules. Further, the solid-state structures of metal anthranilates 2-4 have been established by single-crystal X-ray diffraction studies. While the calcium ions in 2 are heptacoordinated, the strontium and barium ions in 3 and 4 reveal a coordination number of 9 apart from an additional weak metal-metal interaction along the polymeric chains. The carboxylate groups show different chelating and bridging modes of coordination behavior in the three complexes. Interestingly, apart from the carboxylate functionality, the amino group also binds to the metal centers in the case of strontium and barium complexes 3 and 4. However, the coordination sphere of 2 contains only O donors. All three compounds form polymeric networks in the solid state with the aid of different coordinating capabilities of the carboxylate anions and O-H...O and N-H...O hydrogen bonding interactions.
Journal Article↗
Synthesis and structural characterisation of heavy alkaline earth N,N'-bis(aryl)formamidinate complexes.
Treatment of calcium or strontium with 2.0 equivalents of N,N-bis(o-methylphenyl)formamidine (o-TolFormH), N,N-bis(2,6-dimethylphenyl)formamidine (XylFormH) or N,N-bis(o-phenylphenyl)formamidine (o-PhPhFormH) in the presence of 1.0 equivalent of Hg(C6F5)2 in tetrahydrofuran (thf) affords the bis(formamidinate) complexes [Ca(o-TolForm)2(thf)2] (1), [Ca(XylForm)2(thf)2] (2), [Ca(o-PhPhForm)2(thf)2].thf (3), [Sr(o-TolForm)2(thf)3] (4), [Sr(XylForm)2(thf)3].3thf (5) and [Sr(o-PhPhForm)2(thf)3].2thf (6). Analogous reactions with barium were generally unsatisfactory but [Ba(o-PhPhForm)2(thf)3].2thf (7) was successfully prepared. Compounds 1-7 have been characterised by various spectroscopic methods (1H, 13C{1H} NMR and IR), elemental analyses and, for 1, 2 and 4-6, X-ray crystallography. The calcium complexes are monomeric and six-coordinate with either transoid octahedral or trigonal prismatic geometry, whilst the larger radius of strontium accommodates an additional thf solvent donor to give seven-coordinate structures with two types of coordination polyhedra.
Journal Article↗
Gastro-colic fistula complicating benign gastric ulcer in analgesic abusers.
Two cases of gastro-colic fistula occurring in analgesic abusers are described. In both patients, the fistulous communication was diagnosed at endoscopy and subsequently verified by upper gastrointestinal tract barium studies. Gastro-colic fistula is a rare complication of benign peptic ulcer disease. Whilst salcylates and cortico-steroids have been implicated as aetiological agents, abuse of compound analgesics has not previously been reported. Since the first description of gastro-colic fistula in 1755, thirty documented cases associated with benign gastric ulcer have been reported. Most often, gastro-colic fistula occurs secondary to gastric or colonic malignancy. Barium enema examination is the most accurate diagnostic study. Endoscopy has been confined to the visual inspection of the ulcer and establishing the benign nature of these lesions.
Adult↗
Magic alkali-fullerene compound clusters of extreme thermal stability.
The thermal stability of free pure C60-, as well as C60-alkali, and -alkaline-earth metal compound clusters is investigated. We find that small (C60)m-clusters (m<or=6) decay at comparatively low temperatures below 400 K, as a consequence of weak intermolecular van der Waals interaction. Adding barium or potassium to the clusters dramatically increases the decay temperatures for "magic" configurations of (C60)mBa(2m-1) and (C60)mK(2m), which reach values as high as 1780 K. Contrary to common belief, the superstable compound clusters are not characterized by filled geometrical or electronic shells. Density functional calculations show that the delicate interplay of ionic (K, Ba) and covalent (Ba) interaction between C60 and the metal atoms, on the one hand, and entropic contributions to the Gibbs free energy, on the other hand, determine the unusual stability.
Journal Article↗
Combination of microangiography and histochemistry.
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Angiography↗
Effect of tetraethylammonium and barium on the release of noradrenaline from the perfused cat spleen by nerve stimulation and potassium.
The effect of tetraethylammonium (TEA) and barium on release of noradrenaline (NA) from the cat spleen by nerve stimulation or potassium was investigated. 2. In spleens perfused with normal Krebs solution, the NA output at 5 Hz was barely detectable, and the output at 30 Hz was about 5-fold greater than the output at 5 Hz. 3. TEA (1 mM) or barium (2.5 mM) increased NA output at 5 Hz by 5-fold, but did not enhance it at 30 Hz. A maximal effect of TEA was obtained at about 1-3 mM. Enhancement of NA release by TEA was readily reversible. Output of NA induced by high potassium was not affected by TEA or barium. 4. The effect of TEA on release was related to the external calcium concentration. Insignificant outputs obtained at 5 Hz in 0.1 and 0.5 mM calcium-Krebs solutions were markedly increased by TEA, and were 2- and 5-fold greater than the control output at 5 Hz in normal Krebs solution containing 2.5 mM calcium. TEA enhanced release at all calcium concentrations up to 5 mM, but maximum output was still obtained at 2.5 mM. 5. Increasing the potassium concentrations of normal Krebs solution to 10, 15 and 20 mM depressed NA outputs at 5 Hz by 50, 55 and 75% respectively, TEA (1 mM) partially antagonized the inhibitory effect of potassium on release, and in zero potassium-Krebs solution it increased output by about 50% over that obtained in normal Krebs solution. 6. The ratio of NA outputs at 30 and 5 Hz during perfusion with Krebs solution containing TEA was about 0.6, and it approached the normal value as the calcium concentration of the perfusion medium was reduced. TEA facilitated release even at 30 Hz in low-calcium solutions. 7. It is suggested that the enhancement of NA release by TEA and barium is due to the greater influx of calcium ions into the sympathetic nerves during the course of an action potential.
Action Potentials↗
MRI in the diagnosis of small bowel disease: use of positive and negative oral contrast media in combination with enteroclysis.
The aim of the study was to evaluate the additional findings of MRI following small bowel enteroclysis and to compare the efficacy of negative and positive intraluminal contrast agents. Fifty patients with inflammatory or tumorous small bowel disease were investigated by small bowel enteroclysis and consecutive MRI using breathhold protocol (T1-weighted fast low-angle shot, T2-weighted turbo spin echo). Patients were randomly assigned to either receiving a positive oral (Magnevist, Schering, Berlin, Germany) or a negative oral MR contrast media (Abdoscan, Nycomed, Oslo, Norway). The pattern of contrast distribution, the contrast effect, presence of artifacts, as well as bowel wall and extraluminal changes, were determined and compared between the contrast type using Fischer's exact test. Sensitivity, specificity, and diagnostic accuracy for MRI and enteroclysis were calculated. Twenty-seven patients had clinically proven Crohn's disease and two patients surgically proven small bowel tumours. Magnetic resonance imaging had important additional findings as abscesses and fistulae in 20 patients. Surgically compared sensitivities were 100 and 0% for MRI and enteroclysis, for the detection of abscesses, and 83.3 and 17 % for the diagnosis of fistulae, respectively. Bowel wall thickening was more reliably detected with use of positive oral contrast media without intravenous enhancement (p < 0.001), whereas postcontrast negative oral contrast media allow for a superior detection (p < 0.001). T2-weighted sequences were necessary with use of negative oral contrast media, because loop abscesses may be masked. Magnetic resonance imaging should be performed in all patients with suspicion of extraintestinal complications, because the complications are more reliably detected by MRI. Negative oral contrast media show advantages with the use of intravenous contrast but can mask loop abscesses using only T1-weighted imaging.
Abscess↗
Tetrodotoxin-resistant divalent action potentials in an axon of Aplysia.
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Action Potentials↗
In vitro erythemal UV-A protection factors of inorganic sunscreens distributed in aqueous media using carnauba wax-decyl oleate nanoparticles.
This paper describes the in vitro photoprotection in the UV-A range, i.e. 320-400 nm obtained by the use of carnauba wax-decyl oleate nanoparticles either as encapsulation systems or as accompanying vehicles for inorganic sunscreens such as barium sulfate, strontium carbonate and titanium dioxide. Lipid-free inorganic sunscreen nanosuspensions, inorganic sunscreen-free wax-oil nanoparticle suspensions and wax-oil nanoparticle suspensions containing inorganic sunscreens dispersed either in their oil phase or their aqueous phase were prepared by high pressure homogenization. The in vitro erythemal UV-A protection factors (EUV-A PFs) of the nanosuspensions were calculated by means of a sun protection analyzer. EUV-A PFs being no higher than 4 were obtained by the encapsulation of barium sulfate and strontium carbonate, meanwhile by the distribution of titanium dioxide in presence of wax-oil nanoparticles, the EUV-A PFs varied between 2 and 19. The increase in the EUV-A PFs of the titanium dioxide obtained by the use of wax-oil nanoparticles demonstrated a better performance of the sun protection properties of this pigment in the UV-A region.
Barium Sulfate↗
The importance of calcium ions for the regulation of guanosine 3':5'-cyclic monophosphage levels.
Guanosine 3':5'-cyclic monosphosphate (cyclic GMP) levels in the ductus deferens of the rat were increased 2- to 3-fold by acetylcholine (10-1000 muM) or by 125 mM KCl, while adenosine 3':5'-cyclic monophosphate (cyclic AMP) levels were not changed. After incubation for 30 min in the absence of Ca(++), cyclic GMP control levels were decreased by 85% and were not affected by acetylcholine or KCl. The readdition of Ca(++) (1.8 mM) for 3 min to Ca(++)-deprived tissue partially restored basal cyclic GMP levels and the effects of acetylcholine and KCl. The addition of Sr(++) (3.6 mM) or of Ba(++) (1.8 or 10 mM) also caused an increase in basal cyclic GMP in Ca(++)-deprived tissue. Cyclic AMP levels were not significantly changed under any of these conditions. The addition of the phosphodiesterase inhibitor, 1-methyl-3-isobutylxanthine (0.1 mM), to ductus deferentes increased the amount of cyclic AMP about 50% and that of cyclic GMP about 2-fold. The later effect also depended on the presence of Ca(++). 1-Methyl-3-isobutylxanthine (0.1 mM) increased cyclic GMP and cyclic AMP levels in slices of rat submaxillary glands. Methacholine increased cyclic GMP if added in the presence of methyl isobutylxanthine. Cyclic GMP control levels and the effect of methyl isobutylxanthine were unchanged by Ca(++) omission, but the effect of methacholine was abolished.These findings indicate that calcium ions are important for the control of cyclic GMP levels in these tissues.
Acetylcholine↗
Magnetic resonance colonography with fecal tagging: an innovative approach without bowel cleansing.
To date, virtual colonography mandates bowel cleansing in a manner similar to colonoscopy. Because more than half of patients undergoing bowel preparation complain about negative side effects, patient acceptance is negatively impacted. To assure high patient acceptance of MR colonography, bowel cleansing needs to be eliminated. This can be accomplished by fecal tagging, a concept based on altering the signal intensity of stool by adding contrast-modifying substances to regular meals. This article describes different fecal tagging approaches and points out both advantages and limitations of these strategies.
Barium Sulfate↗
The calcium action potential and a prolonged calcium dependent after-hyperpolarization in mouse neuroblastoma cells.
1. Action potentials elicited in solutions with elevated [Ca2+] (1.8-40 mM) have been studied in differentiated cells of mouse neuroblastoma clone N1E-115 in tissue culture. 2. The action potential in high [Ca2+] solutions containing eithr Na+ or Tris is followed by a prolonged after-hyperpolarization (a.h.p.) lasting 0.5-4 sec. The a.h.p. reverses sign between -75 and -85 mV. 3. Externally applied tetraethylammonium (TEA, 15 mM) increases the Ca2+ spike overshoot, prolongs the falling phase and enhances the a.h.p. duration. The a.h.p. is inhibited by Ca2+ antagonists such as La3+, Co2+ and Mn2+. 4. After replacement of Ca2+ by Ba+ or Sr2+ (20mM) action potentials can still be elicited in Na+-free solution, but no a.h.p. is observed. 5. Increasing [Ca2+] from 1.8 up to 20 mM results in an increased capability of neuroblastoma cells to fire repetitively and in a consistent reduction of the firing rate from about 4-10 sec-1 to 0.5-1.8 sec-1. 6. It is concluded that Ca2+ entry during the action potential activates a TEA-resistant K+ conductance which gives rise to the prolonged a.h.p. Data from repetitively firing cells are consistent with the view that the a.h.p. plays a role in the regulation of low-frequency firing.
Action Potentials↗
[ON THE MOLECULAR COMPOUNDS OF OMEGA-AMINO ACIDS WITH ALKALINE EARTH METAL HALIDES].
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Amino Acids↗
The coated wire electrode glucose sensor.
Previous techniques for sensing and measuring glucose are briefly reviewed and compared. The genesis of the glucose coated wire electrode lies in liquid membrane technology, and the basic principle of the electrode is described. The electrode utilizes a quaternary ammonium salt with a sparingly soluble metallic salt of glucose, in a matrix such as poly(vinyl chloride). Fabrication procedures are detailed. Typical sensor responses are illustrated with experimental data. The sensor generally shows a voltage that decreases linearly with increasing glucose concentration over approximately 40 mg/dl to 200 mg/dl. The time response of the sensor is of the order of seconds, and the lifetime observed to date is of the order of several months. Initial studies of mechanism are discussed, using liquid NMR. Preliminary interference effect studies to date are summarized, in which common compounds such as ascorbic acid, uric acid, L-cystine, glycine, and bilirubin were used. Singly these compounds show no significant interference effects.
Barium↗
The influence of certain antibiotics on intestinal motor activity.
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Animals↗
Orthonitridoborate ions [BN3]6- in oxonitridosilicate cages: synthesis, crystal structure, and magnetic properties of Ba4Pr7[Si12N23O][BN3], Ba4Nd7[Si12N23O][BN3], and Ba4Sm7[Si12N23O][BN3].
The isotypic title compounds Ba4Pr7[Si12N23O][BN3], Ba4Nd7[Si12N23O][BN3], and Ba4Sm7[Si12N23O][BN3] were prepared by reaction of Pr, Nd, or Sm, with barium, BaCO3, Si(NH)2, and poly(boron amide imide) in nitrogen atmosphere in tungsten crucibles using a radiofrequency furnace at temperatures up to 1650 C. They were obtained as main products (approximately 70%) embedded in a very hard glass matrix in the form of intense dark green (Pr), orange-brown (Sm), or dark red (Nd) large single crystals, respectively. The stoichiometric composition of Ba4Sm7[Si12N23O][BN3] was verified by a quantitative elemental analysis. According to the single-crystal X-ray structure determinations (Ba4Ln7[Si12N23][BN3], Z= , P6 with Ln = Pr: a = 1225.7(1), c = 544.83(9) pm, R1 = 0.013, wR2 = 0.030; Ln = Nd: a = 1222.6(1), c = 544.6(1) pm, R1 = 0.017, wR2 = .039; Ln = Sm: a = 1215.97(5), c = 542.80(5) pm, R1 = 0.047, wR2 = 0.099) all three compounds are built up by a framework structure [Si12N23O]23- of corner-sharing SiX4 tetrahedrons (X = O, N). The oxygen atoms are randomly distributed over the X positions. The trigonal-planar orthonitridoborate ions [BN3]6- and also the Ln(3)3+ are situated in hexagonal cages of the framework (bond lengths Si-(N/O) 169-179 pm for Ln=Pr). The remaining Ba2+ and Ln3- ions are positioned in channels of the large-pored network. The trigonal-planar [BN3]6- ions have a B-N distance of 147.1(6) pm (for Ln = Pr). Temperature-dependent susceptibility measurements for Ba4Nd7[Si12N23O][BN3] revealed Curie-Weiss behavior above 60 K with an experimental magnetic moment of muexp = 3.36(5) microB/Nd. The deviation from Curie-Weiss behavior below 60 K may be attributed to crystal field splitting of the J = 9/2 ground state of the Nd3+ ions. No magnetic ordering is evident down to 4.2 K.
Journal Article↗