High resolution structural elucidation of macromolecular structure by solid-state nuclear magnetic resonance requires the preparation of uniformly aligned samples that are isotopically labeled. In...Full Text Available
A general method for stable-isotope labeling of large proteins is introduced and applied for studies of the E. coli GroE chaperone proteins by solution NMR. In addition to enabling the residue-specific {sup 15}N-labeling of proteins on a highly deuterated background, it is also an efficient approach for uniform labeling. The method meets the requirements of high-level deuteration, minimal cross-labeling and high protein yield, which are crucial for NMR studies of structures with sizes above 150 kDa. The results obtained with the new protocol are compared to other strategies for protein labeling, and evaluated with regard to the influence of external factors on the resulting isotope labeling patterns. Applications with the GroE system show that these strategies are efficient tools for studies of structure, dynamics and ...
The known biological functions of RNA have expanded in recent years and now include gene regulation, maintenance of sub-cellular structure, and catalysis, in addition to propagation of genetic information. As for proteins, RNA function is tightly correlated with structure. Unlike proteins, structural information for larger, biologically functional RNAs is relatively limited. NMR signal degeneracy, relaxation problems, and a paucity of long-range {sup 1}H-{sup 1}H dipolar contacts have limited the utility of traditional NMR approaches. Selective isotope labeling, including nucleotide-specific and segmental labeling strategies, may provide the best opportunities for obtaining structural information by NMR. Here we review methods that have been developed for preparing and purifying isotopically labeled RNAs, as well as NMR strategies that have ...
Improved NMR detection of mass limited samples can be obtained by taking advantage of the mass sensitivity of microcoil NMR, while throughput issues can be addressed using multiple, parallel...Full Text Available
As part of efforts to develop improved methods for NMR protein sample preparation and structure determination, the Northeast Structural Genomics Consortium (NESG) has implemented an NMR screening pipeline for protein target selection, construct optimization, and buffer optimization, incorporating efficient microscale NMR screening of proteins using a micro-cryoprobe. The process is feasible because the newest generation probe requires only small amounts of protein, typically 30-200 ?g in 8-35 ?l volume. Extensive automation has been made possible by the combination of database tools, mechanization of key process steps, and the use of a micro-cryoprobe that gives excellent data while requiring little optimization and manual setup. In this perspective, we describe the overall process used by the NESG for screening NMRsamples as part of a ...
Orientational constraints obtained from solid state NMR experiments on anisotropic samples are used here in molecular dynamics (MD) simulations for determining the structure and dynamics of several different membrane-bound molecules. The new MD technique is based on the inclusion of orientation dependent pseudo-forces in the COSMOS-NMR force field. These forces drive molecular rotations and re-orientations in the simulation, such that the motional time-averages of the tensorial NMR properties approach the experimentally measured parameters. The orientational-constraint-driven MD simulations are universally applicable to all NMR interaction tensors, such as chemical shifts, dipolar couplings and quadrupolar interactions. The strategy does not depend on the initial choice of coordinates, and...
Orientational constraints obtained from solid state NMR experiments on anisotropic samples are used here in molecular dynamics (MD) simulations for determining the structure and dynamics of several different membrane-bound molecules. The new MD technique is based on the inclusion of orientation dependent pseudo-forces in the COSMOS-NMR force field. These forces drive molecular rotations and re-orientations in the simulation, such that the motional time-averages of the tensorial NMR properties approach the experimentally measured parameters. The orientational-constraint-driven MD simulations are universally applicable to all NMR interaction tensors, such as chemical shifts, dipolar couplings and quadrupolar interactions. The strategy does not depend on the initial choice of coordinates, and is in principle suitable for any flexible molecule. To test the method on three systems of ...
Orientational constraints obtained from solid state NMR experiments on anisotropic samples are used here in molecular dynamics (MD) simulations for determining the structure and dynamics of several different membrane-bound molecules. The new MD technique is based on the inclusion of orientation dependent pseudo-forces in the COSMOS-NMR force field. These forces drive molecular rotations and re-orientations in the simulation, such that the motional time-averages of the tensorial NMR properties approach the experimentally measured parameters. The orientational-constraint-driven MD simulations are universally applicable to all NMR interaction tensors, such as chemical shifts, dipolar couplings and quadrupolar interactions. The strategy does not depend on the initial choice of coordinates, and is in principle suitable for any flexible molecule. To test the method on three systems of ...
Orientational constraints obtained from solid state NMR experiments on anisotropic samples are used here in molecular dynamics (MD) simulations for determining the structure and dynamics of several different membrane-bound molecules. The new MD technique is based on the inclusion of orientation dependent pseudo-forces in the COSMOS-NMR force field. These forces drive molecular rotations and re-orientations in the simulation, such that the motional time-averages of the tensorial NMR properties approach the experimentally measured parameters. The orientational-constraint-driven MD simulations are universally applicable to all NMR interaction tensors, such as chemical shifts, dipolar couplings and quadrupolar interactions. The strategy does not depend on the initial choice of coordinates, and is in principle suitable for any flexible molecule. To test the method on three systems of ...
A method to achieve NMR of dilute samples in the earth's magnetic field by applying para-hydrogen induced polarization is presented. Maximum achievable polarization enhancements were calculated by numerically simulating the experiment and compared to the experimental results and to the thermal equilibrium in the earth's magnetic field. Simultaneous 19F and 1H NMR detection on a sub-milliliter sample of a fluorinated alkyne at millimolar concentration (1018 nuclear spins) was realized with just one single scan. A highly resolved spectrum with a signal/noise ratio higher than 50:1 was obtained without using an auxiliary magnet or any form of radio frequency shielding.
A multi-technique approach was employed to study a decorated Egyptian wooden sarcophagus (XXV?XXVI dynasty, Third Intermediate Period), belonging to the Museo del Vicino Oriente of the Sapienza University of Rome. Portable non-invasive unilateral NMR was applied to evaluate the conservation state of the sarcophagus. Moreover, using unilateral NMR, a non-invasive analytical protocol was established to detect the presence of organic substances on the surface and/or embedded in the wooden matrix. This protocol allowed for an educated sampling campaign aimed at further investigating the state of degradation of the wood and the presence of organic substances by 13C cross polarization magic angle spinning (CPMAS) NMR spectroscopy. The composition of the painted layer was analysed by optical micr...
Syntheses of all five of the singly labeled (/sup 15/N)adenines are now provided. The presence or absence of two-bond /sup 15/N-/sup 1/H spin couplings in their /sup 1/H NMR spectra confirm the location of the isotope in each case. The fragmentation patterns in their mass spectra are indicative of the sequential losses of HCN units and of CH/sub 2/N/sub 2/ from adenine upon electron impact.
Our major goal of our work has been to develop and use NMR techniques to study how methanogenic archaebacteria deal with osmotic stress with the hope of providing insights into increasing the salt tolerance of other cells. The project has three main sections: (i) in vivo studies of methanogens; (ii) use of {sup l3}C- and {sup l5}N- labeled potential precursors and in vitro analyses of specific label uptake for elucidation of osmolyte dynamics and biosynthetic pathways of osmolytes in these organisms, and isolation of key biosynthetic enzymes; and (iii) collaborative studies on identification of organic solutes in other methanogens.
Our major goal of our work has been to develop and use NMR techniques to study how methanogenic archaebacteria deal with osmotic stress with the hope of providing insights into increasing the salt tolerance of other cells. The project has three main sections: (i) in vivo studies of methanogens; (ii) use of [sup l3]C- and [sup l5]N- labeled potential precursors and in vitro analyses of specific label uptake for elucidation of osmolyte dynamics and biosynthetic pathways of osmolytes in these organisms, and isolation of key biosynthetic enzymes; and (iii) collaborative studies on identification of organic solutes in other methanogens.
The effect of treatment of Na-forms of zeolites with HCl solutions and of heat treatment of their NH/sub 4/-forms on the stability of aluminum-oxygen tetrahedra has been studied in this work by high-resolution NMR on /sup 29/Si nuclei, using the synthetic zeolites X, Y, and M (mordenite) as the objects of the study. The exchange capacity with respect to Na/sup +/ ions was determined by analyzing the equilibrium solutions after contact of the samples with 0.5 NH/sub 4/Cl solution on a flame photometer. The high-resolution /sup 29/Si NMR spectra of polycrystalline samples were recorded on an SKhR-200 spectrometer with a superconducting solenoid at a frequency of 39.75 MHz with ultrafast mechanical rotation (3 kHz) of the sample at the magic angle to the external magnetic field. The results obtained are given.
This report covers the progress made on the title project for the project period. Four major areas of inquiry are being pursued. Advanced solid state NMR methods are being developed to assay the distribution of the various important functional groups that determine the reactivity of coals. Special attention is being paid to methods that are compatible with the very high magic angle sample spinning rates needed for operation at the high magnetic field strengths available today. Polarization inversion methods utilizing the difference in heat capacities of small groups of spins are particularly promising. Methods combining proton-proton spin diffusion with [sup 13]C CPMAS readout are being developed to determine the connectivity of functional groups in coals in a high sensitivity relay type of experiment. Additional work is aimed at delineating the role of methyl group rotation in the proton NMR relaxation behavior of coals.
NMR and CD studies indicate that Mg/sup 2 +/ and Ca/sup 2 +/ are able to change the conformation of tetracycline in DMSO solution. This may affect the in vivo effect of tetracycline. Using /sup 23/Na NMR, the formation constant of NaLAS (LAS represents the anion of lasalocid A) was found to be 80 M/sup -1/ which is much smaller than that in less polar solvents. Spin-lattice relaxation measurements were made to study the binding sites of Gd/sup 3 +/ on Las in ChCl/sub 3/-DMF mixed solvent system. No intermediate conformation (between cyclic and open-chain) was found. LAS was found to be a good second-sphere ligand to inert transition-metal amines. NMR studies suggest that LAS is in cyclic conformation when bound to these metal amines. A new method for the synthesis of spin-labeled anticancer Pt(II) complexes was developed. It is very simple and gives high yield of pure spin-labeled ...
We describe the synthesis of metal-chelating polymers (MCPs) with four different pendant polyaminocarboxylate ligands (EDTA, DTPA, TTHA, DOTA) and an orthogonal end-group, either a fluorescein molecule or a bismaleimide linker for antibody attachment. Polymer characterization by a combination of (1)H NMR, UV/vis absorption measurements, and thermal gravimetric analysis (TGA) indicated that each chain of the fluorescein-terminated polymers contained one dye molecule. These polymer samples were loaded with three different types of lanthanide ions as well as palladium and platinum ions. The numbers of metal atoms per chain were determined by a combination of UV/vis and conventional ICP-MS measurements. The experiments with lanthanide ions demonstrated that a net anionic charge on the polymer is important for water solubility. These experiments also showed that at least one type of lanthanide ion (La(3+)) is capable of forming a bimetallic complex ...
{sup 1}H, {sup 13}C, {sup 27}Al, and {sup 29}Si magic-angle-spinning (MAS) NMR was used to elucidate the nature of the catalytic activity of zeolite H-ZSM-5. {sup 1}H MAS NMR of sealed samples after mild hydrothermal dealumination shows that the enhanced activity for n-hexane cracking is not due to an enhanced Bronstead acidity. The concentrations of the various OH groups and aluminous species suggest that the reason for the enhanced catalytic activity is the interaction of the n-hexane molecule with a bridging hydroxyl group and with extra-framework aluminium species, which give rise to the enhanced activity, cannot be easily removed from their positions, and are therefore immobilized by the zeolitic framework.
Conduction properties of Rb"+ ion in Rb-Al-priderite and K"+ ion and Rb"+ ion in (K,Rb)-Al-priderite, were investigated by NMR using "2"7Al in the framework as a probe. Size effect was observed remarkably in the activation energies. Frequency dependence of T_1 in Rb-Al-priderite at a low temperature indicates that the relaxation behavior of "2"7Al in Rb-Al-priderite can be described by the continuum model. Barrier height distributions and 'attempt frequencies' in both samples obtained by a curve-fitting method are discussed in comparison with those of K-Al-priderite. (orig.).
Several lanthanide shift reagents (LSR) were synthesized from praseodymium, europium, dysprosium, and terbium using ethylenediaminetetraacetic acid, trans-1,2-diaminocyclohexane-N,N,N[prime],N[prime]-tetraacetic acid, and diethylenetriaminepentaacetic acid for the purpose of separating overlapping [sup 31]P FT-NMR spectral signals of dissolved organic phosphorus compounds present in concentrated lake-water samples. The extent of change in signal position and line width of several known phosphorus compounds dissolved in pure water was examined as a function of solution pH and the molar ratio of LSR to phosphorus. Praseodymium ethylenediaminetetraacetate (PrEDTA) was determined to be the most effective LSR. Concentrated lake-water samples mixed with PrEDTA were examined with [sup 31]P FT-NMR. The use of PrEDTA provided separation of overlapping signals, indicated that phosphorus compounds were becoming ...
A dense silica glass was prepared by consolidating a highly dispersed silicic acid powder (particle size 1H magic-angle spinning (MAS) NMR confirmed an increase in hydroxyl groups in the sample prepared by SPS relative to that of the conventional SiO2 reference glass. Aside from the comparably high water content, we conclude from the similarity of the IR-reflectance and the 29Si MAS NMR spectra of the SPS sample and the corresponding spectra of the conventionally prepared silica glass, that the short- and medium-range order is virtually the same in both materials. Raman spectroscopy, however, suggests that the number of three- and four-membered rings is significantly smaller in the SPS sample compared to the conventionally prepared sample. Based on these results we conclude that it is possible to prepare glasses by compacting amorphous powders by the SPS ...
Intact rat fat cell exposed to 12.5 ..mu..M (..gamma..-32P)ATP incorporate label into specific proteins within minutes. By solubilizing the reaction mixture with SDS which bypasses the subcellular fractionation steps, the labeled proteins can be identified in autoradiographs of SDS-PAGE gels. The most prominently labeled protein has an M/sub r/ of 42,000. Localization of this component to the cell surface can be made on the basis of inhibition of phosphorylation by addition of a protein derived from the rat brain with protein kinase inhibitory property, susceptibility of the phosphorylated protein to the tryptic digestion, inhibition of phosphorylation of this protein after brief exposure to melittin. To rule out the possibility that the cell surface protein might be a mitochondrial contaminant from broken cells, /sup 32/Pi-labeled and (..gamma..-/sup 32/P)ATP-labeled cells were ...
...) Abstract: Fluorescence microscopic imaging is widely used in biomedical research to study molecular and cellular processes in cell culture or tissue samples. This is motivated by the high inherent sensitivity of fluorescence techniques, the spatial resolution that compares favorably with cellular dimensions, the stability of the fluorescent labels used and the sophisticated strategies that have been developed for selectively labeling target molecules. More recently, two and ...
Trichlorfon is an organophosphorus insecticide, which is extensively being used for protection of fruit crops. Trichlorfon is a thermal labile compound, which cannot be easily determined by gas chromatography (GC) and has no suitable group for sensitive detection by high performance liquid chromatography (HPLC). In this study, a {sup 31}P nuclear magnetic resonance ({sup 31}P NMR) has been described for monitoring of trichlorfon without any separation step. The quantitative works of {sup 31}P NMR spectroscopy has been performed in the presence of an internal standard (hexamethylphosphoramide). Limit of detection (LOD) for this method has been found to be 55 mg L{sup -1}, without any sample preparation, and the linear working range was 150-5500 mg L{sup -1}. Relative standard deviation (R.S.D.%) of the method for three replicates within and between days was obtained {<=}9%. The average recovery efficiency was ...
This report covers the progress made on the title project for the project period. Four major areas of inquiry are being pursued. Advanced solid state NMR methods are being developed to assay the distribution of the various important functional groups that determine the reactivity of coals. Special attention is being paid to methods that are compatible with the very high magic angle sample spinning rates needed for operation at the high magnetic field strengths available today. Polarization inversion methods utilizing the difference in heat capacities of small groups of spins are particularly promising. Methods combining proton-proton spin diffusion with {sup 13}C CPMAS readout are being developed to determine the connectivity of functional groups in coals in a high sensitivity relay type of experiment. Additional work is aimed at delineating the role of methyl group rotation in the proton NMR relaxation behavior of coals.
One of the stiffest challenges in structural studies of proteins using NMR is the assignment of sidechain resonances. Typically, a panel of lengthy 3D experiments are acquired in order to establish connectivities and resolve ambiguities due to overlap. We demonstrate that these experiments can be replaced by a single 4D experiment that is time-efficient, yields excellent resolution, and captures unique carbon-proton connectivity information. The approach is made practical by the use of non-uniform sampling in the three indirect time dimensions and maximum entropy reconstruction of the corresponding 3D frequency spectrum. This 4D method will facilitate automated resonance assignment procedures and it should be particularly beneficial for increasing throughput in NMR-based structural genomics initiatives.
The iodinated oil lipiodol is commonly used as a carrier for in situ delivery of drugs or radioactivity to hepatic tumors. Recently, we reported a new kit formulation for high-activity labeling of lipiodol with the {beta}-emitting radionuclide Re-188. Since the whole preparation involves different steps and complex manipulations of high-activity samples, we describe here an automated synthesis module that allows the easy preparation of sterile and pyrogen-free samples of Re-188 lipiodol ready to be administered to the patient. Important advantages include the possibility to incorporate high Re-188 activity into the lipiodol hydrophobic phase and a sharp reduction of radiation exposure of the operator assisting the labelling procedure. Application of this modular reaction system could be also extended to the preparation of other Re-188 radiopharmaceuticals and to compound labelled ...
Monoclonal antibodies (MAbs) 19-9 and 73-3 specific for human colon adenocarcinoma were labelled with a high number of gadolinium atoms. Twenty five DTPA were chelated per MAb, with only slight loss of immunoreactivity. The NMR contrast agent Gd-25 DTPA-MAb 19-9 or 73-3 ((Gd) 17 mumole/kg, (MAb) 60 microM) was injected into nude mice bearing human colon adenocarcinoma (SW948). Tumors were removed 24 hr after injection and T1 was measured in vitro. T1 relaxation time varied according to MAb specificity against tumour targets; T1 decreased 20% for MAb 19-9 and MAb 73-3 with SW948 tumor. Imaging was performed with this model. Very good contrast was obtained 24 hr after Gd-25 DTPA-MAb injection.
Chitosan was acetylated during 2, 5 and 10 h and physical gels were obtained at different polymer concentrations in N,N-dimethylacetamide containing 5% of LiCl. Acetylation was confirmed by infrared spectroscopy and "1"3C NMR, and degrees of acetylation in the range of 0.82-0.91 were determined by NMR. The O-acetylation degree (0.12-0.15) was exclusively determined by a volumetric method. Rheological studies showed that the storage modulus values were smaller for the more acetylated samples and increased with the temperature and the polymer concentration. All the gels presented storage modulus superior to loss modulus, evidencing more elastic than viscous characteristics. The results obtained in this work suggest a gelation process based on a balance between O and N-acetylation and intermolecular bonds. (author)
We report $^{7}$Li pulsed NMR measurements in polycrystalline and single crystal samples of the quasi one-dimensional S=1 antiferromagnet LiVGe$_2$O$_6$, whose AF transition temperature is $T_{\\text{N}}\\simeq 24.5$ K. The field ($B_0$) and temperature ($T$) ranges covered were 9-44.5 T and 1.7-300 K respectively. The measurements included NMR spectra, the spin-lattice relaxation rate ($T_1^{-1}$), and the spin-phase relaxation rate ($T_2^{-1}$), often as a function of the orientation of the field relative to the crystal axes. The spectra indicate an AF magnetic structure consistent with that obtained from neutron diffraction measurements, but with the moments aligned parallel to the c-axis. The spectra also provide the $T$-dependence of the AF order parameter and show that the transition is either second order or weakly first order. Both the spectra and the $T_1^{-1}$ data show that $B_0$ has at most a small effect on the ...
Crystalline bis(O,O'-di-sec-butyldithiophosphato)platinum(II) was prepared and studied by means of 13C, 31P CP/MAS NMR spectroscopy and single-crystal X-ray diffraction. The unit cell of the platinum(II) compound is comprised of one centrosymmetric mononuclear molecule [Pt{S2P(O-sec-C4H9)2}2], in which the dithiophosphate groups display structural equivalence in both 31P NMR and XRD data. A pair of the dithiophosphate ligands exhibit the same S,S'-bidentate chelating structural function and form two planar four-membered chelate rings, [PtS2P], in this molecule. The planar configuration of the [PtS4] chromophore in structure 1 is governed by the dsp2-hybrid state of platinum(II). The structural states of the dithiophosphate groups in two different samples of complex 1 (one crystallised from...
The nature of extralattice aluminum and its effect on acidity in zeolites was studied. A series of zeolites (some commercial), dealuminated by various methods, were obtained having Si/Al ratios between 1.5 and 20. These were characterized using volumetric sorption, XRD, AA, NMR, and reaction studies. Samples dealuminated using ammonium hexafluorosilicate were found to contain little or no extralattice aluminum. In contrast, steam-dealuminated zeolites had large amounts of extralattice aluminum. In some cases a significant portion of the extralattice aluminum was unobservable by [sup 27]Al NMR, suggesting the existence of an aluminum species of low symmetry. Proton NMR indicated that all the protons were associated with the lattice aluminum atoms. Depending on the preparation history, different groups of H-Y zeolites exhibited different maxima in catalytic activity as a function of aluminum content. The ...
PAH biomineralization measurements of yardwaste compost samples indicated heterogeneous distribution of active microorganisms and substantial sequestration of the non-polar substrate in the compost matrix. - The purpose of the study was to evaluate the potential of phenanthrene and fluoranthene biodegradation in yardwaste compost materials. These polynuclear aromatic hydrocarbons were chosen for this work because they are relatively readily biodegradable and ubiquitous in the environment. Compost samples were incubated in biometers with "1"4C-labeled phenanthrene and the evolution of "1"4CO_2 was assessed as a measure of mineralization. The "1"4CO_2 evolution varied widely among replicate biometers, possibly as the result of (1) uneven and patchy colonization of phenanthrene-degrading microorganisms on compost particles, and (2) non-uniform dispersion of the labeled substrate spike into the yardwaste ...
The wavefunction of a particle extends into the classically forbidden barrier region of the potential energy surface. The consequence of this partial delocalisation is the phenomenon of quantum tunnelling, an effect which enables a particle to penetrate a potential barrier of magnitude greater than the energy of the particle. The tunnelling probability is an exponential function of the particle mass. The effect is therefore an important contribution to the behaviour of light atoms, in particular the proton. The hydrogen bond has long been appreciated to be an essential component of many biological and chemical systems, and the proton transfer reaction in the hydrogen bond is fundamental to many of these processes. The proton behaviour in the hydrogen bonds of benzoic acid, acetylacetone and calix-4-arene has been studied. A variety of techniques, both experimental and computational, were adopted for the study of the three hydrogen bonded systems. The complementary spectroscopic ...
The use of natural products in all over the world has been increased in Brazil as well as in other countries. Maytenus ilicifolia is commonly used in popular medicine. The labeling of red blood cells (RBC) with technetium-99m ("9"9"m Tc) have been for many studies in nuclear medicine. This labeling procedure depends on a reducing agent and stannous chloride is normally used. Here, we investigate if the extract of Maytenus ilicifolia is capable to alter the labeling of RBC and blood proteins with "9"9"m Tc. Blood samples were incubated with Maytenus ilicifolia. Stannous chloride solution and Tc-99m were. Blood was centrifuged and plasma (P) and blood cells (C) were isolated. Samples of P or C were precipitated with trichloroacetic acid, centrifuged and IF and IF were separated. The percentage of radioactivity (% ATI) in C, IF-P and IF-C was calculated. The %ATI in decreased in C from ...
The kinetics of {sup 14}C-photosynthate import by developing wheat grains was followed after pulse-labeling the flag leaf with {sup 14}CO{sub 2}. Samples were collected from four successive points along the transport pathway to and within the grain: exuding aphid stylets on the peduncle, exuding grain pedicels, the grain crease tissues, and the liquid contents of the endosperm cavity. In addition, microautoradiographs were prepared of the grain crease tissues during movement of the {sup 14}C pulse into the grain. At all times, sucrose accounted for 93 to 97% of the total {sup 14}C present at all four sampling sites. The main features of the {sup 14}C kinetics could be accounted for by a simple compartmental model consisting of sucrose pools in series. Microautoradiographs of the crease tissues showed fairly uniform labeling of vascular parenchyma at all times, with a sharp gradient in ...
The information is reported on the kinetics of decomposition of weak hcp "3He-"4He solutions with the starting "3He concentration 0.5#+-#0.1% and 1.20#+-#0.2% under the sample pressure 3.5 to 3.8 MPa before the decomposition. The NMR technique of the prompt control of the phase separation process is developed. To accelerate the metastable phase decomposition, the samples were thermally cycled at temperatures below 100 mK. Using the pulse NMR method, the magnetic susceptibility of "3He nuclei and the spin-lattice T_1 and spin-spin T_2 relaxation times were measured on three samples of the decomposed solid solutions with the starting "3He concentration 0.5% at the pressures 3.53, 3.71 and 3.78 MPa. Above 10 mK the Curie-Weiss constant was two to three times higher than the values typical of bulk bcc "3He of the corresponding density. Below 10 mK the magnetic susceptibility was ...
To make the doubly labelled water method for determining energy expenditure more applicable in a free-living population, collection of a single daily urine or breath sample would have advantages compared to a 24-hr urine collection. Coward et al. reported the use of a single daily urine sample. In the previously described study, a single urine collection and a fasting morning breath sample were collected from four men during two 21-day periods (fall, F, spring, S) while maintaining their body wts. on controlled diets (20% calories from protein, 40% from fat, 60% from CHO [F]; 20% protein, 20% fat, 60% CHO [S]). Urine and breath samples were analyzed to determine disappearance rates of D and "1"8O for up to 21 days. Values were compared with metabolizable energy intake levels (EI), with or without corrections for estimated changes in body composition assessed by several methods. ...
Objective: To develop a method for RIA of transferrin without dilution of the serum sample. Methods: The measurable range was broadened through: Lowering of the specific radioactivity of the labelled antigen, increasing the concentration of the anti-serum and improve the curve fitting method. Results: The antiserum affinity was 3.82 x 10"-"1"0 mol/L, the specific radioactivity of the labelled antigen was 15.3 mg/mic, inter-assay error CV 5.38%, intra-assay error CV = 3.5% and the shape of the curve was good. For 30 normal control specimens, the mean TF content was 2.81 +- 0.972 mg/ml. Conclusion: Development of a method for RIA of TF without previous dilution of the test serum was of clinical value
Examination of a chloroform extract of Dracaena loureiri Gagnep (Agavaceae), a Thia medicinal plant possessing antibacterial activity, has led to the isolation of fifteen flavenoids. The biogenic relationships among these flavenoids isolated were briefly discussed. Definition of the skeleton and the unambiguous assignment of all of the protons of the isolates was achieved through extensive 2D-homonuclear chemical shift correlation, nuclear Overhauser effect (NOE) difference spectroscopy and 2D-NOE experiments. The {sup 1}H and {sup 13}C NMR spectra of staurosporine, a potent biologically active agent from Streptomyces staurosporeus, were unambiguously assigned by using 2D homonuclear chemical shift correlation, NOE, {sup 1}H-detected heteronuclear multiple-quantum coherence via direct coupling and via multiple-bond coupling for resonance assignments of protonated and nonprotonated carbons, respectively. S. Staurosporeus was found to utilize endogenous and exogenous ...
Clove (Caryophyllus aromaticus L.) has been used for clinical procedures. Blood constituents labeled with technetium-99m (99mTc) are used in nuclear medicine. The aim of this work was to evaluate the effects of clove extract on the labeling blood constituents with 99mTc and on the morphology of red blood cells. Blood samples were incubated with clove, stannous chloride and 99mTc. Plasma, blood cells, insoluble fractions of plasma and blood cells were separated. The radioactivity was counted and percentage of radioactivity (%ATI) to each blood fraction was calculated. The shape and morphometric parameter (perimeter/area ratio) were evaluated. Clove extract altered significantly (p<0.05) the %ATI of blood constituents and the shape of red blood cells without modifying the perimeter/area ratio. The results indicate that clove extract presents chemical compounds that interfere with the radiolabeling of blood constituents ...
In Tarapur Atomic Power Station unit-3 and 4, which is 540 MWe pressurized heavy water reactor, tritium is produced in primary heat transport system and moderator system. Tritium is a major contributor to the internal dose. Internal dose contributes about 30% of the collective dose. Internal dose monitoring and its control are important to control the collective dose. Estimation of internal dose is done by analysis of bioassay samples of radiation workers. In a month, about 7000 bioassay samples are analysed for the internal dose assessment during normal operation, and about 12000 during the biennial shut down of the reactor. To enhance the sample preparation and counting performance, minimize the entry errors and reduce the processing time, barcode based label generation system was developed for the internal dose monitoring. This paper discusses about the use of barcode system in the internal dose ...
High resolution of NMR spectroscopic data of biosamples are a rich source of information on the metabolic response to physiological variation or pathological events. There are many advantages...Full Text Available
Full text: HMPAO, a butane monoxime derivative of propylene amine and ECD, ethyl cysteinate dimer, are currently being used as brain imaging agents. In an effort to develop new radiopharmaceuticals for imaging brain, we have synthesized amine and imine derivatives of ethyl cysteinate with butane monoxime, optimized labelling procedure with "9"9"mTc and studied the in vivo behaviour of their "9"9"mTc complexes. Imine derivative of ethyl cysteinate with butane monoxime was synthesized by refluxing equimolar amounts of butane monoxime and ethyl cystinate in dry benzene for 3 hours. The product was purified over silica with 10% ethyl acetate in chloroform as eluent. Amine derivative was prepared by reducing the imine derivative with sodium borohydride. The ligands were characterized by NMR spectroscopy and were found to be pure. The ligands were labelled with "9"9"mTc using stannous chloride as reducing agent. The complexes ...
The determination of the banned anabolic substance zeranol and the metabolites taleranol and zearalanone in bovine urine is complicated by the occurrence of the structurally-related mycotoxin zearalenone and the corresponding {alpha}- and {beta}-zearalenol metabolites which possess similar estrogenic properties. A liquid chromatography-negative ion electrospray tandem mass spectrometric method is presented for the confirmatory analysis of all six resorcylic acid lactones ('zeranols') in urine samples using deuterium-labelled internal standards. The method was validated as a confirmatory method for bovine urine samples according to new draft EU guidelines and showed good precision and linearity, and CC{alpha} and CC{beta} values of 0.02-0.30 and <1.0 ng ml{sup -1}, respectively. The applicability was demonstrated by comparing the results of an incurred sample with previous ...
Microorganisms associated with fractured basalt core were compared to those suspended in groundwater pumped from the same well in the eastern Snake River Plain Aquifer (Idaho, USA). Two wells influenced to different degrees by a mixed-waste plume in the fractured basalt aquifer were examined. In one well, an array of dialysis cells filled with either deionized water or crushed basalt was equilibrated to compare the microorganisms collected in this fashion with those from core and groundwater samples collected in a traditional manner from the same well. Analyses were performed to characterize these samples and to provide a basis for comparison. These included total cell counts by microscopy; total biomass by phospholipid fatty acid analysis; enumerations of viable aerobic heterotrophs, groups of putative aerobic co-metabolic TCE-degraders and aerobic H2-oxidizing bacteria; mineralization of 14C- labeled acetate; and ...
Vulnerability of 25-hydroxy-(26,27-{sup 3}H)vitamin D{sub 3} 3{beta}-N-(4-azido-2-nitrophenyl)glycinate, a photoaffinity analogue of 25-hydroxyvitamin D{sub 3} (25-OH-D{sub 3}) toward standard conditions of carboxymethylationin promoted the authors to synthesize 25-hydroxyvitamin D{sub 3} 3{beta}-3{prime}-(N-(4-azido-2-nitrophenyl)amino)propyl ether (25-ANE), a hydrolytically stable photoaffinity analogue of 25-OH-D{sub 3}, and 25-hydroxyvitamin D{sub 3} 3{beta}-3{prime}-(N-(4-azido-2-nitro-(3,5-{sup 3}H)phenyl)amino)propyl ether ({sup 3}H-25-ANE), the radiolabeled counterpart of 25-ANE competes for the 25-OH-D{sub 3} binding site in rat serum vitamin D binding protein (rDBP). On the other hand, UV exposure of a sample of purified rat DBP (rDBP), preincubated in the dark with {sup 3}H-25-ANE, covalently labeled the protein. However, very little covalent labeling was observed in the absence of UV light or in the presence of ...
The mechanisms of brown adipocyte proliferation and differentiation during cold acclimation (and/or adaptation to hyperphagia) have been studied by quantitative photonic radioautography. (/sup 3/H)thymidine was injected to warm-acclimated (25/sup 0/C) rats and to animals exposed to 5/sup 0/C for 2 days. Samples of interscapular brown adipose tissue were collected for quantitative analysis of mitotic frequencies at various periods of time (4 h-15 days) after the injection of (/sup 3/H)thymidine, the rats being maintained at the temperatures to which they were initially exposed. It was found that cold exposure for 2 days markedly enhanced mitotic activity in endothelial cells, interstitial cells, and brown preadipocytes rather than in fully differentiated brown adipocytes. The total tissue labeling index (percent of labeled nuclei) increased approx.70 times over control values. The authors now report that cellular ...
Spin-polarized liquid helium-3 is prepared by laser optical pumping in low magnetic field and at room temperature, prior to fast liquefaction of the polarized sample. The use of a new helium-3 cryostat enabled us to obtain liquid helium-3 with polarization rates up to 25 % at well-stabilized temperatures (around 0.5 K). We could thereby study the effect of nuclear polarization on liquid-vapour equilibrium, and particularly on the saturated vapour pressure. Very sensitive capacitive gauges were developed. We estimated (to first order in M{sup 2}) the expected effects when the polarization M is suddenly destroyed. These effects were experimentally observed in helium-3/helium-4 mixtures, in pure helium-3, only a transient increase in pressure has been recorded. We then describe in a third part a preliminary experiment which aimed at determining the longitudinal relaxation time T1 in mixtures. Relaxation on the walls is efficiently reduced by a cesium coating and T1s ...
The structural change of the (100-x)(0.6Li{sub 2}S{center_dot}0.4SiS{sub 2})centre dotxLi{sub 3}PO{sub 4} oxysulfide glassesduring crystallization was analyzed by means of solid-state nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopy (XPS). The unique tetrahedral units of SiO{sub n}S{sub 4-n} (n=1,2,3) and PO{sub n}S{sub 4-n} (n=1,2,3) present in the glass samples vanished and the SiS{sub 4}, PS{sub 4}, SiO{sub 4} units increased with proceeding of the crystallization process. Nonbridging sulfur and oxygen atoms decreased while bridging oxygens and S{sup 2-} increased with proceeding of the crystallization process. Large structural difference between the glass and the corresponding crystallized sample explained the high stability against crystallization found in the oxysulfide glass with the composition of X=5. (author)
The structural change of the (100-x)(0.6Li[sub 2]S[center dot]0.4SiS[sub 2])centre dotxLi[sub 3]PO[sub 4] oxysulfide glassesduring crystallization was analyzed by means of solid-state nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopy (XPS). The unique tetrahedral units of SiO[sub n]S[sub 4-n] (n=1,2,3) and PO[sub n]S[sub 4-n] (n=1,2,3) present in the glass samples vanished and the SiS[sub 4], PS[sub 4], SiO[sub 4] units increased with proceeding of the crystallization process. Nonbridging sulfur and oxygen atoms decreased while bridging oxygens and S[sup 2-] increased with proceeding of the crystallization process. Large structural difference between the glass and the corresponding crystallized sample explained the high stability against crystallization found in the oxysulfide glass with the composition of X=5. (author)
Reproductive status influences cell proliferation and the survival of new cells in the dentate gyrus of adult laboratory-reared and wild female meadow voles; reproductively inactive (RI) females have more proliferating cells and more labeled cells that survive 5 weeks vs. 2 h than reproductively active (RA) females. However, the effect of season has only been studied in a wild sample of male meadow voles and factors such as age and experience that have been shown to influence neurogenesis in the dentate gyrus of adult mammals cannot be controlled in a wild sample. Therefore, we investigated whether reproductive status regulates neurogenesis (cell proliferation and/or the survival of new cells) in the dentate gyrus of laboratory-reared adult male meadow voles so that confounding variables could be controlled. Males were acclimated to a short- or a long-photoperiod to simulate the non-breeding or breeding season, ...
The paper studies the effect of crystal structure of LiNbO_3 monocrystals on NMR spectra of "7 Li and "9"3 Nb. Models of defect structure are analyzed via comparison of NMR experimental spectra and gradients of electrical field predicted on the basis of the calculations on "7 Li and "9"3 Nb nuclei using the relevant model. It is shown that no one of the main models of lithium niobate defect structure explains the peculiarities of NMR spectra. Conclusions are made about the independence of the reasons of occurrence of NMR additions lines "7 Li and "9"3 Nb, as well as, about links of "9"3 Nb NMR weak additional lines with the ranges of a different crystalline phase that may form while growing. 18 refs., 2 figs., 3 tabs.
Nuclear magnetic resonance (NMR) techniques coupled with multivariate data analysis were used to conduct monitoring of biochemical changes of black raspberry fruits at different stages of maturation and under various extraction and NMR dissolution solvent conditions: extraction with 50% methanol and D"2O as an NMR dissolution solvent, extraction with 50% methanol and 50% methanol-d"4 as an NMR dissolution solvent, and extraction with 100% ethyl acetate and 100% methanol-d"4 as an NMR dissolution solvent. Partial least-squares discriminant analysis reliably distinguished black raspberry fruits according to the maturation stage, whereby the relative levels of various compounds such as amino acids, organic acids, sugars and phenolic compounds were compared using analysis of variance. Sucrose ...
Gene analysis was used to determined the presence, abundance and phylogenetic affiliation of methanogens that exist in gas-hydrate-bearing sediment samples obtained from 23 drill cores from the JAPEX/JNOC/GSC et al. Mallik 5L-38 gas hydrate research well. Rates of methane production were examined using sediment-inoculated enrichments containing {sup 14}C-labeled carbon substrates, carbon dioxide and acetate. Archaeal 16S rDNA was only detected in 6 of the samples, resulting in 8 sequences with relationships to the Miscellaneous Crenarchaeotic Group (7 clones) and the Subsurface Euryarchaeotic Group (1 clone). The single Euryarchaeota sequence did not appear to be related to methanogens. Subsamples from the cores showed variable results upon DNA extraction and amplification. Methanogenic Coenzyme M (CoM) was detected in 13 of the 20 cores, but methanogenic methyl CoM reductase genes were not amplified from the ...
Purpose: The predictive potential of tumor cell kinetic parameters may be improved when they are studied in relation to other microenvironmental parameters. The purpose of this investigation was to quantitatively categorize human tumor samples according to proliferation patterns. Second, it was examined whether these characteristics are retained after xenotransplantation. Methods and Materials: Fifty tumor samples from head-and-neck cancer patients were immunohistochemically stained for Ki-67 and vessels. Also, parts of the samples were transplanted into nude mice. Tumors were categorized according to previously described patterns of proliferation. Vascular and proliferation patterns were analyzed using an image processing system. Results: The 50 tumors were categorized into four patterns of proliferation by visual assessment: marginal (6), intermediate (10), random (21), and mixed (12). One tumor could not be classified. ...
The binding of amphiphilic molecules to lipid bilayers is followed by 19F NMR using chemical shift and line shape differences between the solution and membrane-tethered states of...Full Text Available
A technique of low-field pulsed proton nuclear magnetic resonance (NMR) spin relaxation is described for assessment of age-related structural changes (dentin and pulp) of human teeth in...Full Text Available
Selectivity control is a key issue in the zeolite facilitated conversion of methanol to hydrocarbons. This work addresses: (a) How the zeolite topology (MFI versus BEA) determines the type of intermediate participating in the catalytic cycle thereby controlling the ethene/propene product selectivity in the methanol to alkenes reaction, and (b) to what extent light alkene formation occurs via aromatic and alkene reaction intermediates for H-ZSM-5. Three catalyst samples have been studied in experiments relying on isotopic labeling. For H-beta, penta- and hexamethylbenzene are involved in an aromatics based hydrocarbon pool type mechanism leading predominantly to propene and the higher alkenes (a very low yield of ethene is observed), whereas for H-ZSM-5, the lower methylbenzenes are the aro...
Severe depletion of nutrients through removal of the above ground litter caused a cessation of growth of a Eucalyptus exserta forest in tropical China. Since there is no above ground input of C in this forest, microbial biomass (C_m_i_c) and soil organic C (C_o_r_g) are maintained by the below ground input only. By determining the maintenance requirement of the soil microflora, it should be possible to estimate the below ground production of this forest. To check this hypothesis the authors performed an experiment with labelled C. Since large scale production and field application of "1"4C labelled Eucalyptus litter were not feasible, 'naturally labelled' C_4 plant litter (Zea mays) was used. Maize litter has a #delta#"1"3C of -12.7 per mille as compared with a #delta#"1"3C of -30.7 per mille for Eucalyptus leaf litter. The "1"3C abundance is used to determine the amount of maize C in each of the soil layers. Investigations ...
Previous work showed that the segl mutant of barley (Hordeum vulgare o Betzes) did not differ from normal Betzes in plant growth, photosynthesis, or fertility, but it produced only shrunken seeds regardless of pollen source. To determine whether defects in sucrose uptake or starch synthesis resulted in the shrunken condition, developing grains of Betzes and segl were cultured in (/sup 14/C)sucrose solutions after slicing transversely to expose the endosperm cavity and free space. In both young grains (before genotypes differed in dry weight) and older grains (17 days after anthesis, when segl grains were smaller than Betzes), sucrose uptake and starch synthesis were similar in both genotypes on a dry weight basis. To determine if sucrose was hydrolyzed during uptake, spikes of Betzes and segl were allowed to take up (fructose-U-/sup 14/C)sucrose 14 days after anthesis and the radioactivity of endosperm sugars was examined during 3 hours of incubation. Whereas less total radioactivity ...
Iodine-125 labelled vinyl and aryl iodides are formed via the reaction of sodium iodide-125 with vinyl- and arylboronic acids. Good yields of isomerically pure products are obtained.
To determine whether PKH26 labeling affects the morphologies, phenotypes, proliferation, and secretion abilities of human umbilical mesenchymal stromal cells (HUMSCs) were investigated. Isolated HUMSCs were labeled with PKH26, and cell morphology was observed under microscope. Cell cycle, apoptotic cell death, expression of PKH26, and the proliferation rate were evaluated. Additionally, fluorescence intensity of PKH26 labeling at different passage times was quantified. There were no detectable differences in cell morphology, cell growth, and proliferation rate after PKH26 labeling. In addition, fluorescence intensity of PKH26 labeling was gradually reduced with increase of the passage times. The PKH26 labeling disappeared after passage six times. In summary, PKH26 labeling is a safe and ef...
A number of ion exchange materials are being evaluated as part of the Tank Waste Remediation System (TWRS) Pacific Northwest Laboratory (PNL) Pretreatment Project for the removal of "1"3"7Cs from aqueous tank wastes. Two of these materials are organic resins; a phenol-formaldehyde resin (Duolite CS-100) produced by Rohm and Haas Co. (Philadelphia, Pennsylvania) and a resorcinol-formaldehyde (RF) resin produced by Boulder Scientific Co. (Mead, Colorado). One of the key parameters in the assessment of the organic based ion exchange materials is its useful lifetime in the radioactive and chemical environment that will be encountered during waste processing. The focus of the work presented in this report is the radiation stability of the CS-100 and the RF resins. The scope of the testing included one test with a sample of the CS-100 resin and testing of two batches of the RF resin (BSC-187 and BSC-210). Samples of the exchangers were irradiated ...
A number of ion exchange materials are being evaluated as part of the Tank Waste Remediation System (TWRS) Pacific Northwest Laboratory (PNL) Pretreatment Project for the removal of {sup 137}Cs from aqueous tank wastes. Two of these materials are organic resins; a phenol-formaldehyde resin (Duolite CS-100) produced by Rohm and Haas Co. (Philadelphia, Pennsylvania) and a resorcinol-formaldehyde (RF) resin produced by Boulder Scientific Co. (Mead, Colorado). One of the key parameters in the assessment of the organic based ion exchange materials is its useful lifetime in the radioactive and chemical environment that will be encountered during waste processing. The focus of the work presented in this report is the radiation stability of the CS-100 and the RF resins. The scope of the testing included one test with a sample of the CS-100 resin and testing of two batches of the RF resin (BSC-187 and BSC-210). Samples of the exchangers were irradiated ...
An attempt to determine lysozyme hydration by employing a proton nuclear magnetic resonance (NMR) spin-echo technique and to correlated such measurements with the 20 "0C sorption equilibrium data is made. Determinations of specific site hydration for lysozyme, as well as proton NMR transverse relaxation rates for five different types of water populations in the lysozyme-water system, are presented over the whole range of lysozyme concentrations. The proton spin-echo NMR results are consistent with a three-component analysis of the sorption isotherm up to 70% water content, above which two additional water populations are identified by 360-MHz proton NMR spin-echoes. On the basis of the proton NMR results, a major component (III) of the lysozyme sorption isotherm is assigned to the water trapped between lysozyem molecules, whose relaxation rate is increased by diffusion barriers. The ...
The present investigation compares the suitability of two radiolabeling techniques for hemoglobin. "1"2"5I labeling of hemoglobin with Iodogen as iodinating agent caused major changes in the chromatographic behaviour and an accelerated plasma clearance of the labeled hemoglobin in rats. A recently developed two-step procedure for "9"9"mTc labeling gave better results. The label had only minimal influence on the chromatographic behaviour of hemoglobin. In vivo, no free label occurred in the circulation and no transfer of the label to other plasma proteins took place. The plasma clearance of "9"9"mTc-labeled hemoglobin in rats was slowed. However, this could be explained entirely by diminishing glomerular filtration, probably by inhibition of the dissociation of the hemoglobin molecule into dimers. The plasma clearance of hemoglobin modified ...
In the present study the authors have shown that glycoproteins are present in the plasma membrane of Acanthamoeba castellanii by utilizing different radioactive labeling techniques. Plasma membrane proteins in the amoeba were iodinated by "1"2"5I-lactoperoxidase labeling and the solubilized radiolabeled glycoproteins were separated by lectin-Sepharose affinity chromatography followed by polyacrylamide gel electrophoresis. The periodate/NaB"3H_4 and galactose oxidase/NaB"3H_4 labeling techniques were used for labeling of surface carbohydrates in the amoeba. Several surface-labeled glycoproteins were observed in addition to a diffusely labeled region with M_r of 55,000-75,000 seen on electrophoresis, which could represent glycolipids. The presence of glycoproteins in the plasma membrane of Acanthamoeba castellanii was confirmed by metabolic ...
The fluorescence properties of protopine and allocryptopine in aqueous and organic environments are described for the first time. The fluorescence of alkaloids and their pH-dependent interconversion to cationic forms (transannular interaction) were studied using steady-state and time-resolved fluorescence techniques. For the analysis of tricyclic base and cis/trans tetracyclic cations of the alkaloids, NMR and X-ray crystallography were used. - Highlights: ? We describe fundamental fluorescence characteristics of alkaloids protopine and allocryptopine. ? We analyzed the pH-dependent transitions and cis/trans isomerization. ? These two alkaloids can be better distinguished by their fluorescence decay characteristics. ? The fluorescence parameters are related to the NMR and crystallographic structural data.
This work has carried out a molecular structure characterization of two Brazilian plants, Harpalyce brasiliana Benth and Bredemeyera floribunda Wild, using {sup 1} H and {sup 13} C NMR spectroscopy. NMR spectra were presented and analysed, then several structures have been proposed based on spectral data, and finally the structural determination was done 3 refs., 4 figs., 1 tab.
The product-operator formalism is the most commonly used tool for describing and designing multidimensional NMR experiments. In spite of its relative simplicity and sound theoretical underpinnings,...Full Text Available
Copper deficiency is associated with impaired brain development and mitochondrial dysfunction. Perinatal copper deficiency was produced in Holtzman rats. In vivo proton NMR...Full Text Available
An assessment is made of the biological effects and physical hazards of static and time-varying fields associated with the NMR devices that are being used for clinical imaging and in vivo spectroscopy. A summary is given of the current state of knowledge concerning the mechanisms of interaction and the bioeffects of these fields. Additional topics that are discussed include: (1) physical effects on pacemakers and metallic implants such as aneurysm clips, (2) human health studies related to the effects of exposure to nonionizing electromagnetic radiation, and (3) extant guidelines for limiting exposure of patients and medical personnel to the fields produced by NMR devices. On the basis of information available at the present time, it is concluded that the fields associated with the current generation of NMR devices do not pose a significant health risk in themselves. However, rigorous guidelines must be followed to avoid ...
We labelled Lipiodol with yttrium-90 and analysed the biodistribution in rats after intrahepatic arterial injection. An RP-18 column was used to separate {sup 90}Y from strontium-90. {sup 90}Y was retained on the column, which had been pretreated with yttrium-selective extraction reagent, di(2-ethylhexyl) phosphate, while {sup 90}Sr was washed out. A hexadentate nitrogen-donor chelating ligand N,N,N`,N`-tetrakis(2-benzymidazolylmethyl)-1,2-ethanediamine (EDTB) was synthesized by condensation of 1,2-benzenediamine and ethylene diamine tetra-acetic acid (EDTA). Lipiodol was covalently conjugated with EDTB. The final product was obtained by eluting the retained {sup 90}Y from the RP-18 column with EDTB-Lipiodol. Sixteen male rats (Sprague-Dawley) were sacrificed at 1 h, 24 h, 48 h and 72 h (four rats at each time) after injection of approximately 0.1 mCi {sup 90}Y-Lipiodol via the hepatic artery. Samples of liver, spleen, muscle, lung, kidney, ...
Hydrolyzates of tissues that had been labeled with (14C)proline often contain significant amounts of cis-4-hydroxy(14C)proline. Since animal cells do not contain an enzyme which can effect formation of cis-4-hydroxyproline, there are only two possible explanations for its presence. Either it is formed during acid hydrolysis of trans-4-hydroxyproline (which is synthesized by cells and is a common constituent of connective tissues), or it is produced by a nonenzymatic mechanism such as attack by oxygen radicals. It is important to resolve this issue because if a nonenzymatic mechanism is active in connective tissues, then it will be necessary to reevaluate currently accepted ideas about production of hydroxyproline. This communication describes a method for distinguishing between the two alternate explanations. Tissues or cells are labeled with (14C)proline, and then a known amount of trans-4-hydroxy(3H)proline is added to each ...
Hydrolyzates of tissues that had been labeled with [14C]proline often contain significant amounts of cis-4-hydroxy[14C]proline. Since animal cells do not contain an enzyme which can effect formation of cis-4-hydroxyproline, there are only two possible explanations for its presence. Either it is formed during acid hydrolysis of trans-4-hydroxyproline (which is synthesized by cells and is a common constituent of connective tissues), or it is produced by a nonenzymatic mechanism such as attack by oxygen radicals. It is important to resolve this issue because if a nonenzymatic mechanism is active in connective tissues, then it will be necessary to reevaluate currently accepted ideas about production of hydroxyproline. This communication describes a method for distinguishing between the two alternate explanations. Tissues or cells are labeled with [14C]proline, and then a known amount of trans-4-hydroxy[3H]proline is added to each ...
BackgroundIn recent years, near-infrared fluorescence (NIRF)-labeled iron nanoparticles have been synthesized and applied in a number of applications, including the labeling of human cells for monitoring the engraftment process, imaging tumors, sensoring the in vivo molecular environment surrounding nanoparticles and tracing their in vivo biodistribution. These studies demonstrate that NIRF-labeled iron nanoparticles provide an efficient probe for cell labeling. Furthermore, the in vivo imaging studies show excellent performance of the NIR fluorophores. However, there is a limited selection of NIRF-labeled iron nanoparticles with an optimal wavelength for imaging around 800 nm, where tissue autofluorescence is minimal. Therefore, it is necessary to develop additional alternative NIRF-labeled iron nanoparticles for application in this area.ResultsThis study ...
Compact bone makes up approximately 80% of the human skeletal mass. This study examines the effect of estrogen deficiency on compact bone turnover and associated geometrical structural adaptation over a 31-month period in a large animal model. Twenty-seven skeletally mature sheep were divided into control (n = 16) and ovariectomy group (OVX, n = 11). Animals were administered five different fluorochrome dyes to label intracortical bone turnover, and sacrificed at 31 months. Compact bone samples were analyzed for cortical geometry, intracortical turnover at five time points, resorption cavities, porosity, and compressive strength. Intracortical bone turnover was significantly increased in OVX, which demonstrated seasonal variation. Cross-sectional area in OVX was significantly greater than control and was associated with an increased section modulus. Intracortical porosity was significantly increased in OVX, however, there was no significant ...
This human investigation of lead absorption from the lungs utilized two forms of lead, lead chloride and lead hydroxide; the former was used in picogram amounts and the latter at microgram levels. These two species of lead were selected in an attempt to simulate the range of physicochemical properties found in atmospheric lead (urban air). Aerosols labeled with lead-203 were made of comparable aerodynamic size by using sodium chloride as the deposition-determining aerosol. After brief, mouthpiece exposures, 17 subjects were followed by serial counting with a thoracic array of scintillation detectors and two leg counters. Serial blood samples were also taken. The two exposure groups showed similar total deposition values (23 vs 26%) and the same biological retention halftimes, viz., 22.6 hr. When the retention data were corrected for blood-borne /sup 203/Pb, the biological halftimes for lung lead retention averaged 13.1 and 14.2 hr, ...
Sheep red blood cells (SRBCs) were labelled with a concanavalin A-luminol-bovine serum albumin conjugate specific for the transmembrane anion transport protein (Band 3) and exposed to 2450-MHz continuous-wave microwave radiation at an average specific absorption rate of 91W/kg for 10 min. The temperature was held constant at 25, 37, 40, 42, or 45C with an airflow heat-exchange system. Following exposure to microwave or air heating, the decrease in residual base-activated chemiluminescence (CL) of the SRBCs was measured as an indication of infield oxidase activity. Air heating resulted in a significant decrease in residual CL at temperatures above 37C (74% decrease at 45C). Microwave radiation inhibited the decline in residual CL above 37C. At 45C the inhibition was 40%. The results suggest microwave radiation either reversibly altered the thermodynamics of oxygen binding to haemoglobin or failed to energize a significant portion of the haemoglobin molecules in each ...
Rats from an inbred Sprague-Dawley strain were fed semisynthetic diets with a low (0.3 energy percent (en %)), normal (3 en %) or high (10 en %) content of essential fatty acids (EFA) for at least three generations. Twenty-nine- to 33-day-old male rats were given a single intragastric dose of (1-14C)linoleic acid in olive oil, and the respiratory CO2, urine and feces were collected for 46 hours (expt 1) or 20 hours (expt 2). The 14C activity in respiratory CO2, feces, urine and the carcass was determined in both experiments. In experiment 2 it was also measured in samples of the brown fat, liver, adrenals, white fat, skeletal muscles and brain. In both experiments the rats fed the low EFA diet retained significantly more 14C activity than the rats fed the normal or high EFA diets. In all groups the concentration of label was highest in the brown fat and the adrenals, but the above differences among the groups with respect to 14C retention were ...
The persistence and binding of the insecticide in soil and its residual effect in tomato plant were studied under green house conditions using "1"4 C -labelled chemical. When the insecticide was applied topically on tomato plant, its residues were detected in different plant parts; the amounts of which varied according to the mode of application and time of sampling. At the end of the experimental period (45 days) about 10% of the applied dose was recovered in the aerial parts of the plant following foliar application as compared with 2.4% recovery after soil application. Soil application of lindane led to higher residual content in the fruits than foliar application. The insecticide was also found to dissipate than to leach to lower soil horizons and was confined to the upper layers with no pronounced degradation capacity. Time to 50% disappearance (Dt_5_0 value) for lindane was estimated to be 18 days. 1 fig., 3 tabs.
Comparisons were made between various LH and FSH radioimmunoassays currently being used to measure avian hormones. The two LH assays were the homologous chicken system of Follett et al. (1972) and the turkey assay of Burke et al. (1979). These assays were also used in heterologous arrangement by interchanging the iodinated LH fractions and antisera. Five FSH assays were analyzed: two homologous chicken systems (Scanes et al., 1977; Sakai and Ishii, 1980) an assay based on mammalian materials (rat FSH and anti-ovine FSH antiserum, and one using labelled turkey FSH (Burke et al., 1979) with an anti-chicken FSH antiserum. The potencies of purified chicken and turkey gonadotrophin preparations and of a range of plasma samples from Japanese quail were measured in each assay. The two LH systems showed some degree of species specificity, such that chicken LH was more active than turkey LH in the chicken assay, whereas the reverse was true in the ...
Manganese is an essential metal of toxicologic concern primarily because of exposure via inhalation. Environmental forms of Mn exist mainly as insoluble oxides, yet much of the research information available relates to the soluble salts. In the present study, adult male Sprague-Dawley rats were intratracheally instilled with either soluble MnCl/sub 2/ or insoluble Mn/sub 3/O/sub 4/ labeled with /sup 54/Mn. Lungs and other major organs were sampled over a span of 3 mo after dosing with the respective chemicals, which were equivalent to 8 ..mu..Ci and 1 ..mu..mol of manganese in 0.2 ml of buffer. There was rapid clearance of Mn from the lungs in the case of both chemicals; the chloride cleared at an initial rate of nearly four times that of the oxide. Despite this early difference, the amount of /sup 54/Mn remaining in the lungs after 2 wk was similar for both compounds. The level of /sup 54/Mn in the liver, kidney, spleen, and testes peaked at ...
In this study, bone mineral density (BMD) of normal (CON), ovariectomized (OVX) and partially nephrectomized (NFR) rats was measured by 31P NMR spectroscopy; bone matrix density was...Full Text Available
Lithium tetrachloroaluminate solutions in thionylchloride, methylacetate and their mixtures are studied by "7Li and "2"7Al NMR. It is found that introduction of methylacetate in the LiAlCl_4-SOCl_2 system results in a change of lithium tetrachloroaluminate formation constant. In the ternary system, Li"+ is solvated by methyl-acetate after complete destruction of tetrachloroaluminate anion. Refs. 9, figs. 2.
Here we report the first 1H NMR metabolomics studies on excised lungs and bronchoalveolar lavage fluid (BALF) from mice exposed to crystalline silica. High resolution 1H...Full Text Available
Interactions of myristic acid with bovine serum albumin were studied by 13C NMR spectroscopy at 50.3 MHz using 90% isotopically substituted [1-13C]-, [3-13C]-, and [14-13C]myristic acids, either individually...Full Text Available
The bioenergetic capacity of skeletal muscle in a 17-year-old patient with a severe defect in complex III of the electron transport chain has been examined by 31P NMR measurements of the molar ratio...Full Text Available
31P nuclear magnetic resonance (NMR) spectroscopy was used to monitor the response of oil palm (Elaeis guineensis) and carrot (Daucus carota) cell suspensions...Full Text Available
Selected derivatives of cyclophosphamide (CP) metabolites were synthesized and the solution chemistry of each was studied by "3"1P nuclear magnetic resonance (NMR) spectroscopy under a standard set of reaction conditions at physiological pH (7.4) and temperature (37"0C). Complementary "2H and "1"3C NMR spectral data was obtained using isotopically ("2G and "1"3C) enriched CP metabolites. The CP derivatives were synthesized by the ozonolysis of substituted 3-butenyl phosphorodiamidates, and were isolated as analogues of either cis and trans 4-hydroperoxy-CP or aldophosphamide (AP). The relative ratios of the tautomeric species, 4-hydroxy-CP and AP, and their half-lives (T/sub 1/2/) were measured by "3"1P NMR spectroscopy. The influence of CP metabolites on perfused U-937 cells, a CP-sensitive human lymphoma, was observed by high resolution "3"1P NMR spectroscopy. In this manner, it was possible to ...
Three photaffinity labeled derivatives of epothilone D were prepared by total synthesis, using efficient novel asymmetric synthesis methods for the preparation of two important synthetic building...Full Text Available
Rat somatotropin (growth hormone) was labelled biosynthetically by incubating anterior pituitary lobes with radioactive amino acids for 24 h in a simple buffered salts medium containing glucose. The...Full Text Available
We describe a clustering method for labeled link network (semantic graph) that can be used to group important nodes (highly connected nodes) with their relevant link's labels by using PARAFAC tensor decomposition. In this kind of network, the adjacency matrix can not be used to fully describe all information about the network structure. We have to expand the matrix into 3-way adjacency tensor, so that not only the information about to which nodes a node connects to but by which link's labels is also included. And by applying PARAFAC decomposition on this tensor, we get two lists, nodes and link's labels with scores attached to each node and labels, for each decomposition group. So clustering process to get the important nodes along with their relevant labels can be done simply by sorting the lists in decreasing order. To test the method, we construct ...
Objective:In this article, we describe a successful low-dose, off-label usage of drotrecogin alfa (Xigris), given at 18 mcg/kg per hour, in a patient with severe sepsis who had an...Full Text Available
Electron spin resonance (ESR) studies have been performed on spin-labeled model membranes aligned using the isopotential spin-dry ultracentrifugation (ISDU) method of Clark and Rothschild. This method...Full Text Available
BackgroundObesity is a major public health threat and policies aimed at curbing this epidemic are emerging. National calorie labeling legislation is forthcoming and requires rigorous...Full Text Available
BackgroundGenotyping analysis using capillary DNA sequencing with fluorescently labeled primer pairs obtained by polymerase chain reaction (PCR) is widely used, but is expensive....Full Text Available
The basic approach to radioactive labeling techniques in hemoglobin identification consists of mixing 14C labeled normal carrier globin with 3H labeled unknown globin and carrying out the subsequent separations and purifications looking at the distribution of 3H and 14C radioactivity. This technique was devised to ascertain the amino acid substitution in Hb Indianapolis and was instrumental in solving the structure of Hb Vicksburg. It was also useful in determining the purity of gamma-chains from cultures of human and baboon erythroid progenitors. Another use of this technique would be in identifying aberrant peaks of radioactivity in chain separation chromatograms, such as ''pre-peaks''.
Astatine conversed into cationic form is shown to form stable complex with diethylenetriaminpentacetic acid. Due to this complex astatine joins RN_2 type monoclonal antibodies. More favorable conditions to prepare astatine labelled antibodies are found. Chromatographical analysis and electromigration experiments have shown that astatine is strongly retained in in-vitro biomolecule. Astatine did not escape from the labelled antibodies even in case of urea effect on them. Immune activity of astatine labelled antibodies remained similar in 20 h. 28 refs., 4 figs.
A useful method for preparing radioiodinated photoaffinity labels from alkyl anilines which offer significant advantages over present methods is described. The one-pot synthesis gives good radiochemical yields (40-64%) of pure, high specific activity (350-1500 mCi/#mu#mol) "1"2"4I labelled iodaryl azides while minimising manipulation of radioactive materials. Purification of the ["1"2"5I]iodoazido photoaffinity labels is achieved by high performance liquid chromatography. (author).
A useful method for preparing radioiodinated photoaffinity labels from alkyl anilines which offer significant advantages over present methods is described. The one-pot synthesis gives good radiochemical yields (40-64%) of pure, high specific activity (350-1500 mCi/{mu}mol) {sup 124}I labelled iodaryl azides while minimising manipulation of radioactive materials. Purification of the ({sup 125}I)iodoazido photoaffinity labels is achieved by high performance liquid chromatography. (author).
Amino acids other than those that serve as ligands have been found to influence the chemical properties of transferrin iron. The catalytic ability of pyrophosphate to mediate transferrin iron release to a terminal acceptor is largely quenched by modification non-liganded histine groups on the protein. The first order rate constants of iron release for several partially histidine modified protein samples were measured. A statistical method was employed to establish that one non-liganded histidine per metal binding domain was responsible for the reduction in rate constant. These results imply that the iron mediated chelator, pyrophosphate, binds directly to a histidine residue on the protein during the iron release process. EPR spectroscopic results are consistent with this interpretation. Kinetic and amino acid sequence studies of ovotransferrin and lactoferrin, in addition to human serum transferrin, have allowed the tentative assignment of His-207 in the ...
The synthesis of (/sup 14/C)-10,11-Epoxy-(2E,6E)-farnesyl diazoacetate in one vessel, starting from (/sup 14/C)-glyoxylic acid, is described. This compound is useful as a potential photoaffinity labeling agent for juvenile hormone binding sites.
Carbohydrate and nucleotide structural determination using modern spectroscopic techniques is dependent on our ability to label oligonucleotides and oligosaccharides with stable isotopes. Uniform Carbon 13 and Nitrogen 15 labeling of oligonucleotides is important to present-day efforts, which are focused on determining the structure of relatively small oligosaccharides and oligonucleotides, which form the elements of larger structures. Because of the relatively recent interest in three-dimensional structure, the development of techniques used to label them has lagged behind parallel techniques used to label peptides and proteins. Therefore, this group`s discussion focused primarily on problems faced today in obtaining oligonucleotides labeled uniformly with carbon 13 and nitrogen 15.
W have introduced template-synthesized metal phosphate nanoparticle labels for electrochemical immunoassay. Such use of an apoferritin template offers a simple and convenient route to prepare metallic nanoparticle labels for electrochemical immunoassays and avoid the complicated and time-consuming nanoparticle synthesis process (QD synthesis). Releasing metal ions from metal phosphate in an acetate buffer (pH 4.6) eliminates the harsh condition in the traditional metallic nanoparticle dissolution (e.g., strong acid dissolution of QDs and gold nanoparticles). This method is ultrasensitive and its DL is low to 77fM. The simultaneous detection of multiple protein targets is easily performed by using different metal phosphate nanoparticle labels (cadmium phosphate and lead phosphate). This approach can be extended to prepare multiple metal (such as zinc, lead, cadmium, copper, indium, gold, silver) phosphate nanoparticle ...
The shifts induced by equimolar mixture of typical lanthanide shift reagent such as 2,2-dimethyl-6,6,7,7,8,8,8-heptafluoro-3,5-octadionato europium with silver trifluoroacetate in /sup 1/H NMR spectra of aromatic hydrocarbons have been used for analytical purposes; the NMR determination of m- and p-xylenes in mixtures has been chosen as an example. The use has been made of the difference between induced shifts of methyl group signals in the /sup 1/H NMR spectra of m- and p-xylenes. The magnitude of induced shifts of methyl groups signal in m-xylene is always larger than that of p-isomer, irrespective of contents of m- and p-xylenes in mixture.
Summary: The surface coverage of amorphous silica gels used in the synthesis of silica polyamine composites has been investigated by 29Si NMR. By diluting the polyamine anchor silane, chloropropyl trichlorosilane, with methyl trichlorosilane it was found that surface coverage could be markedly improved for a range of amine polymers after grafting to the silica surface. The commensurate decrease in the number of anchor points and increase in the number of free amines results in an increase in metal capacity and/or an improvement in capture kinetics. Solid state CPMAS-13C NMR has been employed to investigate the structure and metal ion binding of a series of these composite materials. It is reported that the highly branched polymer, poly(ethyleneimine) (PEI) exhibits much broader 13C NMR res...
MRI diagnosis for malignant tumors are made possible by direct comparison to the results obtained by the brain and it seems possible to differentiate malignant tumors from other benign lesions. Cystic lesions, and mycotic sinusitis sometimes resemble malignant tumors in MR Image. In the present report, we investigated the relationships between the biochemical contents of cystic lesions and NMR-parameters to clarify why some inflammatory lesions appeared similar to malignant tumors in MRI. The variation of relaxation time depends upon the amount of protein in the cystic contents and the amount of glucose affects the relaxation time. We conclude that NMR-parameters are useful for the differential diagnosis of malignant tumors, cystic lesions and mycositic sinusitis by using the multiple variation analysis.
An inclusion complex between imazalil (IMZ), a selected fungicide, and cyclomaltoheptaose (beta-cyclodextrin, betaCD) was obtained using supercritical fluid carbon dioxide. The best preparation conditions were determined, and the inclusion complex was investigated by means of 1H NMR spectroscopy in aqueous solution and 13C CPMAS NMR spectroscopy in the solid state. Information on the geometry of the betaCD/IMZ complex was obtained from ROESY spectroscopy, while the dynamics of the inclusion complex in the kilohertz range was obtained from the proton spin-lattice relaxation times in the rotating frame, T(1rho) (1H). PMID:14553984
Here we present evidence that in water/acetonitrile solvent detailed structural and dynamic information can be obtained for important proteins that are naturally present as oligomers under native conditions. An NMR-derived human insulin monomer structure in H{sub 2}O/CD{sub 3}CN, 65/35 vol%, pH 3.6 is presented and compared with the available X-ray structure of a monomer that forms part of a hexamer (Acta Crystallogr. 2003 Sec. D59, 474) and with NMR structures in water and organic cosolvent. Detailed analysis using PFGSE NMR, temperature-dependent NMR, dilution experiments and CSI proves that the structure is monomeric in the concentration and temperature ranges 0.1-3 mM and 10-30 deg. C, respectively. The presence of long-range interstrand NOEs, as found in the crystal structure of the monomer, provides the evidence for conservation of the tertiary structure. Starting from structures calculated by the ...
The homologous sequences observed for many calcium binding proteins such as parvalbumin, troponin C, the myosin light chains, and calmodulin has lead to the hypothesis that these proteins have homologous...Full Text Available
The conformation of the self-complimentary DNA dodecamer d(br5CGbr5CGAATTbr5CGbr5CG) has been investigated in a variety of salt and solvent conditions by one and two-dimensional 1H NMR. In low salt...Full Text Available
Major breakthroughs have recently been reported that can help overcome two inherent drawbacks of NMR: the lack of sensitivity and the limited memory of longitudinal magnetization. Dynamic nuclear polarization...Full Text Available
The bulky octahedral complex, Rh(bpy)2chrysi3+ (chrysi = 5, 6- chrysenequinone diimine), binds single base mismatches in a DNA duplex with micromolar binding affinities...Full Text Available
... the hydroxyl group with the benzene ring. The molar extinction coefficients for the various species at their respective absorption ... Glya Recorded by 1H-NMR Spectroscopy TABLE 2 Molar Extinction Coeff...
Hydrogen cyanide polymerizes readily under a variety of conditions and significant prebiotic roles have been suggested for these polymers due to the abundance of HCN in universe. However, the structures...Full Text Available
A quantum computer (QC) can operate in parallel on all its possible inputs at once, but the amount of information that can be extracted from the result is limited by the phenomenon of wave function...Full Text Available
The passage of a vascular-injected paramagnetic contrast reagent (CR) bolus through a region-of-interest affects tissue 1H2O relaxation and thus MR image intensity. For longitudinal...Full Text Available
Despite their structural resemblance, a pair of cyclic halogenated compounds, 1-chloro-1,2,2-trifluorocyclobutane (F3) and 1,2-dichlorohexafluorocyclobutane (F6), exhibit completely different anesthetic...Full Text Available
The pattern of biodegradation and the chemical changes occurring in the macromolecular fraction of domestic sludge during autothermal thermophilic aerobic digestion (ATAD) was monitored and characterised...Full Text Available
BackgroundPathophysiological mechanisms involved in amyotrophic lateral sclerosis (ALS) are complex and none has identified reliable markers useful in routine patient evaluation....Full Text Available
The research has involved the characterization of catalyst acidity, [sup 2]D NMR studies of Bronsted acid sites, and kinetic, calorimetric, and spectroscopic studies of methylamine synthesis and related reactions over acid catalysts. Approach of this work was to explore quantitative correlations between factors that control the generation, type, strength, and catalytic properties of acid sites on zeolite catalysts. Microcalorimetry, thermogravimetric analysis, IR spectroscopy, and NMR spectroscopy have provided information about the nature and strength of acid sites in zeolites. This was vital in understanding the catalytic cycles involved in methylamine synthesis and related reactions over zeolite catalysts.
Synaptobrevin is a synaptic vesicle protein that has an essential role in exocytosis and forms the SNARE complex with syntaxin and SNAP-25. We have analyzed the structure of isolated synaptobrevin and its binary interaction with syntaxin using NMR spectroscopy. Our results demonstrate that isolated synaptobrevin is largely unfolded in solution. The entire SNARE motif of synaptobrevin is capable of interacting with the isolated C-terminal SNARE motif of syntaxin but only a few residues bind to the full-length cytoplasmic region of syntaxin. This result suggests an interaction between the N- and C-terminal regions of syntaxin that competes with core complex assembly.
In Nuclear Magnetic Resonance (NMR) imaging, contrast is dependent on the emission of radiofrequency waves by atomic nuclei, balanced by several parameters. The high information content of NMR images is due to the multiplicity of its parameters. However, this advantage introduces a difficulty in the interpretation of the contrast. There are three contrast parameters for each tissue: hydrogen nuclei density; relaxation time T1; relaxation time T2. Contrast may be enhanced towards any of these parameters by increasing the emission of radiowaves by atomic nuclei using particular pulse sequences.
The authors have performed a preliminary design for a persistent GHz NMR magnet at 23.5 T and 1.8 K operating conditions. In this paper the authors shall address the issues of realistic conductor selection, the coil design, the magnetic and mechanical analysis of the coil, and the required field uniformity. In addition, they shall describe the GHz magnet cryostat with a practical 1.8 K J-T refrigerator system. Finally vibration isolation system and field shield design and its associated field harmonics will be analyzed.
This review describes the basic theory and some recently developed techniques for the study of quadrupole nuclei with half integer spins in powder materials. The latter is connected to the introduction of the double rotation (DOR) by A. Samoson et al. (1) and to the introduction of the multiple quantum magic-angle spinning (MQ MAS) technique by L. Frydman et. al. (2). For integer spins, especially the solid-state deuterium magnetic resonance, we refer to the review of G.L. Hoatson and R.L. Vold: ''"2H-NMR Spectroscopy of Solids and Liquid Crystals'' (3). For single crystals we refer to O. Kanert and M. Mehring: ''Static quadrupole effects in disordered cubic solids''(4) and we would like also to mention the ''classic'' review of M.H. Cohen and F. Reif: ''Quadrupole effects in NMR studies of solids'' (5). Some more recent reviews in the field under study are D. Freude and J. Haase ''Quadrupole effects in solid-state NMR'' ...
Full text: Red blood cells (RBCs) labeled with "9"9"mTc are commonly used in the evaluation of cardiac function, gastrointestinal tract bleeding, red blood cell volume or splenic sequestration. Generally stannous ion is used as reducing agent. A proposed mechanism is that once the stannous ion (Sn) and the pertechnetate ("9"9"mTc) reach the interior of the RBC, the radionuclide is mainly house in the #beta#-chain of hemoglobin. The aim of this study was to determine if hemoglobin content reduction, an indicator of iron deficiency anemia, could affect the efficiency of RBC labeling and the biological distribution of this radiopharmaceutical. We studied 30 rats fed for 3 weeks after weaning with diets with iron contents of 6.5 ppm (group A), 18 ppm (group B) and 100 ppm (control). For all groups, the labeling yields were always higher than 97%; the percentage of radioactivity was mostly founded in blood with almost negligible ...
A photoaffinity derivative of the local anesthetic trimethisoquin, 5-azido-["3H]trimethisoquin (5-A["3H]T) labelled bands of app. mol. wt 50 k and 66 k. To explain the rather paradoxical labelling by 5-A["3H]T of two polypeptide chains instead of one, three possibilities were considered: (i) The site for non-competititve blockers is not carried by the 50 k or 66 k chain; however, these chains lie in the vicinity of the binding site and become preferentially labelled since they present chemical groups with which the nitrene group of 5-A["3H]T reacts. (ii) The 50 k and 66 k chains are different but carry binding sites for non-competitive blockers with similar reactivities. (iii) The 50 k chain labelled by 5-A["3H]T derives from the 66 k chain by proteolysis. These results show that the third alternative is the correct one. Under conditions which limit proteolysis, 5-A["3H]T selectively ...
A procedure for high level tritium labelling at the C2-H position of adenosine 5`-triphosphate ([2-{sup 3}H]-ATP, 1), based on the tritiodehalogenation reaction of 2-bromoadenosine 5`-triphosphate (2) has been elaborated. This precursor was prepared in a six-step synthesis from guanosine. The tritiodehalogenation of (2) for three hours over palladium oxide in phosphate buffer yielded tritium labelled ATP with high specific activity, in good chemical yield. (author).
Four /sup 125/I labeled mono- and diamines were prepared and evaluated as potential brain-imaging agents. The diamines are analogues of the previously reported /sup 75/Se labeled diamines, which show high brain uptake and retention. All of the radioiodinated amines display high initial brain uptake in rats after intravenous injection (1.7-2.4% dose/organ). The xylylenediamines show prolonged brain retention (t1/2 approximately 18 h), which is desirable for brain imaging. In contrast, the benzylamine is rapidly cleared from brain tissue (t1/2 approximately 15 min).
Scientists at JPL have developed chemical and biological techniques using microspheres filled with drugs, electron-opaque metals, or radioactive, fluorescent, magnetic or electrically charged materials to label specific groups of cells. Synthetic polymeric microspheres are coupled with specific antibodies to form reagents called immunomicrospheres, which can seek out and attach themselves to any specific group of cells. These cell-labeling techniques, therefore, open new avenues not only to the basic study of cells but also to the diagnosis and treatment of many diseases, including cancer.
Photosynthetic carbohydrates from the leaves are exported through the phloem to growing tips, roots, flowers and fruits. If sucrose labelled with {sup 14}C is applied to the leaves of bean plants, the pathway for sugar movement may be readily observed by autoradiography. Students apply the labelled sucrose during class time and return the next day to press their plants. During the next class, the pressed and dried plants are placed against X-ray film and left in the dark for four weeks. the film is then developed, examined for presence of label and compared to the pressed plants. Source to sink movement is clearly illustrated and information about the mechanism of phloem transport and loading is gained through experimental treatments, which include blocking the phloem pathway and inhibiting energy production.
The binding of iodine-labelled plasminogen to Helicobacter pylori CCUG 17874 was characterized. Inhibition of the binding was observed after preincubation of H. pylori...Full Text Available
The human erythrocyte (RBC) Rh blood group system consists of a complex of distinct integral membrane polypeptides with physical properties common to the aminophospholipid transporter responsible for the transbilayer movement of phosphatidylserine (PS) in RBC. To assess the involvement of Rh polypeptides in PS translocation, the aminophospholipid translocase was labeled with a photoactivatable PS analogue, "1"2"5I-azido-PS, and with an inhibitor of PS transport, "1"2"5I-labeled 2-(2-pyridyldithio)ethylamine. The ability of monoclonal Rh antibodies to immunoprecipitate the labeled transporter was determined. Immunoprecipitated Rh polypeptides were found to be labeled with the aminophospholipid translocase markers, suggesting that Rh proteins are involved in the transbilayer movement of PS.
Additional measurements have been made of deposition and retention of inhaled radioactively labeled iron oxide aerosols generated by a spinning top aerosol generator.
... radiation during clinical therapy and exposures due to radiation accidents or attacks, in which the doses are uncontrolled ... only be used off-label in victims of radiation accidents or attacks. The idea...
This human investigation of lead absorption from the lungs utilized two forms of lead, lead chloride and lead hydroxide; the former was used in picogram amounts and the latter at microgram levels. These two species of lead were selected in an attempt to simulate the range of physicochemical properties found in atmospheric lead (urban air). Aerosols labeled with lead-203 were made of comparable aerodynamic size (MMAD 0.25 ..mu..m +- 0.1) by using sodium chloride as the deposition-determining aerosol. After brief, mouthpiece exposures, 17 subjects were followed by serial counting with a thoracic array of 12 2-in. scintillation detectors and two 2-in. leg counters, all coupled to single channel analyzers. Serial blood samples were also taken. The two exposure groups showed similar total deposition values (23 vs 26%) and the same biological retention halftimes, viz., 22.6 h. When the retention data were corrected for blood-borne /sup 203/Pb, the ...
We have compared the kinetics for repair of UV-induced cyclobutane pyrimidine dimers in the DNA of keratinocytes in human skin and in cell culture. A small area of the buttocks of volunteers was exposed to UVB-irradiation and biopsies were taken at various time intervals. Epidermal keratinocytes in culture from the same subjects were exposed to UVC with doses chosen to elicit comparable yields of dimers in cellular DNA. The initial density of pyrimidine dimers and the kinetics of their removal were assessed utilizing the dimer-specific T4 endonuclease V and sedimentation of the unlabeled DNA through alkaline sucrose gradients. The position of DNA in the gradients was determined using a monoclonal antibody against random sequences of single-stranded DNA in a sensitive immunoassay. The initial dimer frequency was 3.9-6.7 per 10(8) daltons DNA. About 40% of the dimers were removed within 1 h, 70% in 6 h, and 90% in 24 h for both in vivo and in vitro samples. The early ...
We have compared the kinetics for repair of UV-induced cyclobutane pyrimidine dimers in the DNA of keratinocytes in human skin and in cell culture. A small area of the buttocks of volunteers was exposed to UVB-irradiation and biopsies were taken at various time intervals. Epidermal keratinocytes in culture from the same subjects were exposed to UVC with doses chosen to elicit comparable yields of dimers in cellular DNA. The initial density of pyrimidine dimers and the kinetics of their removal were assessed utilizing the dimer-specific T4 endonuclease V and sedimentation of the unlabeled DNA through alkaline sucrose gradients. The position of DNA in the gradients was determined using a monoclonal antibody against random sequences of single-stranded DNA in a sensitive immunoassay. The initial dimer frequency was 3.9-6.7 per 10(8) daltons DNA. About 40% of the dimers were removed within 1 h, 70% in 6 h, and 90% in 24 h for both in vivo and in vitro samples. The early ...
Over the last decade techniques such as confocal light microscopy, in combination with fluorescent labelling, have helped biologists and life scientists to study biological architectures at tissue and cell level in great detail. Meanwhile, obtaining information at very small length scales is possible with the combination of sample preparation techniques and transmission electron microscopy (TEM) or scanning transmission electron microscopy (STEM). Scanning electron microscopy (SEM) is well known for the determination of surface characteristics and morphology. However, the desire to understand the three dimensional relationships of meso-scale hierarchies has led to the development of advanced microscopy techniques, to give a further complementary approach. A focused ion beam (FIB) can be used as a nano-scalpel and hence allows us to reveal internal microstructure in a site-specific manner. Whilst FIB instruments have been used to study and ...
The effect of abatacept, a selective T-cell co-stimulation modulator, on vaccination has not been previously investigated. In this open-label, single-dose, randomized, parallel-group, controlled study,...Full Text Available
Synthesis of the azido substituted non-steroidal anti-inflammatory drug 2-(2,6-dichloroanilino)phenylacetic acid and isotope labeling of this compound have been performed and are described. Initial evaluation of the binding ability and photoreactivity indicates that this compound has potential for photoaffinity labeling as well as enzyme selectivity studies. (author).
The modes of action of the five major endo-(1----4)-beta-D-glucanases (I, II, III, IV and V) purified from Penicillium pinophilum cellulase were compared by h.p.l.c. analysis, with normal, 1-3H-labelled...Full Text Available
The authors have used limited proteolysis of affinity-labeled estrogen receptors (ER), coupled with antireceptor antibody immunoreactivity, to assess structural features of ER and the relatedness of ER from MCF-7 human breast cancer and rat uterine cells. MCF-7 ER preparations covalently labeled with ["3H]tamoxifen aziridine (["3H]TAZ) were treated with trypsin (T), #alpha#-chymotrypsin (C), or Staphylococcus aureus V8 protease prior to electrophoresis on sodium dodecyl sulfate gels. Fluorography revealed a distinctive ladder of ER fragments containing TAZ for each protease generated from the M/sub r/ 66,000 ER. Immunoblot detection with the primate-specific antibody D75P3#gamma# revealed that all immunoreactive fragments corresponded to TAZ-labeled fragments but that some small TAZ-labeled fragments were no longer immunoreactive. In contrast, use of the antibody H222SP#gamma# revealed a correspondence ...
We present evidence that the role of tryptophan and other potential intermediates in the pathways that could lead to indole derivatives needs to be reexamined. Two lines of Lemna gibba...Full Text Available
This case report demonstrates an hepatic amebic abscess by scintigrapy, utilizing a new radiopharmaceutical designed specifically for that purpose. The abscess is delineated as a positive lesion after twenty four hours. The agent, "1"3"1I-labeled bromometronidazole, may prove to be specific for the diagnosis of these abscesses. (orig.).
The rate of appearance of labeled thyroxine (T4) and albumin in lymph from various areas after simultaneous i.v. injection of the labeled substances in conscious ambulatory sheep has been used to estimate...Full Text Available
33 patients with advanced malignant melanoma were studied after intravenous administration of 131I-labeled Fab fragments specific for p97, an oncofetal glycoprotein of human melanoma. In all, 47 gamma...Full Text Available
HIPDM is an "1"2"3I-labeled agent with a distribution in brain reflecting regional perfusion. This compound is neutral and lipid soluble at blood pH and freely crosses the blood-brain barrier. At the lower pH in brain, it picks up a hydrogen ion and becomes positively charged. In this form the molecule is not lipid soluble and it is trapped in brain.
A method is described to smear extremely thin layers of nuclear emulsion on labeled electron microscope preparations and to measure the thicknesses of these layers, Without further separation, preparation and emulsion can be observed after exposure and development in an electron microscope. The source of the tracks formed in the emulsion can be exactly identified and the size and structure determined. This method finds applications in dust research and also in the analysis of medical and biological sections. Further information can be obtained about properties of different emulsions. (auth)
The obtained results in presently study demonstrate that the feasibility of the detection of the sentry ganglion in cervix uterine cancer using a boarding by laparoscopic via, being necessary the use of twice labelled as much with patent blue and radioisotope (colloid of labelled rhenium with "9"9"mTc, total dose of 3 MCi) to achieve the identification of the ganglion. (Author)
High liver uptake and slow body clearance presently limit the usefulness of "1"1"1In labeled antibodies for tumor imaging. We have investigated "2"0"3Pb as an alternate and better antibody label. The DTPA and cyclohexyl EDTA (CDTA) conjugates of an anticolon carcinoma antibody, 17-1A were labeled (bicyclic anhydride method) with "2"0"3Pb and "1"1"1In with 60 and 90% labeling yields, respectively. The biodistribution of "2"0"3Pb-17-1A conjugates was compared with the corresponding "1"1"1In-labeled preparations and with "2"0"3Pb-DTPA, "2"0"3Pb-nitrate and nonrelevant antibody controls in normal and human tumor (SW948) xenografted nude mice at 24, and 96 hr. Lead-203-labeled CDTA and DTPA antibody conjugates gave similar in vivo distributions. Even though the lead bound to these chelate-antibody conjugates was more labile in serum and in vivo, compared to indium, ...
Radioimmunoassays for detecting cell-associated or released virus are described using either 125I- or [3H]acetate-labeled antibodies. In the first assay system, antigen-antibody...Full Text Available
Seventy male Wistar rats were the recipients of labeled small lymphocytes (1.5 X 10(7) each) collected from the peripheral blood of syngeneic donors. The migrating labeled lymphocytes were traced in...Full Text Available
Research is described in the development of organometallic reagents in which the boron was attached to a nonreactive organic or inorganic matrix such as polystyrene, silica, or alumina. We developed the synthesis of oxygen-15 labelled butanol, which has been found to be a valuable blood flow agent in humans. We have also developed a series of polymeric borane derivatives which were used to prepare nitrogen-13 labelled amines.
A simple procedure is described for preparing {sup 125}I-labelling hyluronan of high molecular weight. The reducing terminal group of hyaluronic acid was derivatized with tyramine through the formation of a Schiff base which was subsequently reduced with sodium cyanoborohydride. By radioiodination of the aromatic ring, {sup 125}I-labelled hyaluronic acid was obtained in high yield (40%) and high specific activity, 555 GBq/mmol (15 Ci/mmol). (Author).
Ribosomal protein L 10 from the livers of trout, hen, and rat was found to be the main target for 2-nitro-4-azidobenzoyl-Phe-tRNA in affinity labelling experiments. Therefore, despite somewhat different electrophoretic mobilities, this protein seems to be involved in the organization of the peptidyl transferase centre in ribosomes of various vertebrates. (author).
Two methods were used to label pig kidney microvillar membrane proteins from the luminal and cytoplasmic surfaces of closed membrane vesicles. The first method was lactoperoxidase-catalysed radioiodination. Lactoperoxidase and glucose oxidase were positioned inside or outside the vesicles, iodination being initiated by adding glucose and "1"2"5I. After electrophoresis of the proteins, asymmetric labelling patterns on radioautographs were observed. However the major disadvantage of this method was the high degree of intramembrane labelling of the fatty acid chains of membrane lipids. The second method overcame this disadvantage. A new hydophilic photoreagent, 3,5-di("1"2"5I)iodo-4-azidobenzenesulphonate, was transported by a Na"+-dependent system into microvillar vesicles, thus permitting labelling from either side of the membrane when the vesicles were photolysed. The activity of several microvillar ...
Cell extracts of the thermophile Clostridium thermohydrosulfuricum catalyzed the phosphorylation by (..gamma..-/sup 32/P)ATP of several endogenous proteins with M/sub r/s between 13,000 and 100,000. Serine and tyrosine were the main acceptors. Distinct substrate proteins were found in the soluble (e.g., proteins p66, p63, and p53 of M/sub r/s 66,000, 63,000, and 53,000, respectively) and particulate (p76 and p30) fractions, both of which contained protein kinase and phosphatase activity. The soluble fraction suppressed the phosphorylation of particulate proteins and contained a protein kinase inhibitor. Phosphorylation of p53 was promoted by 10..mu..M fructose 1,6-bisphosphate or glucose 1,6-bisphosphate and suppressed by hexose monophosphates, whereas p30 and p13 were suppressed by 5 ..mu..M brain (but not spinach) calmodulin. Polyamines, including the odd polyamines characteristic of thermophiles, modulated the labeling of most of the phosphoproteins. Apart from ...
The time of appearance of newly synthesized rRNAs and ribosomal proteins (r-proteins) in the ribosomes of pea cotyledons (Pisum sativum L.) during germination was investigated. The ribosomal fraction was isolated and analyzed according to the method of germination of the embryo in the presence of labeled precursors or after pulse labeling of the embryos at different stages of germination. For the identification of newly synthesized rRNAs in the ribosomes we estimated the relative stability of labeled RNAs to the action of RNase, the sedimentation rate, the ability to be methylated in vivo in the presence of (/sup 14/C)CH/sub 3/-methionine, and the localization in the subunits of dissociated ribosomes. The presence of newly synthesized r-proteins in the ribosomes was judged on the basis of the electrophoretic similarity in SDS-disc electrophoresis of labeled polypeptides of purified ribosome preparations ...
The heavy chains of Acanthamoeba myosins, IA, IB and II, turkey gizzard myosin, and rabbit skeletal muscle myosin subfragment-1 were specifically labeled by radioactive ATP, ADP, and UTP, each of which is a substrate or product of myosin ATPase activity, when irradiated with uv light at 0"0C. With UTP, as much as 0.45 mol/mol of Acanthamoeba myosin IA heavy chain and 1 mol/mol of turkey gizzard myosin heavy chain was incorporated. Evidence that the ligands were associated with the catalytic site included the observations that reaction occurred only with nucleotides that are substrates or products of the ATPase activity; that the reaction was blocked by pyrophosphate which is an inhibitor of the ATPase activity; that ATP was bound as ADP; and that label was probably restricted to a single peptide following limited subtilisin proteolysis of labeled Acanthamoeba myosin IA heavy chain and extensive cleavage with CNBr and ...
Reactions of consumers to the appearance and taste of pork with and without information concerning outdoor production of pigs were tested in France, Denmark, Sweden and UK. Consumers in all four countries focussed on colour and fatness rather than marbling and drip to make their choice. Almost half of the British and Danish preferred the paler and the French the darker pork. Most people preferred the leaner pork. When information was provided in the form of labels, the vast majority of consumers preferred the pork labelled as originating from their own country as opposed to 'imported' and that labelled as pork from pigs 'raised outside' as opposed to 'inside'. There was no difference in the taste of grilled pork from indoor and outdoor production systems but pork labelled 'home produced' or 'outdoor' were more appreciated. Consumers' willingness to pay varied widely and was higher for those consumers ...
Energy expenditure (EE) of four adult men on a weight-maintenance diet was estimated by use of doubly labeled water, intake balance, and direct and indirect calorimetry. The doubly labeled water (2H218O) method was used to estimate free-living EE for 13 d. Metabolizable energy (ME) intake was used to estimate free-living EE for 1 wk. The subjects' 24-h EE was measured in a dual direct-indirect room calorimeter on 3 alternate days. Estimates of free-living EE as measured by ME intake and doubly labeled water indicate agreement between the two methods (mean difference +/- SEM, -1.04 +/- 0.63%). Measurements of EE with indirect and direct calorimetry are equivalent (mean difference 0.63 +/- 0.44%). The daily EE measured by doubly labeled water in these free-living adults over a 13-d period was 15.01% greater than the 24-h EE measured within the calorimeter.
A new /sup 99m/Tc-phosphine-isocyanide complex with the general structure (/sup 99m/Tc (DEPE)/sub 2/(CNR)/sub 2/)/sup +/ has been synthesised and tested in animals and one human. In three animal species (rat, rabbit, dog), the complex is an efficient myocardial imaging agent, while in humans it remains in the blood pool. The complex is 100% protein bound in animals and humans, but whereas in humans it is attached to a 51.5 kdalton protein (probably prealbumin), in rabbits it appears to be bound to a larger macromolecule (M.W.>100 kdalton). The efficiency of the complex for blood pool labelling was tested in a human volunteer and compared with the standard in vivo red cell labelling technique with stannous pyrophosphate. A satisfactory radionuclide angiogram could be performed with less than 370 MBq of the complex. The count rate for the complex (cps/MBq) was 15% higher than that obtained with the labelled red cells and ...
The surface coverage of amorphous silica gels used in the synthesis of silica polyamine composites has been investigated by 29Si NMR. By diluting the polyamine anchor silane, chloropropyl trichlorosilane, with methyl trichlorosilane it was found that surface coverage could be markedly improved for a range of amine polymers after grafting to the silica surface. The commensurate decrease in the number of anchor points and increase in the number of free amines results in an increase in metal capacity and/or an improvement in capture kinetics. Solid state CPMAS-13C NMR has been employed to investigate the structure and metal ion binding of a series of these composite materials. It is reported that the highly branched polymer, poly(ethyleneimine) (PEI) exhibits much broader 13C NMR resonances than the linear polymers poly(allylamine) (PAA) and poly(vinylamine) (PVA). These results are understood in terms of the low energy ...
#beta#-SiAlON was synthesized from a zeolite by NH_3 gas nitridation and its formation mechanism was investigated using X-ray diffraction and "2"9Si and "2"7Al NMR spectroscopy. It was revealed that most of the Si and Al atoms react to form #beta#-SiAlON via amorphous forms of Si-Al-O-N and O-SiAlON. Nitridation using NH_3 gas is an effective means of preventing mullite formation and promoting the introduction of nitrogen into aluminosilicate materials at lower temperatures than temperatures required by the carbothermal reduction nitridation process. Further, the NMR spectra showed that the siliceous part of the system changed into low z-value of Si_6_-_zAl_zO_zN_8_-_z (#beta#-SiAlON) and the incorporation of Al components into the #beta#-SiAlON was promoted in the later stages of the reaction. (author)
We have examined the theory of NMR multiple echoes developed for solid {sup 3}He to determine whether multiple echoes could be observed in solid hydrogen. We were particularly interested in the possibility of testing for low frequency quantum tunneling motions in solid hydrogen by the observation of multiple echoes. We find that for easily accessible nuclear spin polarizations, P > 12%, multiple echoes would be observed for HD impurities in solid parahydrogen if motional narrowing is effective in increasing the HD nuclear spin-spin relaxation time T{sub 2} to the order of 1 msec. These values for T{sub 2}, which have been observed for HD impurity concentrations of the order of 1%, are larger than the calculated rigid lattice values and can be attributed to quantum tunneling at frequencies of the order of 1kHz.
Effects of #gamma#-irradiation on synthetic polymers and paper used as packaging materials for irradiated food have been studied by NMR. Polystyrene, polybutadiene and some copolymers were studied before and after the #gamma#-irradiation treatment and in the presence or absence of antioxidants and stabilisers. In the absence of additives, the effect of #gamma#-irradiation on polystyrene is negligible even irradiating at high doses. In turn, the role of antioxidants and stabilisers is crucial in polybutadiene and butadiene-containing copolymers. Wood pulp paper was also studied by NMR. Preliminary measurements on #gamma#-irradiated wood pulp sheets show a shortening in the T_2 relaxation time component due to the bound water, i.e. some of the bound water is lost. (author)
Two new triterpene glycosides, patagonicosides B and C (2 and 3, resp.), together with the known patagonicoside A (1), have been isolated from the EtOH extract of the sea cucumber Psolus patagonicus. The structures of the new compounds were established on the basis of extensive NMR spectroscopic analysis ((1)H- and (13)C-NMR, (1)H,(1)H-COSY, HMBC, HSQC, TOCSY, and NOESY), HR-ESI-MS data, and chemical transformations. Compounds 1-3 and their desulfated analogs showed antifungal activities against the phytopathogenic fungus Cladosporium cladosporoides in a dose-dependent fashion. PMID:21404430
The effects of spin diffusion on the free induction decay (FID) of protons associated with the noncrystalline domains of two polymers, polyethylene and blended Nylon 66 (ZYTEL-408), have been examined using Goldman--Shen NMR pulse sequence ((1/2)..pi..x-t/sub 0/-(1/2)..pi..x-bar-tau-(1/2)..pi..x-t). At tau< or approx. =100 ..mu..s, the FID is drastically distorted from the exponential form while at longer tau(tau> or approx. =500 ..mu..s) an exponential FID is observed; but its transverse spin relaxation rate is smaller than that of the FID obtained after a single (1/2)..pi..x pulse and approaches this value at the limit of large tau. These findings are interpreted in terms of the theory of rapid spin diffusion. The spatial variation in the spin relaxation rate within the noncrystalline domain is inferred.
The purpose of this work is the elucidation of the f"n electronic structure of neutral mono base adducts derived from tris(#eta#"5-cyclopentadienyl)-lanthanide(III) (Cp_2Ln). The available data on related compounds like bis adducts and anionic mono adducts of the same moiety was also analyzed. The first aim was to derive the experimental crystal field splitting pattern from optical, magnetooptical and magnetochemical measurements and to reproduce it using an empirical Hamiltonian operator. The eigenvalues and eigenvectors obtained in this manner were used for a quantitative interpretation of the magnetochemical, EPR- and NMR-spectroscopic properties. For the latter subject it was necessary to develop an own procedure for the NMR analysis of paramagnetic compounds. This method is based on factor analysis and as demonstrated in the second part of this work, is clearly superior to all previous procedures. (orig.).
The endophytic fungus Trichothecium roseum LZ93 from Maytenus hookeri was found to antagonize other pathogenic fungi in vitro. To identify which compound contributed substantially to the antagonism, we fermented the strain and purified its fermentation products. Eleven compounds were obtained, including two trichothecenes, five rosenonolactones, two cardiotonic cyclodepsipeptides, and two sterols. Compound 11?-hydroxyrosenonolactone (1) was assigned according to 1D and 2D-NMR data for the first time. At the same time, the 1H and 13C-NMR assignments for 6?-hydroxyrosenonolactone (2) were revised. Of all of them, only trichothecin (6) showed strong antifungal activity. Based on our observations of the antagonistic activity and the other experimental results, we suggest that the antifungal co...
It is the intention of this paper to point to some of the problems due to molecular motion and to suggest a few solutions to those problems. A few examples will be presented of model systems which demonstrate the effects of motion on the NMR spectroscopy and a very qualitative example of severe spectral distortion in fulvic acids will be shown. In the following discussions we will use concepts derived from the oft repeated thermodynamic picture shown in figure 1. When dealing with a homogeneous, pure compound this picture is sufficient but in a heterogeneous mixture, it is likely that there will be different compounds and different domains all with slightly different versions of figure 1 with poor thermodynamic contact between them. Thus optimal conditions for cross polarization in one domain may be totally inappropriate for another. 59 refs., 10 figs.
Cyclization of deproteinized natural rubber (DPNR) or purified natural rubber latex was effectively performed in latex phase by using trimethylsilyl-trifluoromethane sulfonate or trimethylsilyl triflate (TMSOTF) as a novel catalyst, which is still not reported in the case of natural rubber latex. Various cyclization conditions affecting the degree of cyclization were studied, such as dry rubber contents, temperature, TMSOTF concentrations, and time. The cyclized products were characterized by FTIR, Raman, 1H-, and 13C-NMR spectroscopies, as well as DSC and TGA. The degree of cyclization was estimated by 1H-NMR spectrum. It was found that the degree of cyclization in NR was a function of cyclization conditions. The thermal stability of cyclized DPNR increased with the degree of cyclization....
The mechanism of the IndolPhos-Rh-catalyzed asymmetric hydrogenation of prochiral olefins has been investigated by means of X-ray crystal structure determination, kinetic measurements, high-pressure NMR spectroscopy, and DFT calculations. The mechanistic study indicates that the reaction follows an unsaturate/dihydride mechanism according to Michaelis-Menten kinetics. A large value of KM (KM=5.01+-0.16 M) is obtained, which indicates that the Rh-solvate complex is the catalyst resting state, which has been observed by high-pressure NMR spectroscopy. DFT calculations on the substrate-catalyst complexes, which are undetectable by experimental means, suggest that the major substrate-catalyst complex leads to the product. Such a mechanism is in accordance with previous studies on the mechanism...
The effects of TANOL radical have been examined on chemical shifts and relaxation rates of /sup 109/Ag NMR in aqueous solution of silver salts. The silver ion in aqueous solution is found to coordinate with TANOL radical. A small amount of TANOL is added as a doping agent(0.020M), since /sup 109/Ag signals are obtained for (1.0M) silver ion within 30 minutes. The /sup 109/Ag chemical shifts of silver salt in aqueous solutions were found within the range of 0 to -1000 ppm relative to that of 1.0M AgNo/sub 3/.
Insulitis is considered the histopathological hallmark of type I diabetes. In the non-obese diabetic (NOD) mouse, diabetes has never been observed in the absence of insulitis. The in vivo detection of insulitis could be of relevance for early prediction of diabetes. As approximately 15% of islet-infiltrating lymphocytes express interleukin 2 receptors, the authors have labelled recombinant inter-leukin 2 with "1"2"3I and used this radiopharmaceutical to detect insulitis by gamma camera imaging. The authors studied 71 prediabetic NOD and 27 normal Balb/c mice. Labelled #alpha#-lactalbumin was used as the control protein. In the first set of experiments the tissue distribution of radiolabelled interleukin 2 in isolated organs from animals sacrificed at different time points was studied. Higher radioactivity was detected in the pancreas of NOD mice injected with labelled interleukin 2, as compared to NOD mice receiving ...
The active site of chicken gizzard myosin was labeled by direct photoaffinity labeling with ["3H]UDP. ["3H] UDP was stably trapped at the active site by addition of vanadate (Vi) and Co"2"+. The extraordinary stability of the myosin.Co2+.[3H]UDP.Vi complex (t1/2 greater than 5 days at 0 degrees C) allowed it to be purified free of extraneous ["3H]UDP before irradiation began. Upon UV irradiation, greater than 60% of the trapped ["3H]UDP was photoincorporated into the active site. Only the 200-kDa heavy chain was labeled, confirming earlier results using ["3H]UTP. Extensive tryptic digestion of photolabeled myosin subfragment 1 followed by high performance liquid chromatography separations and removal of nucleotide phosphates by treatment with alkaline phosphatase allowed two labeled peptides to be isolated. Sequencing of the labeled peptides and radioactive counting showed that ...
Four "1"2"5I labeled mono- and diamines were prepared and evaluated as potential brain-imaging agents. The diamines are analogues of the previously reported "7"5Se labeled diamines, which show high brain uptake and retention. All of the radioiodinated amines display high initial brain uptake in rats after intravenous injection (1.7-2.4% dose/organ). The xylylenediamines show prolonged brain retention (t1/2 approximately 18 h), which is desirable for brain imaging. In contrast, the benzylamine is rapidly cleared from brain tissue (t1/2 approximately 15 min).
In this paper, we introduce a new recursive neural network model able to process directed acyclic graphs with labelled edges. The model uses a state transition function which considers the edge labels and is independent both from the number and the order of the children of each node. The computational capabilities of the new recursive architecture are assessed. Moreover, in order to test the proposed architecture on a practical challenging application, the problem of object detection in images is also addressed. In fact, the localization of target objects is a preliminary step in any recognition system. The proposed technique is general and can be applied in different detection systems, since it does not exploit any a priori knowledge on the particular problem. Some experiments on face detection, carried out on scenes acquired by an indoor camera, are reported, showing very promising results. PMID:16181770
A brief survey is presented of the methods of preparation and of the applications of radiopharmaceuticals labelled with short-lived positron radionuclides "1"1C, "1"8F, "1"3N and "1"5O which, thanks to their energy level schemes, short half-life and the 511 keV photon radiation energy are almost ideal tracers in modern nuclear medicine and pharmacology. In conjunction with computerized tomography, they represent one of the most sensitive diagnostic imaging methods, the so-called positron emission tomography. In addition, their incorporation in the molecule of a pharmaceutical does not change the biological and chemical properties of the original molecule unlike those of radiopharmaceuticals labelled with technetium, iodine, etc. (author). 125 refs.
A series of four 125I-labeled 1-substituted-4-phenylpiperazines were prepared and evaluated in rats as potential brain imaging agents. The compounds were labeled using (125I)iodide/chloramine-T or iodine monochloride and isolated in 48-60% radiochemical yields. The tissue distribution studies indicated that a butyrophenone derivative demonstrated the best overall brain-imaging properties. Compared with the compounds having other 1-substituents this agent had a more prolonged retention of activity in the brain and higher brain-to-blood ratios over the 4-h period studied. The in vivo behavior of this agent is comparable to that of radioiodinated N-isopropyl-p-iodoamphetamine, and, because it can be labeled directly via electrophilic methods, it has substantial potential for use in brain imaging with single photon emission computed tomography.
Wheat leaves can be induced by excision to produce fructans. Fructose residues of newly made oligofructans in leaves labeled in vivo with {sup 14}CO{sub 2} are not equally labeled. We report here on a fructosyl transferase activity in wheat leaves catalyzing the reaction: G{sup *}-F{sup *} + G-F-F = G{sup *}-F{sup *}-F + G-F. This activity, described previously in J. artichoke was attributed to fructan:fructan fructosyl transferase (FFT). The rate of this reaction in vitro is much higher than that of net kestose synthesis by SST. Hence, appearance of labeled 1-kestose from sucrose may not be an accurate measure of SST, but a curious reshuffling of hexoses between pools of 1-kestose and sucrose.
The effect of NaCl and Na_2SO_4 treatments on chlorophyll content, rate of "1"4C assimilation and products of photosynthesis in peanut (Arachish hypogaea L.) variety TMV-10 has been investigated. It was observed that chlorophyll content was affected mainly by NaCl, Na_2SO_4 treatment lowered the rate of photosynthetic "1"4CO_2 fixation. The analysis of labelled products revealed that the salts affect the carbon metabolism differently. The radioactivity was found to be accumulated in fractions of sugars and sugarphosphates in the leaves of NaCl treated plants. Na_2SO_4 treatment brought about considerable decline in labelling of sugars and an increase in labelling of amino acids and sugarphosphates. (orig.).
Hydrophobic labelling is frequently used in the study of membrane-inserted domains of intrinsic proteins. However, the published procedures, fail to incorporate sufficient radioactivity into membrane immunoglobulins of B lymhocytes to permit investigation of their subunit structures and associations with other proteins. In order to increase the specific radioactivity of ["1"2"5I]iodonaphtylazide ["1"2"5I]INA), an improved method for the synthesis of the reagent was developed. In addition, the optimal conditions for labelling B lymhpocytes with ["1"2"5I]INA and commercially available reagent 3-(trifluoromethyl)-3-(trifluoromethyl)-3-(3'-["1"2"5Iliodophenyl)diazirine (["1"2"5I]TID were isolated and analysed in detail by SDS-PAGE. The usefulness of the two reagents for the investigation of lipid-embedded domains of membrane proteins is discussed. (author). 28 refs.; 4 figs.
Although good encryption functions are probabilistic, most symbolic models do not capture this aspect explicitly. A typical solution, recently used to prove the soundness of such models with respect to computational ones, is to explicitly represent the dependency of ciphertexts on random coins as labels. In order to make these label-based models useful, it seems natural to try to extend the underlying decision procedures and the implementation of existing tools. In this paper we put forth a more practical alternative based on the following soundness theorem. We prove that for a large class of security properties (that includes rather standard formulations for secrecy and authenticity properties), security of protocols in the simpler model implies security in the label-based model. Combined with the soundness result of (\\textbf{?}) our theorem enables the translation of security results in unlabeled symbolic models to ...
Copper bioavailability was studied in rats using an extrinsic Cu label. Copper absorption from sunflower seeds (46%), peanuts (41%), cooked shrimp (50%), and cooked beef (40%) was as good or better than copper sulfate (46%). Copper from plant foods (sunflower seeds, garbanzo beans, peanuts) was absorbed equally as well as copper from animal foods (beef, shrimp, chicken liver), 39 +/- 7% vs 43 +/- 7%, P greater than 0.05. There was no significant difference in percentage Cu absorption between intrinsically labeled chicken liver and extrinsically labeled chicken liver. In a second experiment, Cu absorption was measured in the presence of glucose, fructose, sucrose, or cornstarch. There were no significant differences in Cu absorption due to different carbohydrates in a single meal.
The authors have studied the distribution of H-3 labelled schistosomicidal drug in mice by autoradiography. The H-3-labelled substances were found in liver and kidney and in successfully decreasing amounts in brain, lung, heart, fat, testis, pancreas and spleen. In various cells the silver granules were present mainly in the cytoplasms but a few in the nucleus. After administration of this labelled schistosomicidal drug, the mice were killed and studied in groups successively at 4, 8, 24 hrs. No difference in the distribution of silver granules were observed. This fact indicated that, this drug was rapidly absorbed and highly concentrated with a long duration of reservation in liver. All of these favours the schistosomicidal effect of the drug. As this drug was highly concentrated in the cytoplasm of liver cells, that might provide a pathophysiologic basis for the explanation of jaundice in the clinical practice. Moreover, ...
The heterogeneous solid catalyst, mercaptopropylsilica (MPS), has been prepared by a modified procedure in water and its structure confirmed by solid state carbon-13 CP-MAS NMR spectrum. This catalyst has been efficiently utilized for the synthesis of a wide variety of tri-, tetrasubstituted imidazoles and their bis-analogues at room temperature. The protocol was further explored for the synthesis of the drug trifenagrel.
Reaction kinetics for the displacement of 5-aminoquinoline (5-Aq) and diethyl sulfide (SEt{sub 2}) from cis-[PtPh{sub 2}(CO)(L)] (L = 5-Aq or SEt{sub 2}) by aliphatic amines was measured for a wide array of amines. Reaction products were characterized by IR and NMR spectroscopies and crystalk structures of selected products were reported. Steric effects on the substitutions were discussed.
In this article, the authors recall the factors apt to influence image quality in NMR Imaging and present the european works that have been developed in MRIQA to set 5 quality assurance tests: EUROSPIN 1 to 5.
The marked difference between the intra- and extracellular "3"1P NMR chemical shifts of various phosphoryl compounds when added to a red cell suspension may be largely understood in terms of the effects of hemoglobin on the "3"1P NMR chemical shifts. The presence of [oxy- or (carbonmonoxy)-] hemoglobin inside the red cell causes the bulk magnetic susceptibility of the cell cytoplasm to be significantly less than that of the external solution. This difference is sufficient to account for the difference in the intra- and extracellular chemical shifts of the two phosphate esters trimethyl phosphate and triethyl phosphate. However, in the case of the compounds dimethyl methylphosphonate, diethyl methylphosphonate, and trimethylphosphine oxide as well as the hypophosphite, phenylphosphinate, and diphenylphosphinate ions, hemoglobin exerts an additional, much larger, effect, causing the "3"1P NMR resonances to shift to lower ...
Phospholamban (PLB) is a 52-amino acid integral membrane protein that helps to regulate the flow of Ca2+ ions in cardiac muscle cells. Recent structural studies on the PLB pentamer...Full Text Available
Titanium and aluminum alkoxide derivatives with polymerizable ligands such as 2-(methacryloyloxy)ethylacetoacetate (HAAEMA), oleic acid and geraniol (HOGE) have been obtained. The various compounds have been characterized by FT-IR and NMR {sup 1}H. Copolymerization with styrene and divinylbenzene affords porous doped organic materials which have been characterized by scanning electron microscopy (SEM), elemental analysis, density measurements.
Analysis of published NMR relaxation data of /sup 6/Li and /sup 7/Li in Li/sub 3/N leads to a unique model fo Li/sup +/ hopping along the c-axis. It is one in which an ion goes directly from one Li(1) plane to another Li(1) plane by passing through the intermediate Li(2) plane.
Temperature-dependent (5-42 degrees C) 13C NMR spectra of albumin complexes with 90% isotopically substituted [1-13C]decanoic acids (3 mol of fatty acid per mol of albumin) showed a single peak at greater...Full Text Available
The susceptibility of solid "3He is deduced from multiple echoes observed in pulsed NMR experiments. It follows a Curie Weiss law at high temperature, increases faster than this law below 5 mK and drops abruptly around 1 mK. (Auth.).
A pulsed field gradient spin echo sequence has been incorporated in a nuclear magnetic resonance (NMR) imaging experiment to provide an image contrast dependent on local molecular self-diffusion. The...Full Text Available
A nonperturbing 13C nuclear magnetic resonance (NMR) method was used to monitor the equilibrium distribution of carboxyl 13C-enriched fatty acids (FA) between distinct binding sites on human serum albumin,...Full Text Available
Aqueous solutions of 2-amino-2-hydroxymethyl-1,3-propanediol (AHPD), a sterically hindered amine, was examined as a potential CO{sub 2} absorbent and compared with the most commonly used absorbent, monoethanolamine (MEA) solution, through equilibrium solubility measurements and {sup 13}C NMR spectroscopic analyses. The solubilities of CO{sub 2} in aqueous 10 mass % AHPD solutions were higher than those in aqueous 10 mass% MEA solutions above 4 kPa at 298.15 K, but lower below 4 kPa. The solubility difference between these two solutions increased with the CO{sub 2} partial pressures above the crossover pressure. Equilibrated CO{sub 2}-MEA-H{sub 2}O and CO{sub 2}-AHPD-H{sub 2} solutions at various CO{sub 2} partial pressures ranging from 0.01 to 3000 kPa were analyzed by {sup 13}C NMR spectroscopy. AHPD contains more hydroxyl groups than nonhindered MEA, and hence the chemical shifts in its {sup 13}C NMR spectra were strongly ...
We have measured, by {sup 1}H and {sup 13}C nuclear magnetic resonance (NMR), the percent deuteration, the tacticity and the purity of several polymers and one solvent used in the preparation of microcellular foams. The percent deuteration was measured for polystyrene, polyacrylonitrile and polyethylene. The tacticities of polystyrene and polyacrylonitrile were determined. The purity and degradation products of polyacrylonitrile and maleic anhydride were examined. This report documents the experimental procedures and results of these measurements.
For the intermetallic system CaCdsub(1-x)Tlsub(x), 0 <= x <= 1, the Knight shift Ksub(s) of the Cd-NMR and the Tl-NMR were calculated as a function of x, Ksub(s) = Ksub(s)(x). The theoretical investigations were performed on the basis of relativistic augmented-plane-wave (RAPW) band-structure calculations for the boundary phases CaCd and CaTl respectively, and by using the rigid band model for the ternary phases. The density of states and the matrix elements of the relativistic hyperfine operator for electron states at the Fermi surface were calculated in detail. The obtained values were compared with nonrelativistic calculations. The effect of using different exchange potentials was studied for Ksub(s)(Tl). For the Cd-NMR the relativistic effects enhance the nonrelativistic results by a factor of about 1.4. The theoretical value for the Knight shift is smaller than the experimental one by a factor of 1.13. The band ...
Besarhanamides A (1) and B (2) are fatty acid amides purified from the marine cyanobacterium, Lyngbya majuscula, collected from Pulau Hantu, Singapore. The structure determination of these secondary metabolites was carried out using extensive 2D NMR spectral data as well as chemical manipulations including the Marfey's method. In addition, besarhanamide A exhibited moderate toxicity with LD50 at 13mM in the brine shrimp toxicity bioassay.
Immunoassays are versatile analytical techniques that had a leading role in various clinical applications, during the last four decades. The studies carried out by Rosalyn Yalow, Solomon Berson and Roger Ekins in the 1960s gave a breakthrough in the development of this novel analytical method. Sensitivity up to femtomolar concentrations, high specificity and universal application to different classes of molecular species made immunoassay a very useful tool in analytical investigation. The expertise acquired by immunochemists in producing antibodies against any antigen and the ability of radiochemists in labeling the antigens with "1"2"5I without affecting the active site are the two main factors responsible for the above development. There are concerns about the safety and health of humans due to the high-level contamination of environment by pesticides, industrial compounds and metals, anabolic steroids in milk and meat products, and presence of mycotoxins in food ...
A commercially available synthetic nucleic acid probe (SNAP) conjugated to alkaline phosphatase was compared with standard culture techniques for detecting Campylobacter species. The SNAP was able to...Full Text Available
... NE Mall Room B-607, EPA Headquarters, 401 M ... formally adopted and initiated a joint strategy for ... CLI kick-off Partner and Task Force meeting. ...
Using nitrogen-13 initial measurements have been made of rumen ammonia-nitrogen pool size and turnover, and rate of incorporation of ammonia into microbial protein. It is also feasible to measure the rate of incorporation of absorbed ammonia into urea and the appearance of label in saliva.
This study describes procedures and outcomes in a functional analysis of problem behavior of 2 public school students. For a 13-year-old honors student, bizarre tacts (labeled as psychotic speech by...Full Text Available
The metabolism of 14C-labeled fatty acids and triacylglycerols was followed in intact germinating oil palm seedlings as well as in tissue slices. In the germinating seedling, the shoot contained...Full Text Available
Microbes in nature frequently function as members of complex multitaxon communities, but the structural organization of these communities at the micrometer level is poorly understood because of limitations...Full Text Available
An immunoassay employing 125I-labeled enterotoxin B and polystyrene tubes coated with specific antibody was used for assaying purified and crude enterotoxin. Antibody was adsorbed to untreated...Full Text Available
By pretreating simian virus 40-infected BSC-1 cells with glucosamine, [3H]uridine labeling of both cellular and viral RNA can be halted instantaneously by addition of cold uridine. We have...Full Text Available
Convection-enhanced delivery (CED) has emerged as a promising method of targeted drug-delivery for treating central nervous system (CNS) disorders, but the influence of brain structure on infusate...Full Text Available
The adenovirus fiber knob causes the first step in the interaction of adenovirus with cell membrane receptors. To obtain information on the receptor binding site(s), the interaction of labeled cell...Full Text Available
The authors studied the flow of carbon ({sup 14}C) from CO{sub 2} through sucrose to oligofructans in wheat (Triticum aestivum L.) leaves that had been induced by excision to accumulate fructan. Leaves were either labeled for 30 min and then chased in ambient air for 2 h or labeled continuously for 2 h. Fructans were chromatographed on BioGel P2 column. During continuous labeling, the specific activity was highest in sucrose and decreased for fructans with DP 3 to 5, and each increased linearly with time for 2 h. During the chase period, sucrose specific activity increased for 60 min and then declined while oligofructans gained in specific activity through the 2 h period. After 30 min of labeling, the specific activity of fructose moiety of sucrose was equal to glucose but, in oligofructans, those of the individual fructose units were not. The results may provide insight into the fructosyl ...
Platelet deposition on bovine pericardial-tissue mitral-valve prostheses in 11 dogs was observed noninvasively by use of "1"1"1In-labeled platelets and quantified after sacrifice at one (n . 3), 14 (n . 3), and 30 (n . 5) days postimplantation (300-400 microCi of labeled platelets having been injected 24 hours previously). Thrombosis on the sewing ring and pericardial leaflets at one and 14 days and on the leaflets at 30 days was delineated in scintiphotos. In vitro quantification (% injected dose) indicated that the leaflets, sewing ring, and perivalvular tissue retained 0.904% of labeled platelets at one day postimplantation, 0.198% at 14 days, and 0.040% at 30 days. Platelet half-life was reduced to 38 hours at 21 days postimplantation but returned toward the normal (50 hours) with fibrous ingrowth in the sewing ring. Microembolism in lung and kidney, as measured by tissue/blood radioactivity ratio, also was decreased ...
Production of dissolved macromolecules by ambient autotrophic and heterotrophic microbial populations was measured in a eutrophic Florida reservoir by in situ labeling with various radioactive substrates....Full Text Available
Skin sensitization is the most commonly reported occupational illness, causing much suffering to a wide range of people. Identification and labeling of environmental allergens is urgently required to...Full Text Available
BackgroundZibotentan (ZD4054) is a specific endothelin A (ETA) receptor antagonist being investigated for the treatment of prostate cancer. As zibotentan is eliminated...Full Text Available
The synthesis of (3-{sup 15}N)-labeled adenine has been reported by several groups. Each of these syntheses followed essentially the same route, in which the {sup 15}N is introduced by nitration of 4-bromoimidazole under forcing conditions using ({sup 15}N)-HNO{sub 3}. The authors have devised an alternate route which uses an azo coupling reaction for introduction of the {sup 15}N and proceeds through the intermediacy of (5-{sup 15}N)-labeled 5-aminoimidazole-4-carboxamide (AICA). An unrelated route to the (5-{sup 15}N)-labeled 5-amino-imidazole ribonucleoside (AIRs) was recently reported. AICA is a versatile precursor, which is most commonly used for entry into the guanine or isoguanine families, although it is usually used as the AICA-riboside rather than the heterocycle itself. The authors have found that AICA also can be used for the adenine family by cyclization to hypoxanthine using diethoxymethyl acetate in DMF at ...
To gain insight into the process of mitochondrial transmission in yeast, we directly labeled mitochondrial proteins and mitochondrial DNA (mtDNA) and observed their fate after the fusion of two cells....Full Text Available
Choline (Cho)-containing phospholipids are the most abundant phospholipids in cellular membranes and play fundamental structural as well as regulatory roles in cell metabolism and signaling. Although...Full Text Available
The somatic sensory system responds to stimuli of distinct modalities, including touch, pain, itch, and temperature sensitivity. In the past century, great progress has been made in understanding the...Full Text Available
To investigate the fate of intrinsic factor and cobalamin during cobalamin absorption, we incubated enterocytes isolated from guinea pig ileum for periods of up to 30 min with 57Co-labeled...Full Text Available
BackgroundWe have recently reported successful treatment of patients with chronic pain syndromes using human pooled intravenous immunoglobulin (IVIG) in a prospective, open-label...Full Text Available
The use of dideoxynucleotide triphosphates labeled with different fluorescent dyes (dye terminators) is the most versatile method for automated DNA sequencing. However, variation in peak heights reduces...Full Text Available
The sucrose derivative 6'-deoxy-6'-(2-hydroxy-4-azido)benzamidosucrose (6'-HABS) was prepared from sucrose (via 6'-deoxy-6'-aminosucrose) and 4-amino-salicylic acid. 6'-HABS is a competitive inhibitor of sucrose influx into protoplasts from developing soybean cotyledons and of sucrose binding to membranes from the bacteria P. saccharophila. The Ki for inhibition in the soybean protoplasts was 75..mu..M. 6'-Deoxy-6'-(2-hydroxy-3-/sup 125/Iodo-4-azido)benzamidosucrose was prepared by lactoperoxidase iodination of 6'-HABS. Upon photolysis in the presence of membranes from P saccharophila, label from the photoprobe is incorporated into a sucrose inducible polypeptide of mass 84 KD in SDS-PAGE. The polypeptide is protected from labeling by the inclusion of sucrose in the photolysis mixture. Photolysis conditions which lead to specific labeling of ...
Fibroblast cell population kinetics in the developing molar periodontal ligament was investigated in 10, 12, 16 and 20 days old mice by autoradiography after the administration of [3H]thymidine. Labelled...Full Text Available
13C metabolic flux analysis (MFA) is the most comprehensive means of characterizing cellular metabolic states. Uniquely labeled isotopic tracers enable more focused analyses to probe...Full Text Available
The Calorie (kcal) of present U.S. food labels is similar to the original French definition of 1825. The original published source (now available on the internet) defined the Calorie as the quantity...Full Text Available
Colonies of toxin-producing Pasteurella multocida were detected with peroxidase-labeled monoclonal antibodies by a membrane assay. Examination of the specificity of the assay with 29 P. multocida cultures...Full Text Available
Dairy products doubly labeled with 45Ca and 47Ca were used to evaluate an extrinsic labeling procedure for calcium bioavailability determination. Nonfat milk, yogurt, and fresh cheese curd were prepared from caprine milk that was intrinsically labeled with 45Ca. The products were then labeled extrinsically with 47Ca and administered to rats by gavage. The 47Ca to 45Ca ratio in bone and teeth averaged about 1.00 with either milk, yogurt, or CaCl2, but the ratio was about 1.04 when dosed with cheese curd. Ca absorption, determined by whole-body counting of 47Ca, was lower (P less than 0.05) in cheese curd (59%) than in either milk (69%), yogurt (72%), or CaCl2 (72%). Expressed as percent of dose, the absorption of 47Ca was highly correlated with bone 47Ca (r = 0.973) and with bone 45Ca (r = 0.946). Correlation between tibia 47Ca and tibia 45Ca was r = 0.923. For the dairy products tested, our results ...
The hypothesis that the internal viscosity of erythrocytes is governed by the intracellular hemoglobin (Hb) concentration is examined. Here viscosity is determined by labeling of the cytoplasmic reduced...Full Text Available
A solid-phase radioimmunoassay employing 125I-labeled enterotoxins and polystyrene tubes coated with specific antibody has been developed for assaying the relative concentrations of antibodies...Full Text Available
The cDNA encoding the B chain of the plant toxin ricin has been cloned and expressed in monkey kidney COS-M6 cells. The recombinant B chain was detected by labeling the transfected cells with [35S]methionine...Full Text Available
This paper reviews the development of cerebral scintigraphy from its early days of planar imaging with simple technetium-99m labelled compounds to the recent revival of the technique in the form of...Full Text Available
Hairpin oligonucleotides were synthesized with stems ending in a double-stranded structure, which can be ligated to double-strand breaks in DNA, and with loops that contain nucleotides modified by the...Full Text Available
A multispecialty panel of physicians evaluated a case series of 53 composite-materials workers in a large aircraft manufacturing facility who filed workers' compensation claims for illness labeled by...Full Text Available
Amino acids labelled with dimethylaminoazobenzenesulphonyl chloride can be separated by reversed-phase high-pressure liquid chromatography and detected in the visible region (436 nm). All 19 naturally...Full Text Available
One- and two-dimensional NMR techniques have been used to investigate the solution structures of (2S,6S,11S,15S)-2,6,11,15-tetramethyl-1,4,7,10,13,16-hexaoxacyclooctadecane (I) and (2R,3R,11R,12R)-2,3,11,12-tetramethyl-1,4,7,10,13,16-hexaoxyacyclooctadecane (II) macrocycle complexes of CaCl{sub 2} and Ca(NO{sub 3}){sub 2} in CDCl{sub 3}. Previous chiroptical studies of these and similar crown complexes by circularly polarized luminescence (CPL), total luminescence (TL), and circular dichroism (CD) spectroscopy have shown that the macrocycle asymmetric carbons in these complexes constrain the ring such that the sense of the ring twist in the S chiral ring complexes is opposite to that in the R chiral ring complexes. These studies have also shown that there is an added chirality element in the di- and trivalent (alkaline earth and lanthanide metal, respectively) nitrate complexes of I and II associated with the twist of the nitrate anions relative to one another as ...
The Food Safety and Inspection Service (FSIS) of the United States Department of Agriculture (USDA) inspects domestic and imported meat and poultry food products to assure the public that they are safe, wholesome, not economically adulterated and properly labeled. The Service also monitors the activities of meat and poultry plants and related activities in allied industries, and establishes standards and approves labels for meat and poultry products. As part of its responsibility, shortly after the Chernobyl accident occurred, FSIS developed a plan to assess this accident's impact on domestically produced and imported meat and poultry
Six kinds of diamino-dithiol compounds are labelled with "9"9Tc"m by ligands exchange reaction. Their ligands exchange percentage is over 95%. The biodistribution of one of these compounds in mice shows 0.88% brain uptake after two minutes and 0.28% after 15 minutes respectively. Although the brain uptake is lower for this compound, it has longer retention in brain. So, the experiment results are valuable to the design of new brain imaging agent in the future.
We describe a compact ultrafiltration system for the removal of pyrogens and bacteria from water labeled with the stable isotopes of deuterium and oxygen-18. The ultrafiltration system is constructed from readily available commercial components and can achieve complete removal of pyrogens and bacteria from 1L contaminated water within 30 min. By use of our procedure, loss of the isotopically labeled water by retention in the filtration system was minimal. The purified water is suitable for both oral and intravenous administration to healthy human subjects participating in nutrition studies.
An isotopic exchange method was used to label lipiodol with [sup 131]I. The labelling efficiency was > 92.5%, and the radiochemical purity of [[sup 131]I]lipiodol was above 98% as determined by ITLC. The influencing factors e.g. the heating temperature, reaction, pH and storage conditions were studied and the optimum conditions were determined. In a pilot study injecting [[sup 131]I]lipiodol for the treatment of hepatoma, about 70% of hepatoma patients had a response to the treatment with a reduction of [alpha]-fetoprotein and decrease of hepatoma sizes. The overall median survival was 9 months (range 2-17 months). (author).
An azido-"1"2"5iodo-ansamycin (1) in the geldanamycin family was prepared in two steps in one reaction vessel from 17-amino-22-(4'-aminophenacyl)-17-demethoxygeldanamycin (3). The title compound was suitable for photoaffinity labeling proteins that interacted with ansamycins. An alternative synthesis is reported for preparation of unlabeled title compound in order to afford practical amounts of (1) for conventional biochemical studies. (Author).
An azido-[sup 125]iodo-ansamycin (1) in the geldanamycin family was prepared in two steps in one reaction vessel from 17-amino-22-(4'-aminophenacyl)-17-demethoxygeldanamycin (3). The title compound was suitable for photoaffinity labeling proteins that interacted with ansamycins. An alternative synthesis is reported for preparation of unlabeled title compound in order to afford practical amounts of (1) for conventional biochemical studies. (Author).
Possibilities of applying the Pb/sup 203/ isotonic solution without a carrier as a label of blood erythrocytes, are found. There is a number of advantages in the Pb/sup 203/ isotonic solution without a carrier, such as a high label efficiency (above 95%), a short half-life (52 hours), and a low radiation dose. These factors prove to be favourable as compared with Cr/sup 51/ widely used for these purposes. Besides, of all preparations used up to now to treat erythrocytes and to scan the spleen, it is only in the case of Pb/sup 203/ isotonic solution without a carrier that no weight amounts of chemical substances do not enter the organism.
Studies of various established human bladder and renal carcinoma cell lines cultured in vitro demonstrated the presence of specific, saturable, high affinity binding sites for /sup 125/I-labeled human interferon Beta ser IFN-beta ser). This recombinant produced interferon labeled with approximately one atom of /sup 125/I/molecule of IFN expressed minimal or no loss of antiviral activity. A single class of binding sites (1000-2000/cell) with an affinity constant of 10(10)-10(11) L/M was measured at 4 degrees C for cells exhibiting widely different sensitivity to the antiproliferative effect of IFN-beta ser. Major fluctuations in the binding of /sup 125/I-labeled IFN-beta ser to cellular receptors were observed during in vitro proliferation of four of five cell lines examined. A significant decrease (P less than 0.001) in specific binding was observed 48 h after cultures were established. Cell cycle analysis suggested that ...
In the use of doxorubicin and radiation for treatment of human malignant tumors in vivo, the relationship between treatment-induced apoptosis and Ki-67 labeling index was investigated. Four human tumor xenografts (ependymoblastoma, NNE; primitive neuroectodermal tumor, YKP; small cell lung carcinoma, GLS; glioblastoma, KYG) were transplanted under the skin of thigh of the nude mice (BALB/cA JcL-nu). The mice were given a single radiation dose of 1 Gy, or doxorubicin alone intraperitoneally at a dose of 8 mg/kg. After treatment, sections of tumor specimens were prepared from paraffin-embedded tissues. Hematoxylin and eosin staining, TUNEL staining, and immunohistochemical analysis of Ki-67 were performed. In NNE, apoptotic cells appeared most frequently after treatment compared with all other tumors, and the incidence of apoptosis in the radiation-treated group was much higher than in the doxorubicintreated group. As the incidence of apoptosis in NNE increased, the ...
The patients studied were referred for routine abscess localization with indium-111 labelled autologous leukocytes. One series (n=15) was studied at 1 day after reinjection of labelled cells and a second series (n=9) was studied between 4 hours and 4 days after reinjection of labelled cells. The leukocytes were isolated by a gravity sedimentation method and labelled with In-111 oxinate according to Roevekamp and co-workers. The labelled cell suspension administered to the patient contained between 11 and 15 MegaBq (300-400 microCi). The indium-111 concentration in the liver and spleen was quantitated using a scintillation camera and an on-line computer system. Phantom studies were carried out to obtain conversion factors from geometric mean counts to MegaBq of activity for both liver and spleen. Once determined, the amount of activity in liver and spleen was corrected for physical ...
The purpose of this work was to develop a high specific activity radioiodinated cell membrane probe for tracking lymphocytes in-vivo to replace the nucleus localizing, cytotoxic lipophilic chelates (In-111 oxine and Tc-99m HMPAO) currently used. Alkylation of parent dye 4-[2-[-N,N-didecylamino]phenyl]ethenyl pyridine with E-1-tributylstannyl-3-tosylpropene (prepared form E-1-tributylstannyl-1-propene-3-ol), gave a tributyltin precursor 1. Radiolabeled 3-[4-[2-[4-(N,N-didecylamino)phenyl]ethenyl]pyridino] E-[I-125]-1-iodopropene (2), was prepared from 1 using peracetic acid in acetonitrile/water. Labeling yields and specific activities achieved were 26% (#approx#2170 Ci/mmol), 40% (1220 Ci/mmol), and 55% (200 Ci/mmol) for nca, 0.4, and 2 nanomole carrier iodide runs respectively. Canine mixed leukocytes (0.5-1.0 x 10"8 cells) were labeled with 2 (67% and 42% yields for 200 Ci/mol and 1220 Ci/mmol preparations) and showed blood clearance similar ...
Insulin receptors on the surface of isolated rat adipocytes were photoaffinity labeled at 12 degrees C with the iodinated photoreactive insulin analogue, 125I-B2 (2-nitro-4-azidophenylacetyl)-des-PheB1-insulin, and the pathways in the intracellular processing of the labeled receptors were studied at 37 degrees C. During 37 degrees C incubations, the labeled 440-kDa insulin receptors were continuously internalized (as assessed by trypsin inaccessibility) and degraded such that up to 50% of the initially labeled receptors were lost by 120 min. Metabolic poisons (0.125-0.75 mM 2,4-dinitrophenol (DNP) and 1-10 mM NaF), which led to dose-dependent depletion of adipocyte ATP pools, inhibited receptor loss, and caused up to 3-fold increase in intracellular receptor accumulation. This effect was due to inhibition of intracellular receptor degradation, and there was no apparent effect of the metabolic poisons on ...
Bone formation and resorption have been measured in patients with idiopathic osteoporosis by histomorphometry of 7.5-mm trephine biopsies and in the whole body by 85Sr radiotracer methodology and calcium balances. The studies were synchronized and most were preceded by double in vivo tetracycline labeling. Correlations between histological and kinetic bone formation indices were better when better when based on the extent of double tetracycline labels than on measurements of osteoid by visible light microscopy. Correction of the kinetic data for long-term exchange, using 5 months' serial whole body counting of retained 85Sr, improved the fit of the kinetic to the histological data. A statistical analysis of the measurement uncertainties showed that the residual scatter in the best correlations (between exchange-corrected bone formation rates and double-labeled osteoid surface indices) could be attributed to ...
Acquisition of three-alternative simultaneous matching-to-sample and oddity-from-sample was investigated. Five goldfish were trained on matching and five on oddity for a minimum of 70 days. Subsequently,...Full Text Available
Boat sampling technique (BST) is a surface sampling technique, which has been developed for obtaining, in-situ, metal samples from the surface of an operating component without affecting its operating service life. The BST is non-destructive in nature and the sample is obtained without plastic deformation or without thermal degradation of the parent material. The shape and size of the sample depends upon the shape of the cutter and the surface geometry of the parent material. Miniature test specimens are generated from the sample and the specimens are subjected to various tests, viz. Metallurgical Evaluation, Metallographic Evaluation, Micro-hardness Evaluation, sensitisation test, small punch test etc. to confirm the integrity and assessment of safe operating life of the component. This paper highlights design objective of boat sampling ...
Aim: Compounds such "9"9"mTc-MDP and "9"9"mTc-HEDP are used regularly in bone scintigraphy for metastasis detection. The therapeutics properties of beta emitter radionuclides like "1"5"3Sm, "1"6"6Ho and "1"7"7Lu has been widely reported in literature being "1"7"7Lu the less developed for medical applications. With the purpose of study different radiopharmaceuticals alternatives, for metastasis bone palliation, we have evaluated, on a comparative basis, the labeling of "1"5"3Sm-MDP, "1"5"3Sm-HEDP, "1"6"6Ho-MDP, "1"6"6Ho-HEDP, "1"7"7Lu-MDP and "1"7"7Lu-HEDP from the exhibited radionuclidic purity and biological distribution point of view. Material and Methods: The radionuclides were produced at La Reina Research Reactor, Chilean Nuclear Energy Commission. The radionuclidic purity was determined by gamma-Ray spectrometry. The labeling was accomplished with MDP (Plenum) and HEDP synthesized in-house. The in-vitro affinity of ...
One of the refinements of modern Nuclear Medicine is the capacity of providing dynamic and kinetics images of the administered radiopharmaceutical, reproducing its transport mechanism, action sites, receptor binding and excretion route. With the continues technological advances new radiopharmaceuticals have been developed in order to express higher specificity and with higher characters of affinity between receptor/complex. One radiopharmaceutical is formed by a reagent or bio molecule that has in its structure a radioisotope, that has the objectives of carrying it to the organs of affinity or to benign or malign tumoral process. Somatostatin inhibits the growing and proliferation of several tumoral cells. Somatostatin analogs bind to somatostatic receptors that are expressed in different kind of neoplasia DOTA-LANREOTIDE (DOTALAN) is an octapeptide analog to somatostatin. The interest of labeling the bio conjugate with gallium-67 in Nuclear Medicine comes from its ...
We have performed multicanonical Monte Carlo simulations of C-peptide of ribonuclease A. It is known by CD and NMR experiments that this peptide has high alpha-helix content in aqueous solution and that the side-chain charges of residues Glu-2$^-$ and His-12$^+$ play an important role in the stability of the alpha-helix. In order to confirm these experimental implications, we have used two analogues of the peptide with charged and neutral side chains of Glu-2 and His-12. Two dielectric functions, distance-dependent and constant, are considered to study the effects of solvent contributions. All the simulations were started from random initial conformations. Various thermodynamic quantities such as average helicity as a function of residue number and average distance between two side chains as a function of temperature are calculated. The results are found to be in accord with the implications of CD and NMR experiments. The lowest-energy ...
A general approach has been designed to synthesize some mononuclear and binuclear cyclometalated platinum(II) complexes, containing aromatic N-donor ligands with the presence of one Cl- trans to carbon. In this way, cyclometalated platinum(II) complex [Pt(C^N)Cl(dmso)], 1, C^N = N(1),C(2prime)-chelated, deprotonated 2-phenylpyridine and dmso = dimethylsulfoxide, was used as a precursor to react with imidazole derivatives (1-methylimidazole, 2a, imidazole, 2b,), monodentate pyridine derivatives (4-methylpyridine, 2c, pyridine, 2d,) and bidentate pyridine derivative (4,4prime-bipyridine, 3 and 4,). Synthesized complexes were fully characterized by using multinuclear NMR spectroscopy (1H, 13C{1H} and 195Pt), correlation NMR spectroscopy (1H-1H COSY, 13C{1H}-1H Heteronuclear Multiple Quantum C...
Polypeptides, copolymers of #alpha#-amino acids and #alpha#-hydroxy acids, could prove to be a valuable new class of synthetic biodegradable polymers. In this paper. steps in synthesis of poly (dl-lactide-co-3, 6-dimethylmorpholine-2,5-dione) from dl-lactide and dl-3,6-dimethylmorpholine-2,5-dione was explained. dl-Lactide was synthesized from lactic acid. In the reaction of 2-bromopropionyl chloride and dl-alanine, N-(2-bromopropionyl)-dl-alanine was prepared and this material was converted to its salt and finally this salt was converted to 3,6-dimethylmorpholine-2,5-dione in a sublime r. These two monomers, that is d l-lactide and dl-3,6-dimethylmorpholine-2,5-dione was polymerized by ring-opening polymerization. F T-IR, "1H NMR, "1"3C NMR Spectra were used for structure elucidation of all intermediate compounds and final product.
The structure of the O-antigen polysaccharide (PS) from Escherichia coli O177 has been determined. Component analysis together with 1H and 13C NMR spectroscopy experiments was used to determine the structure. Inter-residue correlations were determined by 1H,13C-heteronuclear multiple-bond correlation and 1H,1H-NOESY experiments. PS is composed of tetrasaccharide repeating units with the following structure: 2)-a-l-Rhap-(13)-a-l-FucpNAc-(13)-a-l-FucpNAc-(13)-b-d-GlcpNAc-(1 An a-l-Rhap residue is suggested to be present at the terminal part of the polysaccharide, which on average is composed of 20 repeating units, since the 1H and 13C chemical shifts of an a-linked rhamnopyranosyl group could be assigned by a combination of 2D NMR spectra. Consequently, the biological repeating unit has a 3-...
Platinum(II) complexes (1-4) with bidentate N,Nprime-ligands, O,Oprime-dialkyl esters (alkyl = ethyl, n-propyl, n-butyl and n-pentyl), of (S,S)-ethylenediamine-N,Nprime-di-2-(4-methyl)pentanoic acid were synthesized and characterized by IR, 1H NMR and 13C NMR spectroscopy and elemental analysis. DFT calculations were performed for the complexes and it was found that only one diastereoisomer could be formed. Cytotoxic activity of complexes 1-4 was determined against chronic lymphocytic leukemia cells (CLL) and compared to the activity of ligand precursors L12HCl-L42HCl and corresponding palladium(II) complexes, [PdCl2L] (L = L1-L4). The complexes were found to exhibit significantly higher antitumor activities than cisplatin on CLL cells. Cytotoxic effect of platinum(II) complexes on CLL cel...
GSTD1 is one of several insect glutathione S-transferases capable of metabolizing the insecticide DDT. Here we use crystallography and NMR to elucidate the binding of DDT and glutathione to GSTD1. The crystal structure of Drosophila melanogaster GSTD1 has been determined to 1.1 {angstrom} resolution, which reveals that the enzyme adopts the canonical GST fold but with a partially occluded active site caused by the packing of a C-terminal helix against one wall of the binding site for substrates. This helix would need to unwind or be displaced to enable catalysis. When the C-terminal helix is removed from the model of the crystal structure, DDT can be computationally docked into the active site in an orientation favoring catalysis. Two-dimensional {sup 1}H,{sup 15}N heteronuclear single-quantum coherence NMR experiments of GSTD1 indicate that conformational changes occur upon glutathione and DDT binding and the residues that broaden upon DDT ...
Following the successful application of hydrostatic pressure in mechanistic investigations of organic reactions, chemists have launched a vigorous effort to apply this tool to substitution reactions of coordination compounds. The authors began to study pressure effects in the NMR spectra of keton-lanthanide combination with the hope that the increase shifts anticipated might enhance the utility of the method, perhaps even expand its applicability to new classes of compounds. 5-Phenyl- and 5-tert-butyladamantan-2-one, piperidine, tetrahydrofuran, and cyclopentanol exhibited pressure-reduced lanthanide-induced shifts with Eu(fod)/sub 3/; Yb(fob)/sub 3/ and the shielding reagent Pr(fod)/sub 3/ showed the same effect with adamantanone. Solvent variations (CD/sub 2/Cl/sub 2/, CCl/sub 4/) caused minor changes in the magnitude of these shifts but did not reverse any. With the objective of learning whether these effects are due to a suppressed equilibrium population or to ...
The pozzolanic behaviour of compound-activated red mud-coal gangue has been investigated through TG, DTA, XRD, FTIR and {sup 27}Al MAS NMR. From viewpoint of reaction kinetics, it is found that the pozzolanic reaction mechanism of the compound-activated red mud-coal gangue-lime system is clearly consistent with diffusion control up to 14 days, and the reaction rate constant calculated from Jander equation decreases with the increase of CaO addition in the system. The hydration products formed in the red mud coal gangue-lime systems at ambient temperature are essentially aluminous C-S-H and Ca{sub 3}Al{sub 2}O{sub 6} center dot xH{sub 2}O. From TG analysis results, it is thought that the high amount of Ca(OH){sub 2} in the pastes of studied system is not conducive to the continual increase of non-evaporable water content of the hydration products. Of particular interest. {sup 27}Al MAS NMR proved to be an effective technique to obtain valuable ...
The pozzolanic behaviour of compound-activated red mud-coal gangue has been investigated through TG, DTA, XRD, FTIR and 27Al MAS NMR. From viewpoint of reaction kinetics, it is found that the pozzolanic reaction mechanism of the compound-activated red mud-coal gangue - lime system is clearly consistent with diffusion control up to 14 days, and the reaction rate constant calculated from Jander equation decreases with the increase of CaO addition in the system. The hydration products formed in the red mud-coal gangue - lime systems at ambient temperature are essentially aluminous C-S-H and Ca3Al2O6.xH2O. From TG analysis results, it is thought that the high amount of Ca(OH)2 in the pastes of studied system is not conducive to the continual increase of non-evaporable water content of the hydration products. Of particular interest, 27Al MAS NMR proved to be an effective technique to obtain valuable information of Al[4] in C-S-H and Al[6] in ...
A tertiary structure of recombinant A22^G-B31^K-B32^R-human insulin monomer (insulin GKR) has been characterized by ^1H, ^1^3C NMR at natural isotopic abundance using NOESY, TOCSY, ^1H/^1^3C-GHSQC, and ^1H/^1^3C-GHSQC-TOCSY spectra. Translational diffusion studies indicate the monomer structure in water/acetonitrile (65/35vol.%). CSI analysis confirms existence of secondary structure motifs present in human insulin standard (HIS). Both techniques allow to establish that in this solvent recombinant insulin GKR exists as a monomer. Starting from structures calculated by the program CYANA, two different refinement protocols used molecular dynamics simulated annealing with the program AMBER; in vacuum (AMBER_VC), and including a generalized Born solvent model (AMBER_GB). From these calculation...
Ionic motion of a divalent cation, Ba"2"+, in a single crystal of Ba-Al-priderite was studied using "2"7Al as an NMR probe. Several pairs of satellite peaks due to electric quadrupole interaction were observed superposed on broad satellite tails on both sides of the main peak of "2"7Al. These peak pairs indicate the existence of some stable three-dimensional configurations of Ba"2"+ ions in the structure, and the broad shoulders show a random substitution of Al"3"+ for Ti"4"+ sites. The temperature dependence of the spin-lattice relaxation time T"*_l measured in the temperature range from 161 to 1176 K was analyzed by a curve fitting method on the assumption that there are two types of Ba"2"+ ions. An activation energy of 0.47 eV was obtained for the motion of Ba"2"+ ions which are easy to move, and a broad distribution of activation energies spread over a range from 0.95 to 2.45 eV was obtained for the motion of Ba"2"+ ions which form a three-dimensional honeycomb ...
Results of our systematic NMR study in high T_c cuprates are reviewed. The antiferromagnetic spin fluctuations (AFSF) decrease in the order of La_1_._8_5Sr_0_._1_5CuO_4. YBa_2Cu_3O_7 and Tl_2Ba_2CuO_6_+_y. 1/T_1 of "6"3Cu in the CuO_2 plane in the normal state follows essentially a Curie-Weiss law at high temperature and T_1T = const. law at low temperature. The temperature dependence of 1/T_1 and the Knight shift together with their impurity effect in the superconducting state strongly suggest d-wave pairing implying the AFSF to be responsible for the occurrence of superconductivity. From the NQR frequency measurement the density of Cu 3d and O 2p holes decreases and increases, respectively, in the order of La, Y and Tl compounds, which is consistent with the change of AFSF. The relation between T_c and #nu#_Q, and their pressure dependence suggest that there exists and optimum value of the ratio of Cu 3d and O 2p hole density to give a maximum in T_c. (orig.).
Angelin Pedra is a specie found in the north of Mato Grosso State in Brazil, where an expressive volume of waste of this wood is produced. An alternative to recycle this waste is to produce wood plastic composites. However, structural and chemical investigations are fundamental to generate information for this use. In the present work, low field NMR was used to determine the spin-lattice and spin-spin relaxation times with objective to investigate the molecular dynamic behavior of the alburnu and cerne regions of Angelin Pedra aiming at a potential use of this waste wood in polymeric composites. The results of the proton spin-lattice relaxation time (T1H) and the proton spin-spin relaxation time (T2H) showed at least three different mobility domains for both regions. Among the values, one was very flexible and other was rigid. Knowing that wood is a polymer composite basically constituted by cellulose, hemicellulose and lignin can attribute the smaller T1 value and ...
The available experimental data on the specific heat, magnetic susceptibility, magnetization, valence, NMR Knight shift and relaxation rate, and the quadrupolar moment of YbPd_2Si_2 are examined within the framework of the single-ion Anderson model. Such an analysis has previously given excellent agreement between theory and experiment for numerous other light heavy-fermion compounds, where crystalline fields do not play a dominant role. For YbPd_2Si_2, substantial crystalline-field splittings make difficult a quantitative comparison with existing exact solutions of the Anderson model. Inconsistencies with the interpretation that a nearly degenerate ground quadruplet determines the low-temperature thermodynamics are pointed out. It is concluded that at least three of the four Kramers doublets participate in the low-T properties. These three doublets should have a splitting of the order of the Kondo temperature, i.e., about 100 K. A simple resonant-level model ...
The available experimental data on the specific heat, magnetic susceptibility, magnetization, valence, NMR Knight shift and relaxation rate, and the quadrupolar moment of YbPd{sub 2}Si{sub 2} are examined within the framework of the single-ion Anderson model. Such an analysis has previously given excellent agreement between theory and experiment for numerous other light heavy-fermion compounds, where crystalline fields do not play a dominant role. For YbPd{sub 2}Si{sub 2}, substantial crystalline-field splittings make difficult a quantitative comparison with existing exact solutions of the Anderson model. Inconsistencies with the interpretation that a nearly degenerate ground quadruplet determines the low-temperature thermodynamics are pointed out. It is concluded that at least three of the four Kramers doublets participate in the low-{ital T} properties. These three doublets should have a splitting of the order of the Kondo temperature, i.e., about 100 K. A simple ...
The /sup 31/P NMR method was first applied to characterize in vivo phosphorylation of H1 and H5 in calf thymus and chicken erythrocytes as well as in vitro phosphorylation of H1 and H5 by cAMP-dependent protein kinase. The amino acid residues phosphorylated in vivo in the histones were exclusively serine residues, and the mole fraction of phosphoserine was estimated to be 0.34 and 0.27 per molecule of calf thymus H1 and chicken erythrocyte H5, respectively. Interestingly, chicken erythrocyte H1 was not phosphorylated in vivo. Three H1 subtypes from calf thymus H1 varied in the /sup 31/P NMR spectra, and the bisected fragments of calf thymus H1 and chicken erythrocyte H5 exhibited characteristic spectral patterns, indicating that there are considerable diversities of the degree of phosphorylation and phosphorylation sites in very-lysine-rich histones. Furthermore, it was found that the microenvironment of phosphoserine residues phosphorylated in ...
The effect of the external pH on the intracellular pH in mung bean (Vigna mungo (L.) Hepper) root-tip cells was investigated with the T P nuclear magnetic resonance (NMR) method. The T P NMR spectra showed three peaks caused by cytoplasmic G-6-P, cytoplasmic Psub(i) and vacuolar Psub(i). The cytoplasmic and vacuolar pHs could be determined by comparing the Psub(i) chemical shifts with the titration curve. When the external pH was changed over a range from pH 3 to 10, the cytoplasmic pH showed smaller changes than the vacuolar pH, suggesting that the former is regulated more strictly than the latter. The H -ATPase inhibitor, DCCD, caused the breakdown of the mechanism that regulates the intracellular pH. H -ATPase appears to have an important part in the regulation of the intracellular pH.
The effect of the external pH on the intracellular pH in mung bean (Vigna mungo (L.) Hepper) root-tip cells was investigated with the "3"1P nuclear magnetic resonance (NMR) method. The "3"1P NMR spectra showed three peaks caused by cytoplasmic G-6-P, cytoplasmic Psub(i) and vacuolar Psub(i). The cytoplasmic and vacuolar pHs could be determined by comparing the Psub(i) chemical shifts with the titration curve. When the external pH was changed over a range from pH 3 to 10, the cytoplasmic pH showed smaller changes than the vacuolar pH, suggesting that the former is regulated more strictly than the latter. The H"+-ATPase inhibitor, DCCD, caused the breakdown of the mechanism that regulates the intracellular pH. H"+-ATPase appears to have an important part in the regulation of the intracellular pH. (author).
A mixture of long-chain hydrocarbons constituted by nonacosane (29C, 7.5%), hentriacontane (31C, 48.3%), and tritriacontane (33C, 30.1%), the ester 1?-acetyloxymethylpentacosa-20?-enyl 10-hydroxydecanoate (2), ?-amyrin (3), friedelin (4), and lupeol (5), and 3?-hydroxy-D:B-friedo-olean-5-ene (6) were identified as constituents of fruits of Maytenus salicifolia Reissek (Celastraceae). The structural formula and the stereochemistry of compound 6 were established by the data obtained through 1H and 13C NMR spectroscopy, including DEPT-135 and 2D (HMQC, HMBC, and NOESY) experiments. By analysis of the spectral data, it was possible to correct seven chemical shift assignments of compound 6, which were erroneous attributed and published in the scientific literature.
In our evaluation we utilized the Asahi Mark-J NMR-CT system, with a resistive vertical quadrupolar electromagnet (0.1 Tesla) and a proton resonance frequency of 4.5 MHz. Our main imaging methods are the inversion-recovery or IR, saturation-recovery, or SR, and calculated T/sub 1/. Difference, or D images, constructed by subtracting the data of the IR signal from that of the SR signal, have also been obtained in some cases. The system allows averaging of raw data. Hybrid images were constructed from two or more images to obtain clear definition of areas of interest. By using the hybrid image, several tissues of different relaxation times can be shown in the same image. Application in our study of the newly developed hybrid image indicates its importance in the detection and diagnosis of lesion, especially the detection of the differentiation of an edematous lesion from a tumor, and also abnormal fluid collection such as the pleural effusion or ascites. We hope that ...
Solid-state nuclear magnetic resonance (NMR) has been used to explore the nanometer-scale structure of Nafion, the widely used fuel cell membrane, and its composites. We have shown that solid-state NMR can characterize chemical structure and composition, domain size and morphology, internuclear distances, molecular dynamics, etc. The newly-developed water channel model of Nafion has been confirmed, and important characteristic length-scales established. Nafion-based organic and inorganic composites with special properties have also been characterized and their structures elucidated. The morphology of Nafion varies with hydration level, and is reflected in the changes in surface-to-volume (S/V) ratio of the polymer obtained by small-angle X-ray scattering (SAXS). The S/V ratios of different Nafion models have been evaluated numerically. It has been found that only the water channel model gives the measured S/V ratios in the normal hydration ...
The dealumination of mordenite by acidification (HCl, HNO/sub 3/) and by SiCl/sub 4/ and steaming treatments is followed by high-resolution magic-angle-spinning solid-state /sup 29/Si and /sup 27/Al NMR spectroscopy. The combined use of these techniques leads to the determination of the silicon-aluminum ordering. It is demonstrated that aluminum atoms preferentially occupy tetrahedral positions in the four-membered rings of the mordenite structure. In addition, a mechanism of dealumination can be inferred, consisting in removing the aluminum atoms two by two from the four-membered rings. It is also possible to compute the number of SiOH groups left in the unit cell after the progressive removal of aluminum atoms: four groups per extracted Al atom are generated in the beginning of dealumination and this number gradually decreases to two, suggesting that a structural reorganization must necessarily occur for substantial dealumination. These silanol groups are also ...
The murine 3T3-L1 fibroblast under appropriate incubation conditions differentiates into an adipocyte phenotype. This 3T3-L1 adipocyte exhibits many of the morphologic, biochemical, and insulin-responsive features of the normal rodent adipocyte. Using quantitative electron microscopic (EM) autoradiography we find that, when /sup 125/I-insulin is incubated with 3T3-L1 adipocytes, the ligand at early times of incubation localizes to the plasma membrane of the cell preferentially to microvilli and coated pits. When the incubation is continued at 37 degrees C, /sup 125/I-insulin is internalized by the cells and preferential binding to the villous surface is lost. With the internalization of the ligand, two intracellular structures become labeled, as determined by the method of hypothetical grain analysis. These include large clear, presumably endocytotic, vesicles and multivesicular bodies. Over the first hour of incubation the labeling of these ...
A method for the introduction of N-(/sup 3/H)acetyl groups into glycosaminoglycans is described. The procedure is based on (/sup 3/H)acetylation of N-unsubstituted hexosamine residues by treating the polysaccharides with (/sup 3/H)acetic anhydride. Preparations of heparin and heparin sulfate were found to contain significant numbers of N-unsubstituted hexosamine residues, as isolates. In contrast, such units could not be detected in chondroitin sulfate, dermatan sulfate, or hyaluronic acid. These polysaccharides were therefore subjected to partial N-deacetylation by reaction with hydrazine in the presence of hydrazine sulfate. After treatment with (/sup 3/H)acetic anhydride, the specific activities of the resulting labeled polysaccharide preparations ranged between 0.1 X 10/sup 6/ and 0.6 X 10/sup 6/ cpm /sup 3/H/..mu..g of uronic acid. The /sup 3/H-labeled polysaccharide preparations did not differ significantly from the corresponding ...
Tumor imaging using radioiodinated monoclonal antibodies (Mab) suffered from rapid in vivo deiodination. This problem can be circumvented by covalent attachment of a bifunctional chelating group to the Mab followed by chelation with a suitable cationic radionuclide such as In-111. Competition of trace metal contaminants with In-111 for chelating sites, however, is known to lower the labeling yield. Since commercially available reagents may be contaminated with other trace metal ions, the effect of trace metals on Mab-DTPA chelation and the possibility of masking the trace metal effect on the In-111 labeling of Mab-DTPA were, therefore, investigated. Labeling yield of 93% was obtained when 1 mg (20mg/ml) of Mab F(ab')/sub 2/-DTPA (protein to DTPA ratio of --1) was allowed to incubate with 3 mCi In-111 in 2 ml acetate buffer (0.5M, pH 5.5) for 30 min. The yield was drastically decreased to 13-76% when the reactions were ...
An improved labeling procedure for peptides attached to organometallic 99mTc(III) '4+1' mixed-ligand complexes in which the radiometal is coordinated by a tripodal tetradentate chelator 2,2',2''-nitrilotriethanethiol (NS3) and a monodentate isocyanide ligand is presented. The labeling procedure was evaluated by the synthesis of [99mTc(NS3)(L2-RGD)]. The containing radiopharmaceutically interesting RGD-peptide cyclo[Arg-Gly-Asp-D-Tyr-Lys] was modified with 4-isocyanobutanoic acid (L2) as linker conjugated to N6-Lys to get the monodentate ligand L2-RGD. The structural identity of the 99mTc-conjugate was confirmed by comparison to a Re reference compound. The Tc- and Re-conjugates had matching retention times under identical HPLC conditions. The 99mTc-labeling was performed in a novel one-step procedure using the eluate of a 99Mo/99mTc generator, NS3, the isocyanide modified peptide, SnCl2, Na2EDTA, mannitol and ascorbic acid ...
A carrier-free radioiodinated phenylazide derivative of forskolin, 3-iodo-4-azidophenethylamido-7-O-succinyl-deacetyl-forskolin (({sup 125}I)IAPS-forskolin), has been shown to be a highly selective photoaffinity probe for the human erythrocyte glucose transported and the glucose transport proteins found in several mammalian tissues and cultured cells where the glucose transport protein is present at a low concentration. The photoincorporation of ({sup 125}I)IAPS-forskolin into these glucose transporters was blocked by D- (but not L-) glucose, cytochalasin B, and forskolin. In addition to labeling the mammalian glucose transport proteins, ({sup 125}I)IAPS-forskolin also labeled the L-arabinose transporter from E. coli. In muscle and adipose tissues, glucose transport is markedly increased in response to insulin. ({sup 125}I)IAPS-forskolin was shown to selectivity tag the glucose transporter in membranes derived from these cells. In addition, the ...
A carrier-free radioiodinated phenylazide derivative of forskolin, 3-iodo-4-azidophenethylamido-7-O-succinyl-deacetyl-forskolin (["1"2"5I]IAPS-forskolin), has been shown to be a highly selective photoaffinity probe for the human erythrocyte glucose transported and the glucose transport proteins found in several mammalian tissues and cultured cells where the glucose transport protein is present at a low concentration. The photoincorporation of ["1"2"5I]IAPS-forskolin into these glucose transporters was blocked by D- (but not L-) glucose, cytochalasin B, and forskolin. In addition to labeling the mammalian glucose transport proteins, ["1"2"5I]IAPS-forskolin also labeled the L-arabinose transporter from E. coli. In muscle and adipose tissues, glucose transport is markedly increased in response to insulin. ["1"2"5I]IAPS-forskolin was shown to selectivity tag the glucose transporter in membranes derived from these cells. In addition, the covalent ...
A few metal complexes of isatin-isonicotinoylhydrazone with Ni(II), Cr(III), Co(II), Cu(II), Zn(II) and Cd(II) have been prepared and characterized on the basis of elemental analyses, infrared and electronic spectra as well as "1H NMR spectra, conductivity and magnetic measurements. In view of the results obtained, it has been found that two molecules of isatin-isonicotinoylhydrazone are chelated to the central metal ion as bis-uninegative ONO tridentate ligand forming non-electrolytic octahedral metal complexes. (author)
The first preparation and characterization of the platinum (II) complexes containing five phosphorus ligands are reported herein. The complexes are represented by the formulae (Pt(PP/sub 3/)(P(OR)/sub 3/)Cl/sub 2/, where R = Me or Et, and (Pt(PP/sub 3/)(PEt/sub 3/))Cl/sub 2/. The /sup 31/P spectra of the complexes are presented. 10 references, 2 tables.
Polytetrafluoroethylene was obtained by radiation induced polymerization of tetrafluoroethylene in acetone at 195 K. An average diameter of the products was very small compared with commercial one; it was about 0.3 micro-meters. The yield was reached to 100% with a dose of 4 kGy. The crystallinity of the products is decreasing with increasing dose. The products become amorphous, for higher irradiation doses. It was found that PTFE obtained by irradiation of TFE in acetone at 195 K has branching structure. This was demonstrated by means of "1"9F MAS NMR. (Author)
Zeolite Y is the active component of most commercial cracking catalysts. Interaction of H[sub 3]PO[sub 4] with extraframework aluminum of ultra-stable zeolite (USY) leads to the formation of different types of aluminum phosphates, while there is no indication of the formation of SAPO zeotype structures. The total acidity of USY slightly decreases upon the H[sub 3]PO[sub 4] treatment, while the maximum in the distribution of acid strength is shifted to milder acidities. Dealumination of the zeolite and creation of POH sites associated with AIPO[sub 4] are responsible for the modifications observed. 37 refs., 8 figs., 3 tabs.
XVTa and XXTa nuclei were oriented at low temperature as dilute impurities in Fe. The magnetic hyperfine splitting frequencies = B sub(HF)/Ih of the XVTa and XXTa ground states have been measured to be 320.45(11) and 317.552(55) MHz by using the technique of NMR-ON. Taking the known hyperfine field of Y Ta in Fe, the magnetic moments have been deduced: ( XVTa, 7/2 ) =2.270(45) and ( XXTa, 7/2 ) =2.250(45) sub(N). These values of the magnetic moments are discussed in the framework of the rotational model.
"1"7"5Ta and "1"7"7Ta nuclei as dilute impurities in Fe were oriented at low temperatures. Using the technique of NMR/ON the magnetic moments have been measured: "+#mu#("1"7"5Ta, 7/2"+,"+=2.270(45) #mu# sub(N) and "+#mu#("1"7"5Ta, 7/2"+)"+=2.250(45) #mu# sub(N). These values are discussed in the framework of the rotational model. (author).
The authors continued their efforts in studying the mechanism of carbalkoxylation of {sigma}-vinyls bound to platinum(II). In this work, the focus was specifically on the reductive elimination of {alpha},{beta}-unsaturated carboxylic esters form the carbonylated, alkoylated intermediates. Crystal structures of the carbonylated (12) and alkoxylated (13) intermediates were reported. Kinetic and NMR studies indicate that reductive elimination proceeds via a preequilibration involving phosphine dissociation, followed by a rate-determining trans-cis isomerization. 35 refs., 3 figs., 5 tabs.
Decomposition yields of tetracycline hydrochloride (TC.HCl) and chlorotetracycline hydrochloride (ClTC.HCl) in methanol solution saturated with Ar or N/sub 2/O were determined. Rate constants of the reaction esub(s)/sup -/ with some antibiotics were obtained. It was demonstrated by /sup 1/H NMR that the radical formed by degradation of 7-C-Cl group is recombined with the H atoms leading to ClTC.HCl being converted into tetracycline hydrochloride (TC.HCl).
We have designed a new nucleobase, benzodeazaadenine (BDA) that has a stronger charge transport ability than guanine and is not destroyed during charge transport process. By incorporating this new nucleobase into DNA, we demonstrated a protocol for real DNA nano-wire that is far superior to natural DNA. We also demonstrated that the selectivity for the interaction of Mn(II) ion with guanine N7 in G runs is a HOMO-controlled process, and as a consequence, the selectivity for G-metal ion interactions obtained by 15N-NMR studies would directly reflect the HOMO distribution of G-containing sequences in B-DNA. PMID:12903077
The first stage of the continuous coal hydrogenation unit has been used to test a number of coals with different processing strategies. This work has shown that conversion increases with product recycle, however after the second pass the increase is small but operability of the reactor is considerably improved. A kinetic model for the aromatic saturation of the recycle solvent in the second stage has been developed and will be used in the selection of conditions for oil upgrading processes. New insights into the structural composition of coal derived materials have been made due to the refinement of chromatographic or solubility separation analyses into routine operations and the development of a new technique in NMR spectroscopy.
This paper describes the chemical constituents isolated from aerial parts of the plant Galianthe brasiliensis. From a methanol extract, the iridoid glycosides asperuloside, deacetylasperuloside, mixture of Z- and E-6-O-p-coumaroylscandoside methyl ester, the triterpene ursolic acid and the steroids stigmasterol, campesterol, b-sitosterol and 3-O-b-glucopyranosyl sitosterol were isolated. The structures of the natural products were identified on the basis of spectral data, including 2D NMR experiments. The antiproliferative properties of the crude methanolic extract were investigated against a series of nine human cancer cell lines. (author)
The rate of the oxygen-exchange reaction in an aqueous solution of a heterocyclic oxygen compound, 2,4,6-trimethylpyrylium perchlorate, was quantitated. The /sup 18/O isotope effect in /sup 13/C NMR spectroscopy affords a direct, continuous, and relatively simple analysis of the reaction and was used to obtain data on the incorporation of /sup 18/O from solvent H/sub 2//sup 18/O into the pyrylium salt. Due to the low solubility of this salt in aqueous solutions, 2,4,6-trimethyl(2-/sup 13/C)pyrylium perchlorate and 2,4,6-trimethyl(2,6-/sup 13/C/sub 2/)pyrylium perchlorate were synthesized to facilitate the acquisition of the data on an NTC-200 spectrometer operating at 50.31 MHz. Upon incorporation of /sup 18/O into the pyrylium salt, the /sup 13/C NMR signal of the directly bonded carbon atom is shifted upfield 0.038 ppm. A /sup 13/C isotope effect is also detected in the doubly /sup 13/C-enriched pyrylium salt where the /sup 13/C ...
The oxygen vacancies distribution in the rigid lattice and the thermally activated motion of oxygen atoms are studied in La1-xSrxGa1-xMgxO3-x (x=0.00; 0.05; 0.10; 0.15 and 0.20) compounds. For that 71Ga, 25Mg and 17O NMR was performed from 100 K up to 670 K, and ion conductivity measurements were carried out up to 1273 K. The comparison of the electric field gradients at the Ga- and Mg-sites evidences that oxygen vacancies appear exclusively near gallium cations as a species trapped below room temperature in local clusters, GaO5/2-#square#-GaO5/2. These clusters decay at higher temperature into mobile constituents of the structural octahedra Ga(O5/6#square#1/6)6/2. At the same time, the nearest octahedral oxygen environment of magnesium cations persists at different doping levels. The case of two adjacent vacant anion sites is found highly unlikely within the studied doping range. The thermally activated oxygen motion starts to develop above room temperature as is ...
NMR spectroscopy combined with paramagnetic relaxation agents was used to study the positioning of the 40-residue Alzheimer Amyloid {beta}-peptide A{beta}(1-40) in SDS micelles. 5-Doxyl stearic acid incorporated into the micelle or Mn{sup 2+} ions in the aqueous solvent were used to determine the position of the peptide relative to the micelle geometry. In SDS solvent, the two {alpha}-helices induced in A{beta}(1-40), comprising residues 15-24, and 29-35, respectively, are surrounded by flexible unstructured regions. NMR signals from these unstructured regions are strongly attenuated in the presence of Mn{sup 2+} showing that these regions are positioned mostly outside the micelle. The central helix (residues 15-24) is significantly affected by 5-doxyl stearic acid however somewhat less for residues 16, 20, 22 and 23. This {alpha}-helix therefore resides in the SDS headgroup region with the face with residues 16, 20, 22 and 23 directed away ...
This report seeks to address the role of hydrogen bonding with Bronsted acids and bases in proton-coupled electron transfer (PCET) as it pertains to concerted or stepwise pathways of quinone (Q) and hydroquinone (QH_2) electrochemistry. This study was performed using a series of techniques that included cyclic voltammetry (CV), digital simulations, computational chemistry and "1H NMR. Hydrogen bonding was inferred by a decrease in diffusion coefficient (D) values measured using a pulsed gradient echo- (PGE-) "1H NMR technique. Changes of 40.8% and 37.9% in D values were only noted after the addition of two equivalents of acetate to 1,4-hydroquinone (1,4-QH_2) and catechol (1,2-QH_2), respectively. In contrast, the D values for the addition of selected amines (pyridine, N,N-diisopropylethylamine and triethylamine) changed only 3.2% on average. Quantum mechanical calculations were conducted to determine the pK_a of all quinoid species to serve as ...
The synthesis of ["1"1C]phenobarbital, ["1"1C]pentobarbital and["1"1C]amobarbital labelled in the 5-[1-"1"1C]ethyl position is reported. The malonic esters R- CH(CO_2Et)_2 [R phenyl-, 1-methylbutyl-, and 3- methylbutyl- were alkylated with [1-"1"1C]ethyl iodide prepared from ["1"1C]carbon dioxide. Ring closure of the 2-[1-"1"1C]ethyl-labelled malonic esters with urea afforded 5-[1-"1"1C]ethyl-phenobarbital,-phenobarbital, -pentobarbital and -amobarbital synthesis times of 42-47 min, counted from ["1"1C] carbon dioxide. In typical syntheses starting with 3 GBq pentobarbitol and (81 mCi) ["1"1C]carbon dioxide, 150-215 MBq (4-6 mCi) were produced in 25-30% decay corrected -amobarbital radiochemical yields with radiochemical purities greater than 98%. (author).
The measurement of physiological parameters in man is possible with the help of positron emission tomography (PET) and radiopharmaceuticals labeled with short lived positron emitters as C 11, N 13, O 15 and F 18. With the use of this substances it is possible to make a tomographic map defining regional metabolic parameters in normal and diseased brain. This technique has therefore also be named 'in vivo autoradiography'. The possibility of applying C 11 or F 18 labeled deoxyglucose with PET for detecting regional and local changes in cerebral metabolic rate of glucose in brain development in children of 5 days to 1 year of age is discussed. Beyond this a relationship between cerebral metabolic rate of glucose, cerebral blood flow and cerebral metabolic rate of oxygen by use of this technique after inhalation of O 15 and C 11-labeled CO_2 is shown. Attention is drawn to the application of C 11-methyl-spiperone and PET to ...
The radioiodine-labeled amines currently available as brain-imaging agents, based on our previous work and that of others, are prepared either by exchange labeling or by direct iodination of a protected intermediate. The intrinsic slowness of these processes limits their potential for use with the positron-emitting 122I, as it has a half-life of only 3.6 min. This isotope has advantages of a low dose to the patient and availability from a generator containing the parent 20-h 122Xe. To develop a radiopharmaceutical in which 122I could be utilized, we prepared a number of secondary and tertiary amines (maintaining the 2,5-dimethoxy substitution pattern which allows direct iodination at the 4-position) with 131I. The organ distributions of these compounds were studied, and the best properties were found in the N,N-dimethyl homologue (2,5-dimethoxy-N,N-dimethyl-4-iodoamphetamine). This compound was successfully synthesized in a matter of seconds, ...
The radioiodine-labeled amines currently available as brain-imaging agents, based on our previous work and that of others, are prepared either by exchange labeling or by direct iodination of a protected intermediate. The intrinsic slowness of these processes limits their potential for use with the positron-emitting 122I, as it has a half-life of only 3.6 min. This isotope has advantages of a low dose to the patient and availability from a generator containing the parent 20-h 122Xe. To develop a radiopharmaceutical in which 122I could be utilized, we prepared a number of secondary and tertiary amines (maintaining the 2,5-dimethoxy substitution pattern which allows direct iodination at the 4-position) with 131I. The organ distributions of these compounds were studied, and the best properties were found in the N,N-dimethyl homologue (2,5-dimethoxy-N,N-dimethyl-4-iodoamphetamine). This compound was successfully synthesized in a matter of seconds, ...
The contribution of platelets and clotting factors in thrombosis on cardiovascular prostheses had been quantified with several tracers. Thrombus formation in vivo could be measured semiquantitatively in animal models and patients with indium-111, Technetium-99m labeled platelets, iodine-123, iodine-131 labeled fibrinogen, and In-111 and Tc-99m labeled antibody to the fibrinogen-receptor on the platelet- membrane, or fibrin. The early studies demonstrated that certain platelet-inhibitors, e.g. sulfinpyrazone, aspirin or aspirin- persantine increased platelet survival time with mechanical valves implanted in the baboon model and patients. Thrombus localization by imaging is possible for large thrombus on thrombogenic surface of prosthesis in the acute phase. The majority of thrombus was found in the sewing ring (Dacron) in the acute phase in both the mechanical and tissue valves. The amount of retained thrombus in both ...
Sucrose and mannitol are major photosynthetic products and translocates in celery. Assimilate partitioning and transport were studied by pulse-labeling leaves with /sup 14/CO/sub 2/ followed by different length chases in ambient air. After a 2 h chase in the light there was more /sup 14/C in sucrose than mannitol in source leaves and their petioles. In contrast after a 2 h dark chase leaves contained more /sup 14/C in mannitol than sucrose but petioles had more /sup 14/C in sucrose than mannitol. After a 15 h chase (6 h light; 9 h dark) labeled sucrose was higher in source petiole vascular bundles than in adjacent parenchyma tissue but label in glucose and fructose was higher in the parenchyma tissue. After the 15 h chase most of the /sup 14/C remaining in developing sink leaves and their petioles was in mannitol. Although in the light mannitol:sucrose ratios are the same in leaf and petiole tissues, in the dark sucrose is ...
The radiochemical purity of the cobalt-57 complex of bleomycin could be enhanced by adjusting the pH of the final product to a value between 5 and 6. This radiopharmaceutical appeared to have better tumor visualizing properties compared to the not neutralized preparation. The clinical use of the cobalt-57 bleomycin complex is however limited by the long physical half-life of the label, causing a risk of radioactive contamination. It appeared to be possible to label bleomycin with radioactive cations ("1"1"1In"3"+, sup(99m)Tc"4"+, "1"9"7Hg"2"+ and "6"7Cu"2"+) having suitable gamma ray energies and short half-lifes. These bleomycin complexes showed a high radiochemical purity judged by their behaviour on thin layer chromatography, paper chromatography, and electrophoresis, but their application as tumor visualizing radiopharmaceutical turned out to be disappointing compared with cobalt-57 bleomycin. (orig.).
Gel filtration of human erythrocyte (RBC) lysate incubated with labeled thyroxine (Tu) or triiodothyronine (Tt) revealed co-elution of a major iodothyronine-binding fraction (R-2) and hemoglobin. Solutions of purified human hemoglobin and Tt also showed co-elution of hormone and hemoglobin. Because hematin and protoporphyrin were shown to bind labeled Tt, the oxygen-binding site on hemoglobin was excluded as the site of iodothyronine-hemoglobin interaction. Analysis of hormone binding by heme and globin moieties showed Tt binding to be limited to the heme fraction. Addition of excess unlabeled Tt to hemoglobin or heme incubated with labeled Tt indicated 75% to 90% of hormone binding was poorly dissociable. These observations suggested that the presence of hemoglobin in RBC lysate or in serum could influence the measurement of Tu and Tt by specific radioimmunoassay (RIA). Subsequent studies of the addition to serum of human ...
The aim of this study was to assess the utility of a radioimmunoconjugate containing a lead radionuclide for therapy and scintigraphy applications. The radioimmunoconjugate evaluated consisted of a bifunctional DOTA ligand and monoclonal antibody (MAb) B72.3 using athymic mice bearing LS-174T tumors, human colon carcinoma xenografts. In the studies reported here, the lead-203-DOTA complex itself was first demonstrated to have in vivo stability. MAb B72.3 was then conjugated with the DOTA ligand and labeled with "2"0"3Pb, and the immunoreactivity of B72.3 was maintained. The localization of the radioimmunoconjugate to tumor tissue and other select organs paralleled that of DOTA-"1"2"5I-B72.3, suggesting a similar metabolic pattern of the two radioimmunoconjugates. Thus, the DOTA-metal complex does not alter the behavior of the radioimmunoconjugate. Tumor localization of the "2"0"3Pb-DOTA-B72.3 conjugate was demonstrated with biodistribution studies as well as ...
The effects of mouse epidermal growth factor (EGF) on bone formation and resorption were examined in male mice. EGF administration (2-200 ng.g-1.day-1 ip for 7 days) induced a dose-dependent rise in plasma EGF levels that remained within physiological range. Histomorphometric analysis of caudal vertebrae showed that EGF (20 and 200 ng.g-1.day-1) reduced the endosteal matrix and mineral appositional rates after 5 days of treatment as measured by double (3H)proline labeling and double tetracycline labeling, respectively. This effect was transitory and was not observed after 7 days of EGF administration. EGF administered for 7 days induced a dose-dependent increase in the periosteal osteoblastic and tetracycline double-labeled surfaces. At high dosage (200 ng.g-1.day-1) EGF administration increased the osteoclastic surface and the number of acid phosphatase-stained osteoclasts, although plasma calcium remained normal. The ...
Dynamics and metabolism of sugars translocated into the fruit region were investigated in tomato using {sup 14}C-labelled compounds. The translocation substance in tomato is thought to be sucrose, but the amount of sucrose in its fruit is very small. Therefore, the degradation of sucrose in the fruit and its translocation to the fruit was investigated. The sucrose was digested into hexoses such as glucose, fructose, etc. and the degradation rate was considerably low. In the stage of thickening growth, sucrose was more extensively converted into other substances except for sugars compared with the coloring stage. Then, {sup 14}C-labelled fructose was given through its gynophore to investigate the degree of reproduction to sucrose. The fructose level in the fruit reached the platean by 48 hrs after the addition and gradually decreased. The radioactivities were detected in sugars, organic acids and other alcohol soluble substances, etc. These ...
Six men were fed a diet composed of conventional foods with all bread as whole wheat bread. Intrinsically labeled "6"5Cu bread (containing 6.5 ppm Cu and 48 atom % "6"5Cu) was substituted for unlabeled bread for 3 days, and stools were collected for 24 days. Extrinsically labeled bread was then substituted for 3 days and another 24-day stool collection made. "6"5Cu excretion was measured by mass spectrometry. Mean Cu intake was 1.10 mg of Cu/day. Average Cu balance was /minus/0.06 /+-/ 0.08 mg/day. Average absorption of the intrinsic copper was 72.2 /+-/ 9.3% and of extrinsic Cu 64.2 /+-/ 5.8%. The ratio of extrinsic to intrinsic absorption was 0.906 /+-/ 0.164. Absorption of intrinsic and extrinsic tracers did not differ significantly (p > 0.05) by a paired t-test, and the ratio (E/I) was not significantly different from 1. Use of extrinsic Cu tracers to assess Cu absorption is supported by these results.
The circulation in microvascularized rib grafts has been compared with that in conventional rib grafts and in those augmented by a direct vascular bundle implantation into the bone grafts. A new experimental model has been designed to correlate vascular perfusion, bone scan patterns, tetracycline labeling, and histological findings in these bone grafts. Posterior microvascularized rib grafts were found to have a circulatory pattern identical to that of the normal rib. Failed microvascularized rib grafts were revascularized more slowly than conventional rib grafts. Vascular bundles implanted into rib grafts remained patent and increased the rate of revascularization. The stripping or preservation of periosteum had no observable effects on the rate or pattern of conventional rib graft revascularization. The circulation in rib grafts was accurately reflected in technetium 99 bone scans, as was the patency of the anastomoses of microvascularized rib grafts and of ...
Metabolic carbon labelling experiments enable a large amount of extracellular fluxes and intracellular carbon isotope enrichments to be measured. Since the relation between the measured quantities and the unknown intracellular metabolic fluxes is given by bilinear balance equations, flux determination from this data set requires the numerical solution of a nonlinear inverse problem. To this end, a general algorithm for flux estimation from metabolic carbon labelling experiments based on the least squares approach is developed in this contribution and complemented by appropriate tools for statistical analysis. The linearization technique usually applied for the computation of nonlinear confidence regions is shown to be inappropriate in the case of large exchange fluxes. For this reason a sophisticated compactification transformation technique for nonlinear statistical analysis is developed. Statistical analysis is then performed by computing ...
An irradiation head with sample holders is described and measurement geometry is reported. Measurements were made for optimizing the distance between the source and the sample and for optimizing the sample diameter. The optimal distance between the source and the sample does not depend on the collimator diameter. The sample diameter should not exceed 30 - 35 mm. Sensitivity and detection limits were determined for Zn, Pb and Br and calibration curves were plotted. (M.D.) 6 figs., 2 tabs., 4 refs.
This paper describes a method for preparing the sample handling and inlet system of a mass spectrometer for analysis of a subsequent sample following analysis of a previous sample comprising the flushing of the system interior with supercritical CO{sub 2} and venting the interior. The method eliminates the effect of system ``memory`` on the subsequent analysis, especially following persistent samples such as xenon and krypton.
If a closed smooth manifold $M$ with an action of a torus $T$ satisfies certain conditions, then a labeled graph $\\mG_M$ with labeling in $H^2(BT)$ is associated with $M$, which encodes a lot of geometrical information on $M$. For instance, the "cohomology" ring $\\mHT^*(\\mG_M)$ of $\\mG_M$ is defined to be a subring of $\\bigoplus_{v\\in V(\\mG_M)}H^*(BT)$, where $V(\\mG_M)$ is the set of vertices of $\\mG_M$, and is known to be often isomorphic to the equivariant cohomology $H^*_T(M)$ of $M$. In this paper, we determine the ring structure of $\\mHT^*(\\mG_M)$ when $M$ is a flag manifold of classical type directly without using the fact that $\\mHT^*(\\mG_M)$ is isomorphic to $H^*_T(M)$.
Two no-carrier-added "1"2"5I-labelled photoaffinity rapamycin analogs were prepared: 7-demethoxy-7-(4-azido-3-"1"2"5I-benzyloxy) rapamycin and its C_2_8-C_2_9 seco analog. The key reactions of the synthesis were substitution of the C_7 methoxyl of rapamycin with 4-azido-3-tributylstannylbenzyloxy group, exchange of tributyltin with "1"2"5I using Na"1"2"5I and Chloramine-T, and a ZnCl_2 mediated retro-Aldol cleavage of the C_2_8-C_2_9 bond of rapamycin. (author).
Two peptide ligands conjugated adenine, [9-N-(tritylmercapto acetyl diglycyl aminoethyl) adenine, Tr-MAG_2-Ade] and [9-N-(tritylmercapto acetyl triglycyl aminoethyl) adenine, Tr-MAG3-Ade], are synthesized and labeled with "9"9"mTc by directly labeling method. The stability of "9"9"mTc-MAG_2- adenine and "9"9"mTc-MAG_3-adenine in vitro is measured. The uptake radios of tumor to muscle at 3h post-injection are 5.70 and 4.92, respectively. The biodistribution and scintigraphic imaging studies show that the two complexes have high localization in tumor and high contrasted tumor images can be obtained, which suggest their potential utility as tumor imaging agents. But the high radioactivity of abdomen could prevent the tumor imaging in this area. (author)
When labeled cAMP is incubated with isolated mitochondria from rat liver, it penetrates not only through the outer membrane of the mitochondria but also into the mitoplasts, where it is accumulated chiefly in the matrix. Damage to the mitochondrial membrane by freezing-thawing promotes not an influx but an efflux of cAMP out of the mitoplasts. A substantial part of the labeled nucleotide in all the investigated submitochondrial fractions was identified as intact cAMP by the method of thin-layer chromatography. The transport of cAMP into the mitochondria can explain the activation of their functions by the hormones that activate cytoplasmic adenylate cyclase and by extramitochondrial (cytosol) cAMP, as well as the presence of cAMP-dependent protein kinase and cAMP-phosphodiesterase in the mitochondria.
Eight patients with double-velour Dacron aorto-femoral grafts implanted for 2-60 months were studied. Indium-111-labelled platelets were found to have a shortened mean platelet lifespan (MPLS) of 138 +- 32 hours compared with the normal platelet lifespan of 224 +- 23 hours. Labelled platelets accumulated on all grafts, irrespective of graft age, to a maximum of 1,80 +- 0,83% of whole body radioactivity; thereafter graft radio-activity decreased. This suggests that platelets on the graft are in dynamic equilibrium with those in the circulation. Platelets may be lost from the graft by embolization or radioactivity may be released because of platelet lysis. Although MPLS may depend on the age and surface area of the graft, concomitant arterial disease probably also contributes to the shortened MPLS.
This paper describes the design and operating experience with a high performance control system tailored to the requirements of the SuperHILAC accelerator. A large number (20) of the latest 16-bit microcomputer boards are used in a parallel-distributed manner to get a high system bandwidth. Because of the high bandwidth, software costs and complexity are significantly reduced. The system by its very nature and design is easily upgraded and repaired. Dynamically assigned and labeled knobs, together with touch-panels, allow a flexible and efficient operator interface. An X-Y vector graphics system provides for display and labeling of real-time signals as well as general plotting functions. This control system allows attachment of a powerful auxiliary computer for scientific processing with access to accelerator parameters.
Major depressive disorder and alcohol dependence are common and serious mental illnesses. There is a great interest in discovering useful treatments for both mood symptoms and alcohol abuse in those patients with depressive disorders and comorbid alcohol dependence. The primary purpose of this study was to evaluate the effectiveness and tolerability of mirtazapine for the treatment of patients with alcohol dependence comorbid with a depressive disorder in an open label, naturalistic multicentre treatment setting. The 17-item Hamilton Depression Rating Scale (HDRS), the Hamilton Anxiety Rating Scale (HARS) and the Clinical Global Impression-Severity (CGI-S) scale were measured at baseline and at weeks 4 and 8 for the assessment of treatment effectiveness. Alcohol craving was measured using ...
Mineralization and volatilization of ring labelled "1"4C-2,4-dichlorophenoxyacetic acid in soil was studied over a period of six weeks under laboratory conditions at 25 deg. C in three different soils collected from three sites, Delhi, Jaipur and Ludhiana. A very slow rate of both mineralization and volatilization was observed in all the three soils. The observed mineralization, was highest for the Delhi soil, 0.93%, followed by the Ludhiana soil, 0.73% and the Jaipur soil 0.14% in 42 days. The extent of volatilization was 0.46% for the Jaipur soil, 0.37% for the Ludhiana soil and 0.32% for the Delhi soil. (author)
Within the past decade two important groups of radiopharmaceuticals labelled with /sup 123/I were introduced into the clinical application opening new areas of metabolic studies in nuclear medicine: radioiodinated fatty acids were developed for metabolic studies of the myocardium and radioiodinated amphetamine derivatives were prepared for studying brain diseases by means of SPECT. It must be emphasized that the radiochemical problems with both groups of compounds are practically the same since both are radioiodinated by a nucleophilic substitution mechanism using /sup 123/I directly in its anionic form. The clinical application of brain imaging agents, particularly the one of p-/sup 123/I-iodo-N-isopropylamphetamine, is important and will presumably increase as soon as the details of the individual biochemical steps, which are involved in brain uptake mechanisms, are evaluated. It is felt that the potential of the clinical IMP application is greater than the ...
Labelling of "1"4C-M-ISP and its absorption, translocation and distribution in peanut and soybean seedling were studied. The results of experiments showed that the radioactive substance could be translocated in xylem and phloem of two kinds of plants. The root of peanut seedling absorbed "1"4C-M-ISP from the nutrient solution more strong than the root of soybean seedling did. After leaf treatment with "1"4C-M-ISP, the soybean seedling absorbed more radioactive substance than peanut seedling did. But the translocation's speed of radioactive substance in pnloem of two kinds of plants were similar.
This paper aims to explore consumer preference for fresh vegetables labelled as organic in combination with health and environment related quality traits. The study decomposes organic farming into its main quality aspects and measures consumers' preference structure for organic, in general, and for specific organic quality traits in particular. By means of stated choice preference modelling, the following hypotheses are tested: consumers prefer health over environment related quality traits; the organic label plays a significant role in consumers' choice for organic products; organic farming is perceived as healthier and more environmentally friendly than conventional farming; purchase intention is mainly driven by health related quality traits; both health and environmental concerns influ...
Hydrogen cyanide (HCN) production by Pseudomonas aeruginosa in a synthetic medium is stimulated by the presence of glycine. Methionine enhances this stimulation but will not substitute for glycine as a stimulator of cyanogenesis. Threonine and phenylalanine are effective substitutes for glycine in the stimulation of HCN production. Glycine, threonine, and serine are good radioisotope precursors of HCN, but methionine and phenylalanine are not. Cell extracts of P. aeruginosa convert (/sup 14/C)threonine to (/sup 14/C)glycine. H14CN is produced with low dilution of label from either (1-/sup 14/C)glycine or (2-/sup 14/C)glycine, indicating a randomization of label either in the primary or secondary metabolism of glycine. When whole cells were fed (1,2-/sup 14/C)glycine, cyanide and bicarbonate were the only radioactive extracellular products observed.
Summary Background The seventh amendment of the European Union (EU) Cosmetics Directive (March 2005) and the Detergents Regulations of the EU (October 2005) are now legal requirements in Europe. Cosmetic products and detergents must be labelled for 26 individual named fragrances, when present at concentrations of > 10 parts per million (p.p.m.) in leave-on products and > 100 p.p.m. in rinse-off products. Objectives To make an assessment of the exposure pattern to fragrance of the U.K. consumer and to determine the frequency with which the constituent fragrances of fragrance mix I (FM I) and fragrance mix II (FM II) are included in products currently sold in the U.K. Methods A study of perfumed cosmetic and household products available on the shelves of U.K. retailers was carried out in Jan...
Proposed features of the competitive electricity market in Ontario were reviewed. The speaker predicted that demand for renewable energy in Ontario`s competitive electricity market will be affected by green power, emissions trading, labelling, and renewables portfolio standard. Under current regulations retailers can charge customers a premium for purchasing electricity generated by `green` sources. The existing limits on emissions of sulphur dioxide, nitrogen oxides and carbon dioxides will remain in place, but an emissions cap and trading program for all Ontario-based generation is an option to consider. Ontario`s Market Design Committee (MDC) has recommended the implementation of emissions trading for electricity-related air pollutants for all generators located in Ontario. The complex mechanics of emission trading are explained. The MDC recommendation of the use of standard labels to disclose the mix of energy sources used by sellers of ...
Abstract Background: Dementia with Lewy bodies (DLB) is a common dementia of the elderly. A significant cholinergic deficit has been demonstrated that may be responsive to treatment by cholinesterase inhibitors (ChEIs). Methods: A 24-week, open-label study was designed to assess the efficacy and safety of a ChEI, galantamine, in 50 patients with DLB. Results: This study showed beneficial effects with galantamine in 2 of the 3 primary efficacy parameters. The scores on the Neuropsychiatric Inventory (NPI-12) improved by 8.24 points from baseline (p = 0.01) especially in visual hallucinations and nighttime behaviors (p = 0.004). The scores on the Clinician's Global Impression of Change improved by 0.5 points from baseline (p = 0.01). The third primary efficacy parameter, the Cognitive Drug R...
Phenytoin (PHT), phenobarbital (PHB), lamotrigine (LTG), and topiramate (TPM) are some of the most widely used antiepileptic drugs (AEDs). Monitoring of their concentrations in serum is important for the treatment of epilepsy. A reference measurement procedure (RMP) for certification of PHT, PHB, LTG, and TPM in serum has been developed and critically evaluated. Isotopically labeled compounds of PHT, PHB, LTG, and TPM are used as internal standards for the four AEDs. The four drugs and their respective labeled internal standards are simultaneously extracted from serum using solid-phase extraction prior to reversed-phase liquid chromatography?tandem mass spectrometry (LC-MS/MS). Chromatographic separation was performed using a C18 column. Electrospray ionization (ESI) in the positive ion mo...
Methods were developed for the separation of radioactively labeled carbohydrate components of proteoglycans by isocratic ion-moderated partition HPLC. Neutral sugars were separated after hydrolysis in trifluoroacetic acid with baseline separation between glucose, xylose, galactose, fucose, and mannose. N-Acetylneuraminic acid, N-acetylated hexosamines, glucose, galactose, and xylitol were likewise well separated from each other under isocratic elution conditions. Glucuronic acid, iduronic acid, and their lactones were separated after hydrolysis in formic acid and sulfuric acid. Glucosamine, galactosamine, galactosaminitol, and glucosaminitol were separated by HPLC on a cation exchanger with neutral buffer after hydrolysis in hydrochloric acid. THe separation techniques also proved useful in fractionation of exoglycosidase digests of O- and N-linked oligosaccharides. Separations of aldoses, hexosamines, and uronic acids were adapted to sensitive photometric ...
Summary Background- Treatments that achieve sustainable steroid-free clinical remission in Crohn-s disease are needed; however, long-term steroid-sparing efficacy data are limited. Aim- To evaluate steroid-sparing efficacy and the impact of steroid discontinuation on adverse events during treatment of Crohn's disease with adalimumab in the phase III randomised, double-blind 1-year CHARM trial and for an additional 2-years in its open-label extension ADHERE. Methods- Steroid-free remission and response and steroid-sparing (-50% steroid dose reduction) remission rates were evaluated over 3-years in patients who were taking corticosteroids at CHARM baseline. Results- Of 778 patients randomised in CHARM (including those who did not achieve clinical response to open-label induction therapy), 31...
A new procedure for preparing an 211At-labeled radiopharmaceutical is suggested. The 211At? anion forms a strong bond with the Rh3+ cation incorporated in the complex with a thiother ligand, 1,5,9,13-tetrathiacyclohexadecane-3,11-diol (16-S4-diol). The reaction conditions are optimized with 131I as astatine analog. The complexes are studied by paper electrophoresis, ion exchange, and thin-layer chromatography. The kinetics of the addition of the 131I? anion to Rh(16-S4-diol) and the dependence of the yield of the forming complex 131I-Rh(16-S4-diol) on the temperature, solution acidity, and reactant concentrations are examined. Taking into account the results obtained, the complex 211At-Rh(16-S4-diol) is prepared by adding astatide (211 At?) to equivalent amounts of RhCl3 and the tetrathioe...
A multiple probe approach of implanting microdialysis probes into each separate tissue layer would better represent sampling from the stomach. Presently, microdialysis sampling experiments are...Full Text Available
Feed samples from 94 cases involving fungal contamination and suspected mycotoxicosis of farm animals in western Canada were examined during 1982-1994 to assess the incidence of mycotoxins. Samples...Full Text Available
Invasive prenatal testing has become an important way to evaluate fetuses at increased risk for hereditary disorders. In utero sampling of fetal skin, liver, and muscle may be required to diagnose before-birth...Full Text Available
The purpose of this report is to describe the sampling approaches, modifications made to the 100 Area and 300 Area component of the RCBRA Sampling and Analysis Plan, summarize validation efforts, and provide sample identification numbers.
The Rotary Mode Core Sample System (RMCSS) is used to obtain stratified samples of the waste deposits in single-shell and double-shell waste tanks at the Hanford Site. The samples are used to characterize the waste in support of ongoing and future waste remediation efforts. Four sampling trucks have been developed to obtain these samples. Truck I was the first in operation and is currently being used to obtain samples where the push mode is appropriate (i.e., no rotation of drill). Truck 2 is similar to truck 1, except for added safety features, and is in operation to obtain samples using either a push mode or rotary drill mode. Trucks 3 and 4 are now being fabricated to be essentially identical to truck 2.
Removal Sampling is an easy-to-use Windows program which calculates population statistics from removal trapping experiment data. Using maximum likelihood methods it ... ...
Rationale and ObjectivesSample-size estimation is an important consideration when planning a receiver operating characteristic (ROC) study. The aim of this work was...Full Text Available
Here we describe the fabrication, optimization, and application of a microfluidic device that integrates microdialysis (MD) sampling, microchip electrophoresis (ME), and electrochemical detection...Full Text Available
The National Food and Nutrient Analysis Program (NFNAP) was implemented in 1997 to update and improve the quality of food composition data maintained by the United States Department of Agriculture (USDA). NFNAP was designed to sample and analyze frequently consumed foods in the U.S. food supply using statistically rigorous sampling plans, established sample handling procedures, and qualified analytical laboratories. Methods for careful handling of food samples from acquisition to analysis were developed to ensure the integrity of the samples and subsequent generation of accurate nutrient values. The infrastructure of NFNAP, under which over 1500 foods have been sampled, mandates tested sample handling protocols for a wide variety of foods. The majority of these foods were categorized into ...
Positron emission tomography (PET) imaging of {beta}-amyloid (A{beta}) plaques in the brain is a potentially valuable tool for studying the pathophysiology of Alzheimer's disease (AD). It may also be applicable for measuring the effectiveness of therapeutic drugs aimed at lowering A{beta} plaques in the brain. We have successfully reported a series of {sup 18}F-labeled fluoropegylated stilbenes for PET imaging studies. Encouraging results clearly demonstrated the usefulness of {sup 18}F-labeled stilbenes as potential A{beta} plaque-imaging agents. In the present study, we applied a similar approach to a styrylpyridine backbone structure. Among all derivatives examined (E)-2-(2-(2-(2-fluoroethoxy)ethoxy)ethoxy)-5-(4-dimethylaminostyryl) -pyridine (2) displayed high binding affinity in postmortem AD brain homogenates (K {sub i}=2.5{+-}0.4 nM, with [{sup 125}I]IMPY as radioligand). No-carrier-added [{sup 18}F]2 was successfully prepared ...
The authors describe an effect of suppression of invasion of the guinea pig eye conjunctiva and the HEp-2 epithelial cells by virulent Sh. flexneri bacilli, with a simultaneous administration of the same dose of avirulent shigella mutants, genetically connected with them. The data of morphological study and experiments with 3H-glucose labeled shigellae carried out on the cell species model indicated that the bacterial competition for the specific sites for absorption on the epithelial cells underlay the observed phenomenon. PMID:331774
The grafted human glioblastoma cell CB109 was used as a model for intralesional therapy with 131I-labelled hyaluronectin glycoprotein (131I-HN). 131I-HN bound specifically to in situ hyaluronic acid (HA), a main component of the extracellular matrix which is involved in tumour invasion. Labelling experimental conditions were determined and, finally, 25 {mu}Ci/{mu}gHN, 1 {mu}g chloramine-T/{mu}gHN and a 60-s stirring period provided a 131I-HN preparation with an optimal affinity for HA (64% compared to unlabelled HN). Following intratumoral injection, 131I-HN was retained with a limited diffusion outside the tumour. On day 4 the radioactivity concentrated in the tumour was still 25 times greater than that in the liver, spleen and kidneys combined. For therapeutic assays, 65 {mu}Ci 131I-HN was injected into the tumour, resulting in a delivery of 6.8 Gy over a 7-day period. Controls received unlabelled HN, heat-inactivated HN, a mixture of ...
Hyaluronate (HA) distribution patterns were examined in the cranial mesenchyme underlying the mesencephalic neural folds of mouse embryos maintained in roller tube culture. Using standard image-processing techniques, the digitized images of Alcian blue-stained or 3H-glucosamine-labeled sections digested with an enzyme specific for HA, were subtracted from adjacent, undigested sections. The resultant difference picture images (DPI) accurately depicted the distribution of stained or labeled HA within the cranial mesenchyme. 3H-glucosamine-labeled HA was distributed uniformly throughout the cranial mesenchyme as 12, 18, and 24 hr of culture. By contrast, the mesenchyme was uniformly stained with Alcian blue at 12 hr, but stain intensity decreased in the central regions of the mesenchyme at 18 and 24 hr. HA distribution patterns were also examined in the cranial mesenchyme of embryos cultured in the presence of ...
Abstract Overall Numbers Small, But Study Finds SSRI Exposure, Autism Link Additional Drug Safety, Efficacy Data Needed for Pediatric Bipolar Disorder SGA Safety and Efficacy in Children and Adolescents Aripiprazole Safety and Tolerability for Irritability in Autism No Lisdexamfetamine Effect on Sleep Disturbances in Children With ADHD Sickle Cell Disease With Comorbid Depression Homeopathy in Psychiatry Manic Symptoms Induced by Marijuana in a Healthy Adolescent New Warnings Safety Labeling Changes
rho-Iodo-phentermine (IP) and two of its derivatives, N,N,-dimethyl-rho-iodo-phentermine (IDMP) and N-isopropyl-rho-iodo-phentermine (IIP) were synthesized and radiolabelled with iodine by isotopic exchange. They were evaluated as potential brain imaging agents and compared to IAMP. Biodistribution studies in rats did not show that these compounds were superior to IAMP.
The use of stable indole-3yl-acetic acid (IAA) labeled by 6 atoms of 13C allowed, after [13C]IAA treatment, simultaneous gas chromatography-mass spectrometry quantifications of...Full Text Available
Acetylcholine-rich synaptic vesicles were isolated from myenteric plexus-longitudinal muscle strips derived from the guinea pig ileum by the method of Dowe, Kilbinger, and Whittaker [J. Neurochem. 35, 993-1003 (1980)] using either unstimulated preparations or preparations field-stimulated at 1 Hz for 10 min using pulses of 1 ms duration and 10 V . cm-1 intensity. The organ bath contained either tetradeuterated (d4) choline (50 microM) or [3H]acetate (2 muCi . ml-1); d4 acetylcholine was measured by gas chromatography-mass spectrometry. As with Torpedo electromotor cholinergic vesicle preparations made under similar conditions the distribution of newly synthesized (d4 or [3H]) acetylcholine in the zonal gradient from stimulated preparations was not identical with that of endogenous (d0, [1H]) acetylcholine, but corresponded to a subpopulation of denser vesicles (equivalent to the VP2 fraction from Torpedo) that had preferentially taken up newly synthesized transmitter. The density ...
Sulfate activation occurs in Euglena mitochondria the authors now find that the sulfate activating enzymes are absent from Euglena chloroplasts. Cells of mutant W/sub 10/BSmL lacking plastids also lack detectable sulfolipid (SL) when grown on /sup 35/SO/sub 4//sup 2 -/ indicating that SL is absent from the mitochondria and is exclusively in the plastids. Plastids alone will convert /sup 35/S-cysteine to /sup 35/SL in the presence of ATP and Mg/sup 2 +/; light is stimulatory. Under similar conditions, chloroplasts and mitochondria incubated together convert /sup 35/SO/sub 4//sup 2 -/ to plastid-localized /sup 35/SL but either organelle incubated alone fails to effect this conversion. Unlabeled cysteine blocks SL labeling from sulfate in the mixed incubation; since cysteine is formed from sulfate by Euglena mitochrondria, cysteine (and other compounds) may move from the mitochondrion to the chloroplast to provide the sulfo group for SL formation. Although ...
Excision repair in uv irradiated human fibroblasts has been examined in portions of DNA replicating after irradiation versus those remaining unreplicated. Two approaches, one using a uv-endonuclease to estimate pyrimidine dimers remaining in DNA, the other using density labeling to measure excision resynthesis, indicate that the extent of repair is the same for both replicated and unreplicated DNA.
Lead-203 [52.1 h, 279 (80.1%) KeV] has been recognized as a potentially useful tracer for tumor specific radiopharmaceuticals due to its favorable nuclear and chemical properties. This paper reports the cyclotron production of lead-203 and the labelling of monoclonal antibody B72.3, conjugated with 2-(p-isothiocyanatobenzyl)DOTA, with lead-203 in 30% yield. In vivo biodistribution and stability studies in mice are being conducted.
Isolated fifth internodes of Coleus blumei Benth. were supplied with 3H-IAA at their apical ends. Microradioautography, using thin sections (0.25-0.5 microns) of Epon embedded...Full Text Available
In developing new receptor-site specific brain imaging agents labeled with I-123 for single photon emission computed tomography (SPECT), an analog of raclopride, 3-["1"2"5I]-iodo-N-[(1-ethyl-2-pyrrolidinyl)-methyl]-2-hydroxy-6-me-thoxy benzamide (IBZM), was prepared using a method similar to that reported for raclopride and its derivatives. (author).
The synthesis of a new kind of magnetic, fluorescent multifunctional nanoparticles (~30 nm in diameter) was demonstrated, where multiple fluorescent CdTe quantum dots (QDs) are covalently linked...Full Text Available
Positron emission tomography (PET) and magnetic resonance imaging (MRI) studies were performed on a case of neuro-Behcet's syndrome. In accordance with the clinical signs, FDG PET (using /sup 18/F-labeled 2-F-2'-desoxyglucose) revealed disseminated storage defects in the cerebrum and cerebellum. Focal regions of enhanced signal intensity were demonstrated in the parietal white matter of the cerebrum in T2-weighted images and in the brain stem by MRI. (orig.).
Methanobacterium thermoautotrophicum, M. ruminantium, and Methanosarcina barkeri were labeled with 14CO2 (14CO2 + H14CO3- + 14CO32-) for from 2 to 45 s. Radioactivity was recovered in coenzyme M derivatives,...Full Text Available
Anti-TAG-72 monoclonal antibodies target the tumor-associated glycoprotein (TAG)-72 in various solid tumors. This study evaluated the use of anti-TAG-72 monoclonal antibodies, both murine CC49...Full Text Available
This comprehensive, critical review summarizes the use of nanoparticles in enhanced and amplified chemiluminescence detection, illustrated by different reaction strategies, electrogenerated chemiluminescence sensors, immunoassay or hybridization labels and electrogenerated chemiluminescence immunoassay or hybridization sensors. We discuss the analytical applications on the basis of validity, range and sensitivity, and draw some useful conclusions about the most sensitive approach in each type of application.
The "1"3"1I-labelled monoclonal antibodies 791T/36 and 79IT/36 Fab fragments have been evaluated in the imaging of patients with colorectal cancer, with benign colorectal tumours, and with malignant tumours of other parts of the gastrointestinal tract. The results of clinical imaging have been carefully correlated with clinical findings and direct measurement of the preferential uptake of antibody by the tumours. (UK).
This paper describes a method for measuring oil consumption in compressors. The oil is labelled with Zn 65. The consumed radioactive oil is retained in an activated carbon filter and its activity is measured continuously with a plastic scintillator detector. Measuring the oil consumption at a given operating levels takes about 15 minutes. At an oil consumption rate of about 1 g/h the measurement errors are of the order of +- 5%. (orig.).
The alkylation products formed by in vitro treatment of DNA with tritium-labeled 1,3-bis(2-chloroethyl)-1-nitrosourea (3H-BCNU) were identified and quantified. Twelve adducts were resolved...Full Text Available
Objectives1) To establish a protocol for transfection of immortalised type I cells with SiRNA and its effect on cell viability; 2) To optimise silencing of genes involved in endocystosis using SiRNA and confirm successful transfection with western blotting; 3) To investigate the effect of gene silencing on uptake of flourescently-labelled latex nanoparticles.DescriptionTo investigate the mechanisms of particle uptake.
DescriptionAs part of a wider effort to develop new approaches to evaluating and quantifying the benefits of chemicals regulation, this project will review the effectiveness of existing information provision tools (such as classification and labelling for hazardous properties) in terms of affecting user behaviour. As some EC legislation relating to regulation of chemicals has been in place for some time, an assumption is made that the information provided by it is leading to an improvement in the way chem [continued...
Short term (10 min) influx of 86Rb-labeled potassium into corn (Zea mays L. WF9 × M14) root segments was inhibited by La (NO3)3 or LaCl3....Full Text Available
Infections of aortoarterial prostheses are serious, difficult to detect, and difficult to treat. Scintigraphy with indium-111 labeled autologous leukocytes is an accurate noninvasive method of assessing the presence and extent of such an infection. In three cases of aorto-arterial bypass graft infections, the leukocyte study was successful in establishing the diagnosis and in assessing the extent of infection. Other noninvasive diagnostic techniques are useful, but all have serious limitations. The leukocyte study alone appears to be free of likely sources of error.
The affinity label 8-((4-bromo-2,3-dioxobutyl)thio)adenosine 5{prime}-triphosphate (8-BDB-TA-5{prime}-TP) reacts covalently with rabbit muscle pyruvate kinase, incorporating 2 mol of reagent/mol of enzyme subunit upon complete inactivation. Protection against inactivation is provided by phosphoenolpyruvate, K{sup +}, and Mn{sup 2+} and only 1 mol of reagent/mol of subunit is incorporated. The authors have now identified the resultant modified residues. After reaction with 8-BDB-TA-5{prime}-TP at pH 7.0, modified enzyme was incubated with ({sup 3}H)NaBH{sub 4} to reduce the carbonyl groups of enzyme-bound 8-BDB-TA-5{prime}-TP and to introduce a radioactive tracer into the modified residues. Following carboxymethylation and digestion with trypsin, the radioactive peptides were separated on a phenylboronate agarose column followed by reverse-phase high-performance liquid chromatography in 0.1% trifluoroacetic acid with an acetonitrile gradient. Gas-phase sequencing ...
Extending the usual endpoint and midpoint interactions, we introduce numerous kinds of interactions, labelled by a parameter lambda and obtain a non-commutative and associative string field algebra by adding up all interactions. With this algebra we develop a covariant open bosonic string field theory, which reduces to Witten's open bosonic string field theory under a special string length choice.
DNA from 48 hr germinated rice embryos was cut with restriction endonuclease Bam H1 and cloned to the Bam H1 site on plasmid pBR 322. The clones containing recombinant DNA were selected by their sensitivity to tetracycline and resistance to ampicillin. Using /sup 32/P-labelled rice embryos tRNA as a probe two clones were identified to contain tRNA genes by colony hybridization.
A liquid barrier filter for use in fluorescence microscopy of strongly autofluorescent plant tissues is described. The filter consists of a methanol solution of cupric chloride and ferric chloride and isolates fluorescein fluorescence from the strong red autofluorescence of photosynthetic plant tissues. Subcortical actin cables in the giant alga Chara are being visualized through use of this filter together with heavy meromyosin labeling. PMID:90068
This book contains 18 selections. Some of the titles are: Labelling of amphetamines with /sup 123/I: Receptors for amphetamines; New amphetamine derivatives; Potential new approaches for the development of brain imaging agents for single-photon applications; and IM SPECT with the pinhole collimator.
This book contains 18 selections. Some of the titles are: Labelling of amphetamines with /sup 123/I: Receptors for amphetamines; New amphetamine derivatives; Potential new approaches for the development of brain imaging agents for single-photon applications; and IM SPECT with the pinhole collimator.
This Guideline provides a set of procedures for the measurement of organic contaminants and particles in producer gases from biomass gasifiers. The procedures are designed to cover different gasifier types (updraft or downdraft fixed bed or fluidised bed gasifiers), operating conditions (0 - 900C and 0.6-60 bars) and concentration ranges (1 mg/m{sub n}{sup 3} to 300 g/m{sub n}{sup 3}). The Guideline describes a modular sampling train, and a set of procedures, which include: planning and preparation of the sampling, sampling and post-sampling, analysis, calculations, error analysis and reporting. The modular sampling train consists of 4 modules. Module 1 is a preconditioning module for isokinetic sampling and gas cooling. Module 2 is a particle collection module including a heated filter. Module 3 is a tar collection module with a gas quench (optionally by ...
In order to study the neurobiological basis of seasonal changes in hippocampal structure and function, the rate of cell proliferation was examined in male and female wild meadow voles captured during different seasons. We found that the number of [3H]thymidine-labeled cells varied across the seasons and across sex in the meadow vole. Non-breeding female meadow voles had a higher rate of cell proliferation and cell death than males captured during either season or breeding females. These seasonal changes in the female meadow vole were associated with both fluctuating levels of adrenal steroids and gonadal steroids. Estradiol level was highly correlated with both the number of [3H]thymidine-labeled cells and the number of pyknotic cells in female meadow voles, with high levels of estradiol being associated with low levels of cell proliferation and cell death. Corticosterone level was associated with the number of ...
Indium-111 is currently the radionuclide of choice for colonic transit study. However, it is expensive and not available in many hospitals. Technetium-99m has been proposed for colonic transit study but the short half-life has limited its use. Gallium-67 citrate is inexpensive and available in most countries. Most importantly, it has a suitable half-life for colonic transit study. Attempts have been made in some studies to use {sup 67}Ga citrate to label activated charcoal, but the results have not been good because of poor stability. In this study, we successfully labelled activated charcoal with {sup 67}Ga citrate by adding alcohol and 5% glucose solution. To evaluate the in vitro stability, the {sup 67}Ga-activated charcoal was incubated in a milieu mimicking the intestinal content, containing lipase, trypsin and glycochenodeoxycholate at different pH values (6.0, 7.0, 7.4 and 8.0) and for different durations (0 h, 24 h, 48 h, 72 h and 96 ...
Serotonin is one of the neurotransmitters found in the brain and mediates brain functions. It is very well known that serotonin related brain abnormalities are exerted mainly via serotonin receptors in a similar manner to other neurotransmitters found in the brain. Recently, it has also been found that serotonin is involved in Alzheimer's disease either directly or indirectly by its actions on serotonergic neurons. To understand and treat the diseases caused by abnormalities in the serotonergic system in the brain, it is certain that its mechanism of function has to be well investigated. So far several 5-HT receptors and receptor subtypes have been well characterized. Moreover, serotonin agonists and antagonists acting on specific receptors are chemically synthesized and are now available for the prevention or treatment of serotonergic related diseases. In recent years, a great demand for developing neuroimaging agents has emerged for the diagnosis of abnormal brain functions in the ...
A procedure for the determination of lead in soil samples by "2"0"3Pb radioisotope dilution substoichiometric method is described. Japan NIES No.2 river clay standard sample and 83-40 Tibet soil standard sample were determined. The obtained values were in good agreement with reference values. The standard deviation of the method was less then 5%. Detection limit was about 0.1 #mu#g Pb.
The applicability of the radionuclide X-ray fluorescence analysis (RXFA) for qualitative and quantitative evaluation of environmental plant samples is discussed and examples of determination of Mn, Fe, Ni, Cu, Zn, Pb in samples of apple trees are given. The instrumentation, the standard and sample preparation are also presented.
We describe a procedure for correcting the systematic errors in the Moessbauer f-factor measurement due to non-homogeneous effective thickness of the sample. To be more precise, we show that, if the mass of the sample is determined by means of X- or {gamma}-ray absorption, it is possible to establish experimental conditions so that the error on f due to material non-homogeneity in the sample is minimized.
The quality of molecular dynamics (MD) simulations of proteins depends critically on the biomolecular force field that is used. Such force fields are defined by force-field parameter sets, which are generally determined and improved through calibration of properties of small molecules against experimental or theoretical data. By application to large molecules such as proteins, a new force-field parameter set can be validated. We report two 3.5 ns molecular dynamics simulations of hen egg white lysozyme in water applying the widely used GROMOS force-field parameter set 43A1 and a new set 45A3. The two MD ensembles are evaluated against NMR spectroscopic data NOE atom-atom distance bounds, {sup 3}J{sub NH{alpha}} and {sup 3}J{sub {alpha}}{sub {beta}} coupling constants, and {sup 1}5N relaxation data. It is shown that the two sets reproduce structural properties about equally well. The 45A3 ensemble fulfills the atom-atom distance bounds derived from ...
This sampling and analysis plan (SAP) identifies characterization objectives pertaining to sample collection, laboratory analytical evaluation, and reporting requirements for vapor samples obtained during the operation of mixer pumps in tank 241-AZ-101. The primary purpose of the mixer pump test (MPT) is to demonstrate that the two 300 horsepower mixer pumps installed in tank 241-AZ-101 can mobilize the settled sludge so that it can be retrieved for treatment and vitrification. Sampling will be performed in accordance with Tank 241-AZ-101 Mixer Pump Test Data Quality Objective (Banning 1999) and Data Quality Objectives for Regulatory Requirements for Hazardous and Radioactive Air Emissions Sampling and Analysis (Mulkey 1999). The sampling will verify if current air emission estimates used in the permit application are correct and provide information for future ...
Two ent-rosane- (cuzcol, 1 and 6-dehydroxycuzcol, 2) and a abietatriene- (salvadoriol, 3) type diterpenoids have been isolated from Maytenus cuzcoina and Crossopetalum uragoga, respectively, along with five known diterpene compounds (4-8). Their stereostructures have been elucidated on the basis of spectroscopic analysis, including 1D and 2D NMR techniques, and computational data. The absolute configuration of cuzcol was determined by application of Riguera ester procedure. This is the first instance of isolation of ent-rosane diterpenoids from species of the Celastraceae. The isolated diterpenes were found to be potent anti-tumour-promoter agents, and carnosol (7) also showed a remarkable chemopreventive effect in an in vivo two-stage carcinogenesis model.
The use of microwave in chemistry has known benefits over conventional heating methods, e.g. reduced reaction times, chemical yield improvement and the possibility if reducing or eliminating the use of organic solvents. We describe herein a procedure for the nitration of salicylaldehyde in water using a domestic microwave oven, which can be used as an experiment in the undergraduate chemistry laboratory. The experiment involves safe and rapid preparation and identification of the position isomers by thin layer chromatography and {sup 1}H NMR, or by their melting points. (author)
A series of novel triazolinones were synthesized and their structures were characterized by 1H NMR, elemental analysis and single-crystal X-ray diffraction analysis. The herbicidal activities were evaluated against Echinochloa crusgalli (L.) Beauv., Digitaria adscendens, Brassica napus and Amaranthus retroflexus. The herbicidal activity data indicated that the title compounds had higher activities with substituted benzyl group moieties than with other groups such as sulfonyl, alkyl, etc. To further investigate the structure-activity relationship, comparative molecular field analysis was performed on the basis of herbicidal activity data. Both the steric and electronic field distributions of comparative molecular field analysis are in good agreement in this work. The results showed that a b...
In the present work, quaternary chitosans as water-soluble compounds were prepared based on three-step process. Schiff bases were firstly synthesized by the reaction between the amino groups of chitosan with aliphatic aldehydes followed by a reduction with sodium borohydride (NaBH4) to form N-(alkyl) chitosans. N,N,N-(dimethyl alkyl) chitosans were then obtained by a reaction of chitosan containing N-butyl, N-pentyl, N-hexyl, N-heptyl, and N-octyl substituents with methyl iodide. The compounds were characterized using IR and NMR spectroscopy. Subsequent experiments were conducted to test their antimicrobial activities against the most economic plant pathogenic bacteria of crown gall disease Agrobacterium tumefaciens, soft mold disease Erwinia carotovora, fungi of grey mold Botrytis cinerea...
An amphiphilic azobenzene diblock copolymer {2-[4-(4-methoxy phenyl azo)phenoxy]hexyl acrylate co-acrylic acid} was synthesized via reversible addition-fragmentation chain transfer polymerization in a hydrothermal reactor. The products were characterized by 1H-NMR, DSC, GPC and UV-Vis spectroscopy. Different self-assembly behaviors of this amphiphilic diblock copolymer in different organic solvent with different water content were investigated. In THF/H2O solution, the diblock copolymer self-assembled into spheres and the spheres would then change to vesicles with smaller size by increasing the volume of H2O. However, in DMSO/H2O solution, the sizes and morphologies of the self-assembled spheres would not change significantly with an enhanced amount of H2O. Photochromic behaviors of the am...
The relationship between microstructure and macro properties of different cementitious materials has been investigated. This study consists of the following tasks: using NMR and IR to better characterize the amorphous and poorly crystalline phases that occur in blended cements; characterizing the microstructure of the hydration products of modified Portland cement as a function of different percentages of pozzolan replacements by ESEM, SEM, and EDS; comparing the properties of blended cement pastes with a control group of normal Portland cements; and studying the engineering aspects of blended cement that are important for identifying and characterizing fundamental phenomena that are responsible for their durability. The overall influence of the nanoscale and microscale structure of blended and Portland cement on the properties of the resultant composite will be discussed.
Here we reported a two-step procedure for preparing a novel polymeric based solid-solid phase change heat storage material. Firstly, a copolymer monomer containing a polyethylene glycol monomethyl ether (MPEG) phase change unit and a vinyl unit was synthesized via the modification of hydrogen group of MPEG. Secondly, by copolymerization of the copolymer monomer and phenyl ethylene, a novel polymeric based solid-solid phase change heat storage material was prepared. The composition, structure and properties of the novel polymeric based solid-solid phase change material were characterized by IR, "1H NMR, DSC, WAXD, and POM, respectively. The results show that the novel polymeric based solid-solid phase change material possesses of excellent crystal properties and high phase change enthalpy.
Premnalatifolin A (1), a unique icetexane diterpene dimer was isolated from the stem-bark of Indian medicinal plant, Premna latifolia. Its structure and relative stereochemistry were elucidated on the basis of detailed spectroscopic analysis, including HRESIMS and 2D NMR (COSY, HSQC, HMBC, and NOESY) spectra. The compound has dimeric carbon skeleton composed of two icetexane skeletal diterpenes linked via ether bond. Further, premnalatifolin A (1) was also evaluated for its cytotoxicity against cancer cell lines (HT-29, A-431, MCF-7, Hep-G2, PC-3, A-549, B-16 F10, and ACHN), which displayed potent activity against HT-29 and MCF-7 cell lines with the IC50 values of 12.15 and 1.11mg/mL, respectively.
In order to investigate the antioxidant properties of the polysaccharides from the brown alga Sargassum fusiforme, the crude polysaccharides from S. fusiforme (SFPS) were extracted in hot water, and the lipid peroxidation inhibition assay exhibited that SFPS possessed a potential antioxidant activity. Hence, two purely polymeric fractions, SFPS-1 and SFPS-2 were isolated by the column of DEAE (2-diethylaminoethanol)-Sepharose Fast Flow, with their molecular weights of 51.4 and 30.3 kDa determined by high performance gel permeation chromatography (HPGPC). They were preliminarily characterized using chemical analysis in combination of infrared (IR) and nuclear magnetic resonance (NMR) spectroscopies and found to contain large amounts of uronic acids and ?-glycosidical linkages. The antioxida...
Abstract Poly(butylene terephthalate) (PBT) composites containing multiwalled carbon nanotubes (MWCNTs) were prepared using a melt-blending process and used to examine the effects on the composite structure and properties of replacing PBT with acrylic acid-grafted PBT (PBT-g-AA). PBT-g-AA and multihydroxyl-functionalized MWCNTs (MWCNTs-OH) were used to improve the compatibility and dispersibility of the MWCNTs within the PBT matrix. The composites were characterized morphologically using transmission electron microscopy, and chemically using Fourier transform infrared, solid-state 13C NMR and UV-visible absorption spectroscopy. The antibacterial and electrical conductivity properties of the composites were also evaluated. MWCNTs or MWCNTs-OH enhanced the antibacterial activity and electric...
This paper describes the search for new potential chemotherapeutic agents based on transition metal complexes with planar ligands. In this study, palladium polypyridyl complexes were synthesized and characterized by elemental analysis, NMR, UV-VIS and IR spectroscopies. The interaction of the complexes with DNA was also investigated by spectroscopic methods. All metal-to-ligand charge transfer (MLCT) bands of the palladium polypyridyl complexes exhibited hypochromism and red shift in the presence of DNA. The binding constant and viscosity data suggested that the complexes [PdCl{sub 2}(phen)] and [PdCl{sub 2}(phendiamine)] interact with DNA by electrostatic forces. Additionally, these complexes induced an important leishmanistatic effect on L. (L.) mexicana promastigotes at the final concentration of 10 {mu}mol L{sup -1} in 48 h. (author)
Chemical modification of poly(?-caprolactone) PCL by oxidation with potassium permanganate in solution was investigated. According to the data obtained from Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance 1H NMR, after the oxidation reactions the PCL chains exhibited new functional groups (vinyl and hydroxyl) and possible intermolecular recombination, producing an oxidized-polycaprolactone (PCL-OX). Solution viscometry indicated that degradation also occurred during the oxidation reactions (30% drop in viscosity average molecular weight was detected). Differential scanning calorimetry (DSC) also indicated that PCL was chemically modified and degraded. The successive self-nucleation/annealing (SSA) treatment confirmed that a reduction (or interruption) in line...
"1"7"5Ta and "1"7"7Ta nuclei were oriented at low temperature as dilute impurities in Fe. The magnetic hyperfine splitting frequencies #nu#="+#mu#B sub(HF)/Ih"+ of the "1"7"5Ta and "1"7"7Ta ground states have been measured to be 320.45(11) and 317.552(55) MHz by using the technique of NMR-ON. Taking the known hyperfine field of "1"8"1Ta in Fe, the magneticmoments have been deduced: "+#mu#("1"7"5Ta, 7/2"+)"+=2.270(45) and "+#mu#("1"7"7Ta, 7/2"+)"+=2.250(45)#mu# sub(N). These values of the magnetic moments are discussed in the framework of the rotational model. (author).
Nuclear magnetic resonance (NMR) images of live rats with sterile and pyogenic abscesses, hematomas, and various implanted and spontaneous neoplasms demonstrated good contrast differentiation between pathologic and surrounding normal tissues. This differentiation was maximal when both the T1 and T2 tissue relaxation times were used as criteria. Neoplasms have a broad range of T1 and T2 values and may be confused with abscesses or hematomas. Tissue rate constants (1/T1 and 1/T2) are mainly dependent on total water content, the exception being fat, which has a 1/T2 value much shorter than that expected on the basis of water content alone.
The crystal structure of Ca{sub 2}RuD{sub 6} has been determined by neutron powder diffraction: space group Fm3m, K{sub 2}PtCl{sub 6} structure, as found for other hexahydride salts of group 8 metals with alkaline earth or lanthanide counter ions. No structural phase transition was observed between 340 K and 50 K. The deuterium nuclear quadrupole coupling constant, 54.7 kHz, leads to an ionic character of the Ru-D bond of 76%. The known trends in the behaviour of A{sub 2}MH{sub 6} salts are interpreted in terms of the ionization energies of the cation and the central metal atom.
The crystal structure of Ca2RuD6 has been determined by neutron powder diffraction: space group Fm3m, K2PtCl6 structure, as found for other hexahydride salts of group 8 metals with alkaline earth or lanthanide counter ions. No structural phase transition was observed between 340K and 50K. The deuterium nuclear quadrupole coupling constant, 54.7kHz, leads to an ionic character of the Ru-D bond of 76%. The known trends in the behaviour of A2MH6 salts are interpreted in terms of the ionization energies of the cation and the central metal atom.
Protein motions on all timescales faster than molecular tumbling are encoded in the spectral density. The dissection of complex protein dynamics is typically performed using relaxation rates determined at high and ultra-high field. Here we expand this range of the spectral density to low fields through field cycling using the nucleocapsid protein of the SARS coronavirus as a model system. The field-cycling approach enables site-specific measurements of R{sub 1} at low fields with the sensitivity and resolution of a high-field magnet. These data, together with high-field relaxation and heteronuclear NOE, provide evidence for correlated rigid-body motions of the entire {beta}-hairpin, and corresponding motions of adjacent loops with a time constant of 0.8 ns (mesodynamics). MD simulations substantiate these findings and provide direct verification of the time scale and collective nature of these motions.
An aliphatic thiol ligand of CuInS2/ZnS core/shell quantum dots is replaced with a hydroxyl-terminated thiol ligand by utilizing `on-off state' of ligands during growth stage of the quantum dots. After the ligand-exchange, negligible differences were observed on both photoluminescence spectrum and luminescent quantum efficiency. The reason for the high retention of luminescent efficiency comes from no local agglomeration and no surface deterioration of QDs. It is also observed that 70% of initial ligands are exchanged by the replacing ligand, determined by FT-IR and 1H NMR. The proposed method provides the quantum dots with an excellent dispersibility in polar solvents, supported by identical luminescence decay characteristics of the QDs.
Asphaltenes precipitated from an Arabian Mix vacuum residue were hydrocracked in a batch autoclave at 435 and 460{degree}C for 5-90 min. Experiments without catalyst, with modified red mud and with an industrial Co Mo/Al{sub 2}O{sub 3} catalyst were compared. The products were fractionated into gas, naphtha, oil, asphaltenes and coke. Feed asphaltenes and several product fractions were characterised by elemental analysis, by average molecular mass and by {sup 1}H n.m.r. Due to the hydrogenation activity, both catalysts caused - with similar efficiency - the decrease of coke formation and the increase of quantity and quality of oil. 21 refs., 9 figs., 5 tabs.
A novel heteropolyanion-based ionic hybrid was prepared by combining the divalent ionic liquid (IL) cation of 1,1'-(butane-1,4-diyl)-bis(3-methylimidazolium) with the Keggin-structured V-containing heteropolyanion, and characterized by ^1H NMR, FT-IR, ESI-MS, XRD, SEM, TG, BET surface area, melting point, and elemental analysis. Its catalytic activity was evaluated in the hydroxylation of benzene with aqueous H2O2, including the testing of the influence of organic cations, catalytic reusability and optimization of reaction conditions. This hybrid is characterized to be semi-amorphous nanoparticles with a IL-like composition. The hybrid catalyst leads to the liquid-solid biphasic reaction system for hydroxylation of benzene with H2O2, presenting such advantages as high catalytic activity, c...
A series of [60]fullerene-substituted phenylalanine (Baa) and lysine derivatives have been prepared by the condensation of 1,2-(4prime-oxocyclohexano)fullerene with the appropriately protected (4-amino)phenylalanine and lysine, respectively. Conversion of the imine to the corresponding amine is achieved by di-acid catalyzed hydroboration. The reduction of the imine is not accompanied by hydroboration of the fullerene cage. The [70]fullerene phenylalanine derivative has also been prepared as have the di-amino acid derivatives. The compounds were characterized by MALDI-TOF mass spectrometry, UV/Vis spectroscopy, and cyclic voltammetry. 1H and 13C NMR spectroscopy allowed the observation of diastereomers. Fullerene-substituted peptides may be synthesized on relatively large scale by solid-pha...
The leaf extract from the plant Piliostigma reticulatum was found to exhibit antimicrobial activity against some bacteria and fungi such as Staphylococcus aureus (NCTC 6571), Escherichia coli (NCTC 10418), Bacillus subtilis (NCTC 8236), Proteus vulgaris (NCTC 4175), Aspergillus niger (ATCC 10578) and Candida albicans (ATCC 10231). Upon investigation of the chemical constituents present in the leaf extract, a total of seven compounds were isolated and their structures were unambiguously established by spectroscopic methods including HR-MS and NMR spectrometry. Four of the isolated compounds were novel, namely 6-C-methyl-2-p-hydroxyphenyloxychromonol (piliostigmol), 1, 6,8-di-C-methylquercetin-3,3prime,7-trimethyl ether, 2, 6,8-di-C-methylquercetin-3,3prime-dimethyl ether, 3 and 3prime,6,8,-...
Extraction of 25 L fermentation broth of the newly isolated Streptomyces sp. strain TN58 and various separation and purification steps led to the isolation of five bioactive metabolites, namely brevianamide F (C1), reported from a streptomycete for the first time, N?-acetyltryptamine (C2), thiazolidomycin (C3), and two rhamnopyranosides (C4 and C5). These two rhamnopyranosides were produced directly, without precursor addition. The chemical structure of these five active compounds was established on the basis of 1H, 13C/APT and 2D NMR spectra, ESI and EI-MS data, and by comparison with data from the literature. According to the biological studies, we show in this work that the compounds C1, C2, C4 and C5 possess antimicrobial activities.
The adhesion of microorganisms onto materials surface mediated by extracellular polymeric substances (EPS) lead to an important modification of the metal-solution interface. The requirement of modern civilization with the heightened sense of environmental responsibilities and quality of life can be met by using some eco-friendly microbiocides with different spectra of activity. Some N{sub 2}O{sub 2} donor Schiff base compounds were synthesized and characterized by IR, NMR and ESR spectroscopy. These compounds were found effective in controlling the growth of biofilm of E. coli, Pseudomonas fluorescens and Thiobacillus thiooxidans on copper surface. The optimum concentration of these compounds are in the range of 1--10 ppm. Various electrochemical, microbiological and surface-analytical techniques were used to monitor the biofilm in the presence of microbiocides.
2,6-Diacetyl pyridine based ligand was synthesized by the reaction of 2,6-diacetyl pyridine with thiocarbohydrazide in presence of acetic acid. The coordination compounds with Cr(III) and Ni(II) metal ions having [Cr(L)X]X2 and [Ni(L)X]X compositions (where L=ligand and X=NO3^-, Cl^- and CH3COO^-) were synthesized and characterized by physicochemical and spectral studies. The studies like elemental analyses, molar conductance measurements, magnetic susceptibility measurements, IR, UV-Vis, NMR, mass and EPR reveal that the complexes are octahedral. The compounds were examined against the pathogenic fungal and bacterial strains like Alternaria brassicae, Aspergillus niger, Fusarium oxysporum, Xanthomonas compestris and Pseudomonas aeruginosa. A. niger causes the diseases Apergillosis and Oto...
The paper describes the chemical constituents isolated from aerial parts of the plant Galianthe brasiliensis. From a methanol extract, the iridoid glycosides asperuloside, deacetylasperuloside, mixture of Z- and E-6-O-p-coumaroylscandoside methyl ester, the triterpene ursolic acid and the steroids stigmasterol, campesterol, b-sitosterol and 3-O-b-glucopyranosyl sitosterol were isolated. The structures of the natural products were identified on the basis of spectral data, including 2D NMR experiments. The antiproliferative properties of the crude methanolic extract were investigated against a series of nine human cancer cell lines. (author)
The phytochemical investigation of Chomelia obtusa leaves led to the isolation of four triterpenes (3-O-#beta#-D-quinovopyranosyl-28-O-#beta#-D-glycopyranosyl quinovic acid, 3-O-#beta#-D-quinovopyranosyl-28-O-#beta#-D-glycopyranosyl cincholic acid, and a mixture of ursolic and oleanolic acids), two flavonoids (3-O-#beta#-D-glycopyranosyl quercetin, 3-O-[#alpha#-L-rhamnopyranosyl-(1#->#6)-#beta#-D-galactopyranoside] quercetin), besides bornesitol and a mixture of 3,5- and 4,5-O-dicaffeoyl quinic acids. The structures of the isolated compounds were assigned on the basis of spectroscopic data, including two-dimensional NMR methods. The anti-inflammatory and antioxidant activities of the crude methanolic extract and of its fractions were evaluated. This is the first report on the chemical and biological investigation of the Chomelia genus. (author)
Eremostachys laciniata (L) Bunge (family: Lamiaceae alt. Labiatae; subfamily: Lamioideae) is one of the 15 endemic Iranian herbs of the genus Eremostachys. A decoction of the roots and flowers of E. laciniata has traditionally been taken orally for the treatment of allergies, headache and liver diseases. Three antibacterial iridoid glucosides, phloyoside I (1), phlomiol (2) and pulchelloside I (3) have been isolated from the rhizomes of this plant. The structures of these compounds were elucidated unequivocally by a series of 1D and 2D NMR analyses. The antibacterial activity and brine shrimp toxicity of these compounds were assessed using the resazurin microtitre assay and the brine shrimp lethality assay, respectively. All three iridoid glycosides 1-3 exhibited from low to moderate level...
This is a report of extraction and identification of 1-O-alkyl glycerol present in the dried leaves of Bauhinia scandens. Fifty percent aqueous ethanolic extract of the plant at room temperature was fractionated over petroleum ether and diethyl ether. The diethyl ether soluble fraction showed positive bioactivity in Brine Shrimp bioassay. Isolation and purification of the active principle was subsequently done from diethyl ether fraction. The diethyl ether fraction was separated into acidic and neutral part. The acid free fraction was screened to be positive in Brine Shrimp bioassay. The NMR spectra (in CDCl3) indicated the probability of its lipoidal nature. The total lipid fraction was resolved into neutral, glyco, and phospho-lipids by column chromatography. Only the neutral fraction sh...
The monoanionic bidentate Schiff base, N-(phenolyl)-benzaldimine (HL), has been employed to synthesize a new vanadium(IV) complex of general composition [VO(L)2] (where L = O, N donor of Schiff base). The ligand and complex have been fully characterized by elemental analyses, molar conductance data, FT-IR, 1H- and 13C-NMR, and UV-Vis spectroscopies. Oxidation of alcohols to their corresponding aldehydes and ketones was conducted by this complex catalyst using Oxone as oxidant under biphasic reaction conditions (CH2Cl2/H2O) and tetra-n-butylammonium bromide as phase transfer agent under air at room temperature.
This study illustrates the way to perform protocols, collect samples, and conduct laboratory analyses in order to characterize the physical properties of wood used in the industrial sector of the Valle de Aburra metropalitan area and the gains obtained by characterizing the properties of the most frequently used woods. In this investigation some of the most important sampling parameters are presented, such as taking samples in piles or accumulations of waste, handling of these samples in the laboratory and others of great importance such as the ignition point. the proposed methodology is based upon some of the international astm coal norms, for the similarity it has with wood and for the lack of information on sampling this type in wood
This paper describes a novel Fourier transform infrared (FTIR) spectroscopic method that can be used to rapidly screen soil samples from potentially hazardous waste sites. Samples are heated in a thermal desorption unit and the resultant vapors are collected and analyzed in a long-path gas cell mounted in a FTIR. Laboratory analysis of a soil sample by FTIR takes approximately 10 minutes. This method has been developed to identify and quantify microgram concentrations of explosives in soil samples and is directly applicable to the detection of selected volatile organics, semivolatile organics, and pesticides.
A series of dinuclear platinum(II) complexes, [(dien)Pt(NH{sub 2}(CH{sub 2}){sub n}NH{sub 2})Pt(dien)]Cl{sub 4} (dien = diethylenetriamine, n = 8, 9, 10, and 12) and their corresponding [2]rotaxanes with {alpha}-cyclodextrin ({alpha}-CD), [(dien)Pt{l_brace}NH{sub 2}(CH{sub 2}){sub n}NH{sub 2}{center_dot}{alpha}-CD{r_brace}Pt(dien)]Cl{sub 4}, have been synthesized and characterized by {sup 1}H, {sup 13}C, and {sup 195}Pt NMR spectroscopy and electrospray mass spectrometry. The rotaxanes were prepared by reacting the {l_brace}NH{sub 2}(CH{sub 2}){sub n}NH{sub 2}{center_dot}{alpha}-CD{r_brace} pseudorotaxanes with [Pt(dien)]Cl, to stopper the included linear {alpha},{omega}-diaminoalkane chains with the inert Pt(II) end groups. The kinetics of the self-assembly and dissociation of the {beta}-CD rotaxane, [(dien)Pt{l_brace}NH{sub 2}(CH{sub 2}){sub 10}NH{sub 2}{center_dot}{beta}-CD{r_brace}Pt(dien)]{sup 4+}, were investigated by using {sup 1}H NMR ...
Small unilamellar vesicles which form when gel-state long-chain phosphatidylcholines are mixed with micellar short-chain lecithins undergo an increase in size as the long-chain species melts to its liquid-crystalline form. Analysis of the vesicle population with quasi-elastic light scattering shows that the particle size increases from 90-A radius to greater than 5000-A radius. Resonance energy transfer experiments show total mixing of lipid probes with unlabeled vesicles only when the Tm of the long-chain phosphatidylcholine is exceeded. This implies that the large size change represents a fusion process. Aqueous compartments are also mixed during this transition. 31P NMR analysis of the vesicle mixtures above the phase transition shows a great degree of heterogeneity with large unilamellar particles coexisting with oligo- and multilamellar structures. Upon cooling the vesicles below the Tm, the original size distribution (e.g., small unilamellar vesicles) is ...
The photophysical investigation of different para-substituted tetraphenylporphyrins (TP), viz., meso-tetra(4'-hydroxyphenyl)-21H-23H-porphyrin(1),meso-tetrakis (4'-hex-5-enyloxyphenyl)-21H-23H-porphyrin(2), meso-tetrakis(4'-oct-7-enyloxyphenyl)-21H-23H-porphyrin(3) and meso-tetrakis(4'-undecyloxyphenyl)-21H-23H-porphyrin (4) revealed that except for quantum yield (#phi#) the para-substitution has little effect on any other photophysical properties like lifetime, excitation, emission wavelength, etc. The host-guest type interactions of these tetraarylporphyrins (TP 1-4), with [60]-fullerene (F) have been studied with "1H NMR and fluorescence spectrometric techniques in carbon tetrachloride medium. Fluorescence studies revealed that the Q band of the TPs was sufficiently quenched upon addition of F. All the fullerene/porphyrin systems were found to produce stable complexes with 1:1 stoichiometry. Binding constants (K) of all the fullerene/porphyrin complexes have ...
Structure and magnetic properties of UNi_1_0_-_xFe_xSi_2 intermetallics and "2"9Si nuclear magnetic resonance (NMR) in UNi_1_0Si_2 are investigated in a wide temperature range. Solid solutions in the exactly single-phase tetragonal form, ThMn_1_2 type, exist for x<2. The Ni and Fe atoms occupy the 8(f), 8(i) and 8(j) positions statistically, whereas the U atoms occupy the 2(a) and the Si atoms the 8(j) sites. The lattice parameters roughly follow Vegard's law. The magnetic susceptibility does not exhibit Curie-Weiss behaviour and, at about 630 K, an anomaly in the temperature dependence is observed. At low temperature, other anomalies are observed at 32 K and 45 K, for x=0.5 and 1.0 respectively. These low temperature anomalies are probably connected with magnetic ordering of a ferromagnetic character, whereas that at 630 K might result from the superparamagnetic state of Ni. Two "2"9Si NMR lines in UNi"1"0Si"2 were observed with the Knight ...
"2"7Al and "2"9Si solid-state NMR spectra and X-ray diffraction (XRD) patterns were obtained for #alpha#-SiAlON powders prepared by combustion synthesis, according to which the phase transformation and structure evolution of #alpha#-SiAlON were studied. It was found that in #alpha#-SiAlON "2"9Si chemical shift values (-48 < #delta# _S_i < -47) were close to those in #beta#-Si_3N_4 and #alpha#-Si_3N_4, indicating that Si atoms kept SiN_4 coordination to a large extent in #alpha#-SiAlON despite the presence of O atoms. Dissimilarly, "2"7Al chemical shift values in #alpha#-SiAlON deviated clearly from that corresponding to AlN_4 coordination (#delta# _A_l #approx# 112) and occurred in a range from #delta# _A_l 95.5 to 99.9, which should be assigned to tetrahedral AlO _xN_4_-_x (0 #<=# x #<=# 4) coordination. The broadening effect of AlO _xN_4_-_x peaks was noticed, which was suggested to induced by slight dispersion of #alpha#-SiAlON compositions. "2"7Al ...
The kainoid amino acids are biologically important compounds because they show remarkable neuroexcitatory and excitotoxic activities. For exhibiting potent activity, the stereochemical relationship of the substituents on the pyrrolidine ring is crucial. We found simple methods for determining the relative stereochemistry of these compounds on the basis of the (1)H NMR chemical shifts of H-2 and H-4 in D(2)O solution. The signals of H-2 appear at fields higher than 4.2 ppm when the compounds have 2,3-trans stereochemistry whereas, in the 2,3-cis compounds, they appear lower than 4.2 ppm, irrespective of the C-4 substituent. This criterion holds when the solution is in the range of pD 3-8. Moreover, when an epimeric pair at C-2 is available and the spectra are recorded at the same or nearly equal pD, the H-2 chemical shift of the 2,3-trans isomer is higher than that of the corresponding 2,3-cis isomer. Similarly, the relative stereochemistry between C-3 and C-4 can ...
The performance of 250 different computational protocols (combinations of density functionals, basis sets and methods) was assessed on a set of 165 well-established experimental (1)H-(1)H nuclear coupling constants (J(H-H)) from 65 molecules spanning a wide range of "chemical space". Thereby we found that, if one uses core-augmented basis sets and allows for linear scaling of the raw results, calculations of only the Fermi contact term yield more accurate predictions than calculations where all four terms that contribute to J(H-H) are evaluated. It turns out that B3LYP/6-31G(d,p)u+1s is the best (and, in addition, one of the most economical) of all tested methods, yielding predictions of J(H-H) with a root-mean-square deviation from experiment of less than 0.5 Hz for our test set. Another method that does similarly well, without the need for additional 1s basis functions, is B3LYP/cc-pVTZ, which is, however, ca. 8 times more "expensive" in terms of CPU time. A selection of the better ...
The use of platinum(II) complexes as tags and probes for biomolecules is indeed advantageous for their reactivities can be selective for certain purposes through an interplay of mild reaction conditions and of the ligands bound to the platinum. The use of {sup 195}Pt NMR as a method of detecting platinum and its interactions with biomolecules was carried out with the simplest model of platinum(II) tagging to proteins. Variable-temperature {sup 195}Pt NMR spectroscopy proved useful in studying the stereodynamics of complex thioethers like methionine. The complex, Pt(trpy)Cl{sup +}, with its chromophore has a greater potential for probing proteins. It is a noninvasive and selective tag for histidine and cysteine residues on the surface of cytochrome c at pH 5. The protein derivatives obtained are separable, and the tags are easily quantitated and differentiated through the metal-to-ligand charge transfer bands which are sensitive to the ...
Nitrous oxide is methylated with CH/sub 3/F ..-->.. SbF/sub 5/F/sub 2/ or with CH/sub 3/O/sup +/SOClF in SO/sub 2/ClF to give the stable methoxydiazonium ion CH/sub 3/ON/sub 2//sup +/ (1), which was characterized by NMR (/sup 15/N, /sup 13/C, /sup 1/H) and FT IR spectroscopic studies. It is stable below -30 /sup 0/C, above which it decomposes, regenerating N/sub 2/O. When reacted with aromatics, such as toluene, 1 gives only methylation products and no methoxy derivatives are formed. Spectroscopic and chemical data indicate that the mesomeric form CH/sub 3/O-N=N/sup +/ is a significant contributor to the overall structure of 1. Consideration of computed charge distribution (4-31 G with full geometry optimization and 4-31 G*) also supports this conclusion. Independent generation of 1 was also studied by solvolysis of methylazoxy triflate and diazotization of methoxylamine with NO/sup +/BF/sub 4//sup -/. Preparation of the elusive hydroxydiazonium ion HON/sub ...
Nuclear magnetic resonance is a powerful technique that can be used in a wide range of applications, such as the structural characterization of high molecular weight molecules, conformational studies on enzymes in solution, enzyme-substrate or DNA-protein interactions, monitoring of cell metabolism in vivo, and for diagnostic purposes, employing spectroscopic and imaging techniques. This course was organized in order to introduce the participants to the fundamentals of NMR spectroscopy, and offer practical advice on performing NMR experiments on cell systems, cell and tissue extracts and animal models. The main implications regarding human experiments were also discussed. Finally the quantification of information and the interpretation of data were considered with regard to the main nuclei observed. [Italiano] La risonanza magnetica nucleare e` una delle tecniche spettroscopiche che meglio risponde all`ampio spettro di condizioni imposto dalla ...
A triangular antiferromagnet UNi_4B experiences a partially disordered state, in which two-thirds of U 5f moments order in a vertex-like structure and one-third of U 5f moments remain paramagnetic. Magnetization and NMR measurements of UNi_4B have been performed to study the dynamical properties of U magnetic moments in the partially disordered state. The value of the effective moment above T_N derived from the fitting of the Curie-Weiss law suggests a significant crystal field splitting and the Kondo effect. The Weiss temperature was also estimated to be -28 K, which suggests that the exchange interaction is antiferromagnetic. Furthermore, the exchange interaction estimated from the relaxation rate T_1"-"1 above 50 K is 18 K, which is close to the Weiss temperature. These results suggest that the dominant interactions between U moments are antiferromagnetic in the basal plane. The relaxation rate T_1"-"1 decreases abruptly below T_N down to 15 K and is almost ...
The amino acid residues 114-118 in actin were found to be implicated strongly in the binding of nucleotide, and as would be expected for such an important binding site, they are located in a completely conserved region of the actin sequence. A 19-residue peptide with the actin sequence 106-124 was synthesized in order to span the putative triphosphate binding site. Proton NMR spectra of the actin peptide 114-118 in the presence and absence of ATP indicated that Arg-116 and Lys-118 are particularly involved in binding ATP. A strong binding of ATP to the peptide 106-124 also was measured. Tripolyphosphate bound to the peptide 106-124 somewhat more weakly than ATP. Binding involved residues 115-118 and 121-124, indicating the presence of a reverse turn between these segments. Proton resonances were assigned by using two-dimensional double quantum correlated spectroscopy, one-dimensional spin decoupling techniques, one-dimensional nuclear Overhauser enhancement ...
Three major monomeric hemoglobins have been isolated from the erythrocytes of Glycera dibranchiata. Their importance to structure-function studies of heme proteins lies in the fact that they have been shown to possess an exceptional amino acid substitution. In these proteins, the E-7 position is occupied by leucine rather than the more common distal histidine. This substitution alters the polarity of the heme ligand binding environment compared to myoglobin. Due to this, the G. dibranchiata monomer hemoglobins are attracting much attention. However, until now no purity criterion has been developed. Here the authors demonstrate that, for all of the Glycera momomer hemoglobins, multiple line patterns are shown on high-voltage isoelectric focusing (IEF) gels. Most of these lines are shown to be a consequence of heme-related phenomena and can be understood on the basis of changes in oxidation and ligation state of the heme iron. The multiple line pattern does not indicate significant ...
The fundamentals and the technical application methods of the imaging procedures are discussed in detail with regard to their application in medicine. The development of the X-ray contrast media has led to a better tolerance and a significant reduction of risks. Problems relating to radiation protection and radiation exposure are discussed critically. The general point gives an overview of the radiological examination methods and is meant to deepen the understanding of the special techniques and their rationally determined application. The following special part deals with diagnosing of organs in the region of the neck and the thorax. The general basis is the conventional radiological examination. The great increase in information achieved by means of the new imaging methods becomes clear if we look at the diagnostics of the soft tissue of the neck. Computerized tomography and NMR imaging open the view at the fine structures of the mediastinum. Mammography is an ...
A series of pentaamminerhodium(III) complexes, Rh(NH/sub 3/)/sub 5/Z/sup n+/, has been prepared with 80% enrichment in /sup 15/N (Z = H/sub 2/O, OH/sup /minus//, Cl/sup /minus//, Br/sup /minus//, I/sup /minus//, NH/sub 3/, /minus/ONO/sup /minus//, /minus/NO/sub 2//sup /minus//, /minus/NCS/sup /minus//, /minus/SCN/sup /minus//, /minus/NCO/sup /minus//, CN/sup /minus//). The /sup 1/H-decoupled /sup 15/N NMR spectra show two doublets (from coupling to /sup 103/Rh) with approximate intensity ratio 4:1. /delta//sub N/ and /sup 1/J(rh-N) are sensitive to Z, especially for the unique amine trans to Z. Good correlations exist between /delta//sub N/ in this series of /delta//sub N/ in this series and /delta//sub N/ in the corresponding cobalt(III) complexes Co(NH/sub 3/)/sub 5/Z/sup n+/ and platinum(II) complexes Pt(NH/sub 3/)/sub 3/Z/sup m+/, J(Rh-N) trans to Z also correlates well with H(Pt-N) trans to Z in the platinum series. 16 refs., 2 figs., 1 tab.
This paperwork explain the method of water sampling to obtain the precipitate of BaCO3 solutions that will be used to analyze 13C from field work in Kelana Jaya, Selangor, Langkawi, Kedah and Taiping, Perak. The sampling involves collecting of water samples for groundwater from boreholes and surface water from canal, river, pond and ex-mining pond from several locations at the study sites. This study also elaborates the instruments and chemicals used. The main purpose of this sampling is to obtain the precipitate of BaCO3 for 13C analysis of dissolved inorganic carbon (DIC). A correct sampling method according to standard is very important to ensure an accurate and precise result. With this, the data from the laboratory analysis result can be fully utilized to make the interpretation of the pollutants movement. (Author)