bluuebunny/crossref_metadata_2025 huggingface dataset:
Common complaints, difficult diagnosis: Multiple myeloma
Authors: Dvorak Colleen
Published: May 2006

Purpose: To review the presenting signs and symptoms of multiple myeloma, its pathophysiology, diagnostic evaluation, and treatment options.

Data sources: A literature review of research articles and publications by oncology experts who specialize in multiple myeloma, supplemented by a case study.

Conclusions: Multiple myeloma is a cancer of the geriatric population, with the average age at diagnosis between 65 and 68 years. As the population of those over age 65 is predicted to double by the year 2050, the incidence of myeloma is expected to increase. Nurse practitioners (NPs) must become familiar with the signs, symptoms, and complications of myeloma for patients to be diagnosed and referred to specialists in a timely manner.

Implications for practice: Patients with multiple myeloma often present with vague, common symptoms such as back pain, bony pain, fatigue, and anemia. These symptoms may be treated as separate medical conditions if NPs fail to include multiple myeloma in their differential diagnosis. If NPs are educated on this malignancy, they will have the expertise to look for other signs of the disease such as hypercalcemia, pathological fractures, osteopenia, or renal failure. Without early recognition of multiple myeloma and referrals to oncology specialists, patients are left with a delayed diagnosis and poor symptom control.
Direct Visualization of Red Fluorescent Lipoproteins Indicates Conservation of the Membrane Sorting Rules in the FamilyEnterobacteriaceae
Authors: Lewenza Shawn , Vidal-Ingigliardi Dominique , Pugsley Anthony P.
Published: May 2006

Chimeras created by fusing the monomeric red fluorescent protein (RFP) to a bacterial lipoprotein signal peptide (lipoRFPs) were visualized in the cell envelope by epifluorescence microscopy. Plasmolysis of the bacteria separated the inner and outer membranes, allowing the specific subcellular localization of lipoRFPs to be determined in situ. When equipped with the canonical inner membrane lipoprotein retention signal CDSR, lipoRFP was located in the inner membrane inEscherichia coli, whereas the outer membrane sorting signal CSSR caused lipoRFP to localize to the outer membrane. CFSR-RFP was also routed to the outer membrane, but CFNSR-RFP was located in the inner membrane, consistent with previous data showing that this sequence functions as an inner membrane retention signal. These four lipoproteins exhibited identical localization patterns in a panel of members of the familyEnterobacteriaceae, showing that the lipoprotein sorting rules are conserved in these bacteria and validating the use ofE. colias a model system. Although most predicted inner membrane lipoproteins in these bacteria have an aspartate residue after the fatty acylated N-terminal cysteine residue, alternative signals such as CFN can and probably do function in parallel, as indicated by the existence of putative inner membrane lipoproteins with this sequence at their N termini.
Characterization of theYersinia enterocoliticaType III Secretion ATPase YscN and Its Regulator, YscL
Authors: Blaylock Bill , Riordan Kelly E. , Missiakas Dominique M. , Schneewind Olaf
Published: May 2006

Type III secretion is a mechanism used by a broad range of gram-negative bacteria to neutralize eukaryotic defenses by enabling translocation of bacterial proteins directly into the cytoplasm of host cells. The bacterial energy source for secretion is ATP, which is consumed by an ATPase that couples ATP hydrolysis to the unfolding of secreted proteins and the dissociation of their chaperones just prior to secretion. By studying the biochemical properties of YscN and YscL ofYersinia enterocolitica, we have characterized them as the ATPase and ATPase regulator, respectively, of the type III secretion system of this organism. In vivo, YscL and YscN interact with each other, and the overexpression of glutathioneS-transferase-YscL abolishes secretion and down-regulates the expression of secretion apparatus components.
Identification of a Mutation in the
Bacillus subtilis S
-Adenosylmethionine Synthetase Gene That Results in Derepression of S-Box Gene Expression
Authors: McDaniel Brooke A. , Grundy Frank J. , Kurlekar Vineeta P. , Tomsic Jerneja , Henkin Tina M.
Published: May 2006

Genes in the S-box family are regulated by binding of
S
-adenosylmethionine (SAM) to the 5′ region of the mRNA of the regulated gene. SAM binding was previously shown to promote a rearrangement of the RNA structure that results in premature termination of transcription in vitro and repression of expression of the downstream coding sequence. The S-box RNA element therefore acts as a SAM-binding riboswitch in vitro. In an effort to identify factors other than SAM that could be involved in the S-box regulatory mechanism in vivo, we searched for
trans
-acting mutations in
Bacillus subtilis
that act to disrupt repression of S-box gene expression during growth under conditions where SAM pools are elevated. We identified a single mutant that proved to have one nucleotide substitution in the
metK
gene, encoding SAM synthetase. This mutation, designated
metK10
, resulted in a 15-fold decrease in SAM synthetase activity and a 4-fold decrease in SAM concentration in vivo. The
metK10
mutation specifically affected S-box gene expression, and the increase in expression under repressing conditions was dependent on the presence of a functional transcriptional antiterminator element. The observation that the mutation identified in this search affects SAM production supports the model that the S-box RNAs directly monitor SAM in vivo, without a requirement for additional factors.
d
-Alanyl Ester Depletion of Teichoic Acids in
Lactobacillus plantarum
Results in a Major Modification of Lipoteichoic Acid Composition and Cell Wall Perforations at the Septum Mediated by the Acm2 Autolysin
Authors: Palumbo Emmanuelle , Deghorain Marie , Cocconcelli Pier Sandro , Kleerebezem Michiel , Geyer Armin , Hartung Thomas , Morath Siegfried , Hols Pascal
Published: May 2006

The insertional inactivation of the
dlt
operon from
Lactobacillus plantarum
NCIMB8826 had a strong impact on lipoteichoic acid (LTA) composition, resulting in a major reduction in
d
-alanyl ester content. Unexpectedly, mutant LTA showed high levels of glucosylation and were threefold longer than wild-type LTA. The
dlt
mutation resulted in a reduced growth rate and increased cell lysis during the exponential and stationary growth phases. Microscopy analysis revealed increased cell length, damaged dividing cells, and perforations of the envelope in the septal region. The observed defects in the separation process, cell envelope perforation, and autolysis of the
dlt
mutant could be partially attributed to the
L. plantarum
Acm2 peptidoglycan hydrolase.
Variable Expression Patterns of
Mycobacterium tuberculosis
PE_PGRS Genes: Evidence that PE_PGRS16 and PE_PGRS26 Are Inversely Regulated In Vivo
Authors: Dheenadhayalan Veerabadran , Delogu Giovanni , Sanguinetti Maurizio , Fadda Giovanni , Brennan Michael J.
Published: May 2006

Evaluation of expression of 16 PE_PGRS genes present in
Mycobacterium tuberculosis
under various growth conditions demonstrated constitutive expression of 7 genes, variable expression of 7 genes, and no expression of 2 genes. An inverse expression profile for genes PE_PGRS16 and PE_PGRS26 was observed to occur in macrophages and in mice infected with
M. tuberculosis
. Variable expression of PE_PGRS proteins could have implications for their role in the immunopathogenesis of tuberculosis.
REACTIONS OF AMIDES AND RELATED COMPOUNDS: II. NUCLEAR MAGNETIC RESONANCE INVESTIGATION OF ADDUCTS OF N-METHYLFORMAMIDE WITH HCl AND HBr AND N,N-DIMETHYLFORMAMIDE WITH PROTONATING ACIDS AND SILVER SALTS
Authors: Kuhn Stephen J. , McIntyre John S.
Published: May 2006

The proton magnetic resonance spectra of dimethylformamide – proton acid and dimethyl-formamide – silver salt complexes in 2-nitropropane solution as well as N-methylformamide-HCl and HBr adducts in tetramethylene sulfone solution have been investigated. The results indicate that the protonation takes place on the carbonyl oxygen. For most of the acids investigated, the acid strength correlates with shifts of both the methyl proton and the proton complexed at the carbonyl oxygen. The dimethylformamide – silver salt complexes have a structure similar to the DMF – Lewis acid or protonating acid adducts.
GAS–LIQUID CHROMATOGRAPHY OF TERPENES: PART XIII. THE VOLATILE OIL OF THE LEAVES OF JUNIPERUS HORIZONTALS MOENCH
Authors: Couchman F. M. , Rudloff E. Von
Published: May 2006

The neutral leaf oil of the creeping juniper from the Prairies was analyzed by gas–liquid chromatography. d-Sabinene (36.5%) was found to be the major constituent, and smaller amounts of d-limonene (17.5%), p-cymene (3.0%), d-α-pinene (1.6%), γ-terpinene (0.4%), d-terpinen-4-ol (4.6%), linalool (0.8%), citronellol (0.8%), γ-cadinene (1.3%), l-elemol (3.8%), α-cadinol or γ-eudesmol (1.6%), and impure α-cyperone (3.9%) were isolated. α-Thujene (3.0%), camphene (0.2%), β-pinene (0.3%), myrcene (3.0%),β-phellandrene (0.2%,), terpinolene (0.1%), 2,4-(8)-p-menthadiene (0.1%), methyl citronellate (0.4%), and geraniol (0.2%) were tentatively identified. The composition of this oil closely resembles that of Rocky Mountain juniper leaves. A small amount of the oil from a hybrid of these two species was analyzed and the possibility of detecting hybridization by analysis of the leaf oil is discussed.
CHARGE TRANSFER AND ELECTRON CAPTURE IN THE RADIOLYSIS OF ALIPHATIC HYDROCARBONS
Authors: Dyne P. J.
Published: May 2006

A mechanism is suggested for the radiolysis of hydrocarbons. Both ions and excited molecules are produced in the initial excitation. Ion–electron recombination leads to the formation of excited molecules which have similar properties to those formed initially; all subsequent decomposition proceeds through these excited molecules. In mixtures of hydrocarbons, ions and molecules may undergo positive charge exchange and additives reduce the hydrogen yield by capturing electrons or reacting with the positive ion. The mechanism provides a rationalization for a variety of observations.
CATION EXCHANGE IN ANHYDROUS ETHYLENEDIAMINE
Authors: Heumann Walter R. , Dionne Onil , Tremblay Gilles
Published: May 2006

The swelling of the strongly acid cation exchangers Dowex 50 W of various degrees of cross-linking is markedly less in ethylenediamine than in water. However, it is sufficient for exchange reactions to occur. In contrast with aqueous solutions, electrolytes dissolved in ethylenediamine cause the swelling to increase, which is attributed to the low degree of dissociation attainable in this solvent. This explanation is supported by the observation that in water slightly dissociated electrolytes also produce a slight increase in swelling. Exchange reactions were carried out successfully with the slightly cross-linked resin Dowex 50 W-X2. The bromide, ethoxide, aminoethoxide, and 2-aminoethylamide of lithium exchanged the latter cation with other alkali metals or tetrabutylammonium easily.
REFINEMENT OF THE CRYSTAL STRUCTURE OF β-Mg2P2O7
Authors: Calvo Crispin
Published: May 2006

The crystal structure of Mg2P2O7 reported by Lukaszewicz has been refined by least squares analysis. Data of the hkl type with O ≤ k ≤ 6 have been used to obtain improved atomic parameters. The central oxygen atom of the P2O7−4 is found to have enhanced thermal motion in the plane perpendicular to the P—P vector. Thus the P—O—P bond angle appears to be linear in this phase because of a thermal averaging of the position of the central oxygen atom. This conclusion is in agreement with that obtained by Lazarev from infrared studies.
ON THE FORMATION OF "Ag2O3" ON SILVER ELECTRODES
Authors: Casey E. J. , Moroz W. J.
Published: May 2006

"Ag2O3" was examined electrochemically in eutectic KOH−H2O at −40 °C by coulombic measurements of quantities formed, open circuit potential decays, variation of potential as a function of anodic current density, and temperature coefficients of decomposition rates. It can be formed directly from Ag2O on Ag at current density (c.d.) > 15 μA/cm2, with a maximum thickness during the first oxidation cycle (25 layers, assuming a surface roughness factor of one) occurring at 65 μA/cm2. Potential decay (−∂E/∂ log t ≡ b) curves have protracted linear regions where 0.045 < b < 0.078, sometimes higher. One-tenth of a layer of adsorbed species superimposed on the higher oxide exists on the surface during O2 evolution. Reduction curves show a minimum in the potential decay of the higher oxide preceding the formation of Ag2O. The "Ag2O3" decomposes in approximately 1 h at −40 °C to either AgO or Ag2O. The activation energy for its thermal decomposition is 12.0 ± 2.0 kcal/mole. Under most experimental conditions studied the results indicated that the material is not true Ag2O3 but it is probably better described as Ag2O[O] where [O] is trapped oxygen.The evidence does point to the probable existence of a thin layer, which may be true Ag2O3, on the surface in a steady state which is maintained at high anodic current density ( > 100 μA/cm2 at −40°).
POTENTIAL ANTICANCER AGENTS. I. URETHANE-TYPE NITROGEN MUSTARDS OF SOME SYNTHETIC ESTROGENS
Authors: Grant E. , Niculescu-Duvăz I.
Published: May 2006

not available
SYNTHESIS OF SOME TETRAZOLE SALTS
Authors: Tremblay Méude
Published: May 2006

not available
SYNTHESIS OF α-ALKYL-SUBSTITUTED AMINO ACIDS AND DERIVATIVES
Authors: Abshire C. J. , Berlinguet L.
Published: May 2006

not available
ELECTRONIC EFFECTS IN E2 REACTIONS: II. t-BUTOXIDE-INDUCED ELIMINATIONS OF 2-METHYL-3-PENTYL ARENESULFONATES
Authors: Colter Allan K. , McKelvey Donald R.
Published: May 2006

As part of a study of the influence of electronic effects imposed by the leaving group on orientation in E2 reactions, a study of elimination in a series of 2-methyl-3-pentyl arenesulfonates (I) has been carried out. The compositions of the olefin mixtures resulting from reaction of selected members of this series with potassium t-butoxide in t-butanol (1a, Id), 50% (by volume) t-butanol – dioxane (Ia–Ig), 25% (by volume) t-butanol – dioxane (Id–If), and 25% (by volume) t-butanol – dimethyl sulfoxide (Ia, Id, If, Ig), at 50 °C, have been determined using vapor phase chromatography. Second-order rate constants were measured for these reactions in t-butanol (Ie), and 50% t-butanol – dioxane (Ia, Ic–Ig) at 50 °C and in 25% t-butanol – dimethyl sulfoxide (Ia, Id, Ie) at 25 °C.The compositions of the olefin mixtures vary in a fairly regular way with changes in the electronic nature of the leaving group, the fraction of 2-methyl-2-pentene and ratio of trans-to cis-4-methyl-2-pentene for the most part increasing with increasing electron withdrawal. The E2 reactions in 25% t-butanol – dimethyl sulfoxide produce trans- and cis-4-methyl-2-pentene in ratios (20 to 35) considerably higher than those in an equilibrium mixture (ca. 6).The results are discussed in terms of recent views on the E2 transition state.
PHOTOCHEMICAL TRANSFORMATIONS OF SOME 4′-AMINO-2-STYRYLPYRIDINES AND THEIR SALTS
Authors: Williams J. L. R. , Carlson J. M. , Adel R. E. , Reynolds G. A.
Published: May 2006

The photochemical behavior of 4′-amino-, 4′-dimethylamino-, 4′-diethylamino-, and 4′-di-n-propylamino-substituted trans-2-styrylpyridine were studied. Ultraviolet irradiation of aqueous solutions of the bishydrochlorides and methiodide–hydrochlorides for moderate periods of time produced mixtures of the corresponding cis and trans isomers. Long irradiation times produced the corresponding dimers in all cases except that of trans-4′-di-n-propyl-amino-2-styrylpyridine. The cis isomers of the free bases and methiodides were isolated from the cis–trans mixtures. The trans-methiodides are not photochemically labile. The spectra of each pair of isomers were determined in water and in 50% methanol–water, with the exception of the 4′-di-n-propylamino derivative, which is not sufficiently water soluble. In addition, the spectra of the corresponding methiodides, hydrochlorides, bishydrochlorides, and methiodide–hydrochlorides were determined. The basic strengths of the nitrogens in the cis–trans isomer pairs of the free bases and methiodides have been determined spectroscopically in water and in 50% methanol-water.
SUBSTITUTED QUINODIMETHANS: VIII. SALTS DERIVED FROM THE 7,7,8,8-TETRACYANOQUINODIMETHAN ANION–RADICAL AND BENZOLOGUES OF QUATERNARY PYRAZINIUM CATIONS
Authors: Melby L. Russell
Published: May 2006

Our continued study of derivatives of the 7,7,8,8-tetracyanoquinodimethan anion–radical (TCNQ−•) has shown that the simple N-methylphenazinium salt (IIa) exhibits a volume electrical resistivity of 7 × 10−3 Ω cm and thus is the most highly electrically conductive organic compound known. In contrast, the N-ethyl analogue has a resistivity of 109 Ω cm. Electrical properties of pyrazinium, quinoxalinium, and phenazinium analogues, including phenazine-derived cation–radical salts of TCNQ−•, are discussed. Qualitative observations are made concerning the electron paramagnetic resonance of the N,N′-dimethyldihydrophenazinylium cation–radical.
MECHANISM OF ACTION OF UDPGal-4-EPIMERASE: ISOTOPE EFFECT STUDIES
Authors: Bevill III Rardon D. , Hill E. Alexander , Smith F. , Kirkwood S.
Published: May 2006

The synthesis of uridine diphosphate glucose and uridine diphosphate galactose labeled with tritium in the 4-position permits the observation of the isotope effect associated with the UDPGal-4-epimerase reaction. This isotope effect has been measured for the reaction proceeding in both directions and the values of kT/kHfall in the range 1.5 to 3.0. This allows certain conclusions to be drawn concerning the mechanism of this important enzymatic catalysis. The direction and magnitude of the effect indicate that the 4-hydrogen is removed from the hexose in the course of the reaction. They also appear to dispose of several mechanisms that have been proposed for the epimerase. Specifically, mechanisms involving cleavage of the C—O or C—C bonds at carbon-4 of the hexose moiety, such as cleavage of the carbon chain, elimination and readdition of the carbon-4 hydroxyl as water, or ionization to form a carbonium ion, are not supported by the observed data. A mechanism consistent with all observations involves transfer of the hydrogen at carbon-4 to the enzyme in a step that is not rate determining. This is followed immediately by the rate-determining step, which may well be the reorganization of the enzyme–substrate complex to allow return of the hydrogen in the opposite configuration. The larger estimate of the isotope effect indicates a transfer of the carbon-4 hydrogen to a nitrogen atom located in the enzyme's structure; the smaller estimate is consistent with transfer to oxygen or carbon. Transfer to sulfur appears to be definitely eliminated.During this work a degradative procedure that will permit the location and quantitation of the carbon-bound tritium in any hexose or pentose was developed.
NUCLEAR MAGNETIC RESONANCE STUDIES: IX. THE CHEMICAL SHIFT OF THE FORMYL PROTON IN ALIPHATIC ALDEHYDES
Authors: Klinck R. E. , Stothers J. B.
Published: May 2006

The effects of structure on the shielding of formyl protons of aliphatic aldehydes have been examined. The survey included examples of acyclic, alicyclic, and α, β-unsaturated aldehydes. The potential use of these results as an aid for structural elucidations is discussed, and the limitations are noted.
GAS CHROMATOGRAPHY OF ESTRONE AND RELATED COMPOUNDS
Authors: Montalvo Rafael , Wheeler Owen H.
Published: May 2006

not available
ORGANOPHOSPHORUS–URANYL COMPLEXES STUDIED BY NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY
Authors: Burdett Jane L. , Burger L. L.
Published: May 2006

The effect of extraction of uranyl nitrate on certain neutral organophosphorus compounds has been observed by nuclear magnetic resonance (n.m.r.) spectroscopy. Proton and phosphorus chemical shifts have been measured for the complexed and uncomplexed material. The effect of complexation on proton–proton and proton–phosphorus coupling constants has been noted.
REACTIONS OF ORGANOTIN COMPOUNDS: VI. THE REACTIONS OF TIN HYDRIDES WITH PERFLUOROVINYL TIN COMPOUNDS
Authors: Beveridge A. D. , Clark H. C. , Kwon J. T.
Published: May 2006

The reactions of methyltin hydrides with methylperfluorovinyltin compounds have been examined under heat or ultraviolet irradiation. In no case is there evidence of addition to the C=C bond. Instead, extensive reduction of the vinyl group occurs to give cis-1,2-difluorovinyltin derivatives as the principal products, with smaller amounts of the trans-1,2-difluorovinyltin isomers, 2,2′-difluorovinyltin compounds, and products containing one or more —C2H2F groups. Trimethyl- or dimethyl-tin fluoride is formed quantitatively from the corresponding hydride. In the reaction of dimethyl bis(perfluorovinyl)tin with dimethyltin dihydride, vinyl-hydrogen exchange occurs at 60° in the dark to give dimethylperfluorovinyltin hydride, while under ultraviolet irradiation partially fluorinated vinyltin compounds are formed. On the other hand, no reaction takes place between dimethyl bis(perfluorovinyl)tin and 2 moles of trimethyltin hydride in the dark at 50°, but under ultraviolet irradiation at 25°, partial vinyl-hydrogen exchange occurs, accompanied by reduction, to yield both trimethyl and dimethyl partially fluorinated vinyltin compounds. The infrared and proton magnetic resonance spectra of the products are discussed.
KINETIC STUDIES OF CHLORO COMPLEXES OF RHODIUM AS HYDROGENATION CATALYSTS
Authors: James B. R. , Rempel G. L.
Published: May 2006

The anionic complexes [RhCl6]3−, [Rh(H2O)Cl5]2−, and [Rh(H2O)2Cl4]− activate molecular hydrogen for the reduction of ferric ion in aqueous acid solution; the catalytic activity increased with increasing number of chloride ligands present. Cationic and neutral chloroaquorhodium(III) complexes did not homogeneously catalyze the reduction of ferric ion, the complexes themselves being reduced to metallic rhodium, a powerful heterogeneous catalyst.Chloro complexes of rhodium(III) and rhodium(I) were not effective catalysts in aqueous solution for the homogeneous hydrogenation of the olefinic bond in maleic acid. Anionic chlororhodate(III) complexes were reduced by hydrogen to the univalent state, this state being stabilized against further reduction to the metal by complexing with the maleic acid present. Preliminary studies indicate that in dimethylacetamide solution rhodium (III) trichloride is an effective homogeneous catalyst for the reduction of maleic acid to succinic acid by hydrogen, the reaction proceeding through a rhodium (I) – maleic acid complex.
THE RADIOLYSIS OF TRIFLUOROETHANOL
Authors: Russell J. C. , McCallum K. J.
Published: May 2006

not available
COMMENT: DEFINITION OF BIRADICAL
Authors: Freeman G. R.
Published: May 2006

not available
PROTONATED CARBONYL GROUPS: VIII. ALKYLURACIL SALTS
Authors: Cook Denys
Published: May 2006

With 1,3-dimethyluracil and 1,3,6-trimethyluracil as models for nucleic acid bases, it was found by infrared spectroscopic methods that the site of protonation is a carbonyl group. Analysis of other evidence makes it likely that it is the carbonyl group in position 4. In 1,3,6-trimethyluracil salts, activation of the 5 position under acid conditions permits ready hydrogen–deuterium exchange.Some anomalous 2 base – 1 acid salts with complex acids are considered in the light of base pairing errors in nucleic acids.
THE SOLVENT ISOTOPE EFFECT AND THE PARTIAL MOLAR VOLUME OF IONS
Authors: Robertson R. E. , Sugamori S. E. , Tse R. , Wu C.-Y.
Published: May 2006

The partial molar volume of ions in water furnishes an indication, if not precise information, about the nature of ionic solvation (1–5). Accordingly, it was hoped that differences in this term and particularly the effect of temperatures on the differences in the apparent partial molar volume for a series of ions in light and heavy water would provide a basis for decisions on the nature of solvation of the benzenesulfonic ion. This ion is of considerable interest in the study of solvolysis, but very little is known about the characteristics of solvation.
THE THERMAL DECOMPOSITION OF ETHANE: PART I. INITIATION AND TERMINATION STEPS
Authors: Lin M C. , Back M. H.
Published: May 2006

The rates of production of methane and butane in the pyrolysis of ethane have been measured over the temperature range 550–620 °C and at pressures of 40–600 mm. At high pressure the rates of formation of both products were first order in ethane, but below 200 mm the first-order rate coefficients decreased. The ratio of methane to butane was consistent with the interpretation that methane is a measure of the initiation reaction and that the combination and disproportionation of ethyl radicals is the main termination step. The order of the decomposition of the ethyl radical with respect to ethane varied between 0.38 and 0.59. The results are discussed in terms of the mechanism of the overall process.
A SOLVENT-EXTRACTION STUDY OF THE THERMODYNAMICS OF ANILINE AND ITS NITRATE
Authors: Aboul-Seoud A. , Doheim M.
Published: May 2006

The distribution coefficients of aniline between n-heptane and aqueous sodium nitrate solutions were measured at different temperatures. The activity coefficients of aniline in aqueous sodium nitrate solutions were determined. The effect of sodium nitrate on the dissociation of the anilinium ion was studied at different temperatures by a modified distribution method. Attention was directed to the choice of the extracting solvent and of the analytical method. The effect of the presence of undissociated anilinium ions on the distribution coefficients was taken into consideration.K0, Kb, ΔH, ΔF, and ΔS for the dissociation of the anilinium ion were evaluated.
PHOTOLYSIS OF MIXES OF PERFLUOROACETONE AND PERFLUORODIETHYL KETONE REACTIONS OF CF3 AND C2F5 RADICALS
Authors: Gordon Alvin S.
Published: May 2006

not available
HYDROXYL PROTON MAGNETIC RESONANCE IN RELATION TO RING SIZE, SUBSTITUENT GROUPS, AND MUTAROTATION OF CARBOHYDRATES
Authors: Perlin A. S.
Published: May 2006

Some magnetic resonance properties of hydroxyl protons are described for a variety of sugars and derivatives in dimethyl sulfoxide. Spectral information of this kind is shown to be useful, particularly for differentiating between certain types of interconvertible molecular species. For example, a reducing sugar may be characterized as pyranose or furanose depending upon whether it exhibits a resonance signal that can be ascribed to OH-4 or OH-5, respectively. According to the data obtained, α-D-glucose, α-D-xylose, β-D-arabinose, α-D-lyxose, and α- and β-D-ribose are pyranoses when freshly dissolved, whereas the 2,3-carbonate of D-mannose or D-lyxose is in a furanose form. Selective deuteration and spin decoupling were of primary importance in making some of the spectral assignments.Although arabinose, ribose, and galactose exist partly as furanoses in mutarotated aqueous solutions, their tendency to adopt the structure of the five-membered ring is much greater in dimethyl sulfoxide. Such variability may be due to an interplay of effects; for example, the furanose forms are relatively stable, but this property is masked in water by preferential solvent stabilization of the pyranose structures.Depending on the number and kinds of hydroxyl proton signals detected, it is possible to distinguish between cyclic and acyclic forms of certain sugar derivatives, as illustrated with hydrazones and with dialdehydes obtained by oxidative glycol scission. Hydroxyl proton magnetic resonance data are of value also for characterizing partially acetylated sugars.
SYNTHESIS OF 4-ACETAMIDO-4-DEOXY-SUGARS
Authors: Dick A. J. , Jones J. K. N.
Published: May 2006

not available
ÉTUDE DE LA FORMATION DES COMPLEXES DU PROTACTINIUM AVEC LES ACIDES DI- ET POLY-CARBOXYLIQUES PAR LA MÉTHODE D'ÉCHANGE D'IONS
Authors: Galateanu Ioan
Published: May 2006

The formation of the protactinium complexes with malic, tartaric, trioxyglutaric, oxalic, aconitic, citric, and ethylenediaminetetraacetic acids has been studied by the ion-exchange method, and the instability constants have been calculated. The stability of the complexes increases in the following order: aconitic, malic, tartaric, oxalic, trioxyglutaric, citric, ethylenediaminetetraacetic acid.
THE TRANSMISSION OF POLAR EFFECTS: PART III. THE KINETICS OF THE ACID-CATALYZED ESTERIFICATION OF 3-SUBSTITUTED ACRYLIC ACIDS AND THE ALKALINE HYDROLYSIS OF THE METHYL ESTERS
Authors: Bowden Keith
Published: May 2006

The rate coefficients for the acid-catalyzed esterification in methanol at 35.0° of fourteen 3-substituted acrylic acids have been determined. Rate coefficients have also been determined for the alkaline hydrolysis in 70% v/v dioxin–water at 18.8° of 13 methyl esters and the carbonyl-stretching frequencies of the esters have been examined. The effect of trans-substitution is assessed by use of the Hammett equation. In the alkaline hydrolysis, the transmission of polar effects is approximately 1.9 that of the meta- and para-substituted benzoates. An analysis of the steric effects in the cis-isomers in both reactions shows that the steric effects of the halogeno-substituents in the two reactions differ and an explanation is offered. The application of the Taft–Ingold equation to ortho-substituted benzoates is criticized. The carbonyl-stretching frequencies of the cis-halogeno-esters exhibit a shift of +8 cm−1 compared with the trans-isomers; this shift is attributed to an electrostatic effect.
ISOTOPE EFFECTS IN MIXTURES OF LIQUID H2O AND T2O
Authors: Salomon Mark
Published: May 2006

Calculations are presented for the equilibrium tritium isotope effect involving water, hydronium ion, and hydroxide ion. The results are used to predict the kinetic isotope effect in the transfer of protons to a mercury cathode.
PREPARATION AND CHARACTERIZATION OF SULFONATED POLYSTYRENE LATEXES
Authors: Chan F. S. , Goring D. A. I.
Published: May 2006

The purpose of the work was the preparation of aqueous suspensions of model spherical particles stabilized by ionizable groups covalently bound to the surface. Starting material.was a 80/20 styrene/divinylbenzene latex. The latex had an average particle diameter of 500 Å as determined in the electron microscope. The copolymer was sulfonated in dichloroethane with a 3/1 SO3/triethylphosphate complex in a concurrent-flow fast-reaction apparatus and was purified by dialysis and ion exchange.Three main fractions with neutralization equivalents, Ne of 0.9, 1.8, and 2.7 meq g−1 were prepared. Elemental analysis revealed that the varying Ne in these fractions resulted from the absorption of Ca2+ and Mg2+ ions which were tightly bound to the inner-lying sulfonic groups of the particles. Treatment with strong acid followed by ion exchange eliminated the bivalent ions and increased Ne, but the titration pattern was markedly changed after such treatment. Sulfonation caused both the partial specific volume and the refractive index increment to decrease. Electron micrographs showed that the latex particles were only slightly polydisperse and that there was little change in size and shape after sulfonation. Light-scattering measurements established the absence of aggregates in the sulfonated latex. Particle sizes, determined from the intrinsic viscosities, indicated some swelling of the particles in 1 M aqueous NaCl. The extent to which the sulfonated latex satisfies the criteria required of a model colloid to be used for a study of electroviscous behavior is discussed.
INFRARED SPECTRA OF GeH2Br2 AND GeD2Br2
Authors: Beach Alexander L. , Griffiths James E.
Published: May 2006

not available
THE ISOTROPIC ELECTRON PARAMAGNETIC RESONANCE SPECTRUM OF THE 1 -HYDROXY-2,2,2-TRIFLUOROETHYL RADICAL
Authors: Smith P. , Pearson J. T. , Tsina R. V.
Published: May 2006

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HYDROGEN EXCHANGE INs-TRINITROBENZENE
Authors: Buncel E. , Symons E. A.
Published: May 2006

Hydrogen exchange in s-trinitrobenzene has been observed in the medium 90% dimethylformamide – 10% deuterium oxide containing sodium deuteriooxide (0.01 M). The proton transfer process between s-trinitrobenzene and base is therefore established. The factors which may contribute to the importance of the proton transfer process relative to the formation of Meisenheimer-type complexes are considered.
STEROIDS AND RELATED NATURAL PRODUCTS XXVI. SYNTHESIS OF 3β-ACETOXY-20-OXO-5β-PREGNA-14,16-DIENE
Authors: Pettit George R. , Piatak David M.
Published: May 2006

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STUDIES ON HYDROGEN–OXYGEN SYSTEMS IN THE ELECTRIC DISCHARGE: I. THE REACTIONS OF HYDROGEN ATOMS WITH HYDROGEN PEROXIDE
Authors: Ata Norisuke H , Glguère Paul A.
Published: May 2006

Hydrogen gas partly dissociated in an electrodeless discharge was mixed downstream with hydrogen peroxide vapor at low pressure (0.1 mm Hg) in a liquid nitrogen trap. The reaction products condensed readily on the wall as a clear, yellowish glass resembling that from dissociated water vapor and other related systems. A manometric study of the warming-up process has revealed four distinct steps. The first two, in which only traces of gas are given off, look like the recombination of trapped free radicals. The major evolution of oxygen upon crystallization of the glassy deposit at 160 °K is ascribed to the decomposition of hydrogen peroxide under the influence of some unidentified species generated in the electric discharge through hydrogen. Experimental evidence for this is presented. In any case the stoichiometry cannot be reconciled with the formation of a metastable intermediate, such as the hypothetical polyoxide H2O4.In the last step beginning around 215 °K more peroxide is decomposed during the eutectic melting of the solid. Qualitatively these phenomena are similar to those shown by the condensate from dissociated water vapor.
THE ENERGY OF HYDROGEN BONDING IN THE SYSTEM: ACETONE–BROMOFORM
Authors: Campbell A. N. , Kartzmark E. M.
Published: May 2006

A study of the equilibrium freezing-point diagram for the system acetone–bromoform shows that no solid-phase compound forms between acetone and bromoform. The diagram is of the simple eutectic type, the eutectic lying at −101° and 84 mole % acetone. The enthalpies of mixing have been determined for various compositions of mixture and the numerical value of ΔH (per mole of acetone or bromoform) extrapolated to infinite excess of bromoform or of acetone, to obtain the value for completely undissociated complex. This figure is −1.3 kcal per mole of complex (assumed mole to mole). The dipole moments, excess volumes of mixing, viscosities, and total and partial vapor pressures of the system have been measured. From these data, the excess free energy and excess entropy and other thermodynamic functions have been evaluated.
THE SYSTEMS SODIUM CHLORATE – WATER – DIOXANE AND LITHIUM CHLORATE – WATER – DIOXANE, AT 25°
Authors: Campbell A. N. , Kartzmark E. M. , Maryk W. B.
Published: May 2006

The phase diagrams of the systems sodium chlorate – water – dioxane and lithium chlorate – water – dioxane have been determined at 25 °C.The sodium chlorate – water – dioxane diagram is relatively simple, anhydrous sodium chlorate being the only solid phase. The occurrence of two liquid layers in contact with sodium chlorate is found between dioxane concentrations of 67.7 and 88.8%.The lithium chlorate – water – dioxane system exhibits both complex formation and a ternary miscibility gap. The lithium chlorate hydrate, [Formula: see text] exists from 0 to 2.2% dioxane. A mole to mole compound of lithium chlorate and dioxane, LiClO3•C4H8O2, exists from 2.2% dioxane to 100% dioxane. There exists a ternary miscibility gap between dioxane concentrations of 81.5 and 93.6%The X-ray powder data for anhydrous lithium chlorate, its quarter hydrate, and the compound of lithium chlorate and dioxane have been obtained.
MOLECULAR MOTION IN WEAK CHARGE TRANSFER COMPLEXES
Authors: Gilson D. F. R. , McDowell C. A.
Published: May 2006

"Wide line" nuclear magnetic resonance studies of several charge transfer complexes are reported. Line width transitions and comparisons of theoretical and experimental second moments indicate that molecular rotation occurs in several of these complexes. Estimates of the barriers to reorientation in the complexes show these to be lower than those observed for the corresponding pure compounds.
THE PHOTOLYSIS OF PERFLUOROAZOETHANE AT ROOM TEMPERATURE
Authors: Dacey J. R. , Kent W. C. , Pritchard G. O.
Published: May 2006

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AQUEOUS SOLUTIONS OF "SODIUM PERNITRITE" FROM ALKALINE HYDROGEN PEROXIDE AND NITRIC OXIDE
Authors: Petriconi Glanna L. , Papee Henry M.
Published: May 2006

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THE STEREOSELECTIVE ADDITION OF DIHALOCARBENES TO cistrans, trans-CYCLODODECA-1,5,9-TRIENE AND THE SYNTHESIS OF CYCLOTRIDECANONE
Authors: Nozaki H. , Katô S. , Noyori R.
Published: May 2006

The addition reactions of dibromo- and dichloro-carbenes to cis,trans,trans-cyclododeca-1,5,9-triene (I) followed a stereoselective scheme analogous to that of other reagents forming a three-membered ring on addition to an olefinic bond. The carbenes attacked preferentially one of the trans double bonds of I and then added to the cis double bond of the resulting bicyclic cis,trans dienes. Skattebøl's ring cleavage of dihalocarbene adducts of cis-cyclo-dodecene as well as of the monoadducts of I, followed by several steps, gave cyclotridecanone in fairly good yields.
POLAROGRAPHIC HALF-WAVE POTENTIALS OF SOME β-NITROSTYRENES AND RELATED COMPOUNDS
Authors: Silver R. F. , Holmes H. L.
Published: May 2006

The polarographic half-wave potentials of a number of β-nitrostyrenes, β-nitropropenylbenzenes, and β-nitrobutenylbenzenes have been determined in aqueous ethanolic solution at an apparent pH of 6.54. A linear relationship exists between these values and Hammett sigma constants, but not with their ultraviolet absorption maxima or with their dipole moments.The polarographic wave of 11 diethyl benzalmalonates, under the same conditions, was masked by the hydrogen wave.
CARBONYL AND THIOCARBONYL COMPOUNDS: X. SYNTHETIC EXPERIMENTS WITH COUMARIN-2-THIONE AND BENZOXANTHIONES
Authors: Latif N. , Fathy I.
Published: May 2006

The benzoxanthene ethers Ia–IIb are obtained in good yields by the action of tetrachloro-and tetrabromo-o-benzoquiuone on 1,2- and 3,4-benzoxanthione, respectively. The benzopyran analogues IIIa–IIIb are obtained by the interaction of the corresponding haloquinone and coumarin hydrazone. The latter, which is now readily obtained by the action of hydrazine hydrate on coumarin-2-thione, condenses with thioketones to give coumarin azines. The benzopyran ethers IIIa and IIIb are cleaved by malononitrile, cyanoacetic ester, hydrazine hydrate, phenylhydrazine, and benzoylhydrazine, yielding the unsaturated nitriles (Va–Vb) and the corresponding hydrazones, respectively.1,2-Benzoxanthione reacts with 9-diazoxanthene, diphenyldiazomethane, and diphenylenediazomethane to give the ethylene sulfides VI–VIII, respectively. However, coumarin-2-thione reacts with the diazo compounds in a different manner; it gives the ethylenes X and XI directly, together with the symmetrical thiiranes XII and XIII, in the cases of diphenyldiazomethane and 9-diazoxanthene, respectively, whereas the cyclopropane derivative XIV is produced in the case of diphenylenediazomethane. XIV is also obtained by the photochemical interaction of coumarin itself and the diazo compound.
PREPARATION OF cis- AND trans-OCIMENE FROM CATALYTIC PYROLYSIS OF LINALYL ACETATE
Authors: Mitzner Bernard M. , Lemberg Seymour , Theimer Ernst T.
Published: May 2006

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A GRAVIMETRIC STUDY OF HYDRATION OF POLYNUCLEOTIDES
Authors: Falk Michael
Published: May 2006

The hydration of soluble ribonucleic acid, of two forms of polyriboadenylic acid, and of nucleohistone was determined gravimetrically as a function of relative humidity (r.h.). The curves are smooth functions of r.h., similar to those obtained earlier for deoxyribonucleic acid. The general similarity of the hydration curves of the polynucleotides so far investigated is in agreement with the suggestion that the ionic phosphate groups are the primary hydration sites in polynucleotides. The hydration data fit the Brunauer–Emmett–Teller equation up to about 75% r.h. and the Harkins–Jura equation at higher values. Both equations yield a value of about 2.0 molecules of H2O per nucleotide for the "monolayer content" for all the polynucleotides investigated.
THE SULFURIC ACID SOLVENT SYSTEM: PART VII. SOLUTIONS OF SOME TIN(IV) AND LEAD(IV) COMPOUNDS
Authors: Gillespie R. J. , Kapoor R. , Robinson E. A.
Published: May 2006

Solutions of tetramethyl tin trimethyl tin sulfate, di-n-butyl tin diacetate, tetraphenyl tin, and triphenyl tin hydroxide in. 100% sulfuric acid have been investigated by cryoscopic and conductimetric methods. Tetramethyl tin reacts with sulfuric acid with the evolution of methane and the formation of trimethyl tin hydrogensulfate. Trialkyl tin hydrogensulfates and dialkyl tin dihydrogensulfates behave as strong bases. It is probable that the cationic species formed are protonated hydrogensulfates rather than "stannonium" ions. Phenyl-substituted tin compounds are cleaved in sulfuric acid with the formation of benzene sulfonic acid and the complex hexa(hydrogensulfato) stannic acid, H2Sn(HSO4)6, and its anions. Lead tetraacetate gives yellow solutions containing hexa(hydrogensulfato) plumbic acid, H2PB(HSO4O6, and its anions.
A NEW SYNTHESIS OF GERMYL IODIDE
Authors: Griffiths James E. , Beach Alexander L.
Published: May 2006

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STEREOCHEMICAL STUDIES: VIII. SYNTHESIS OF cis-1-OXA-10-METHYLDECAL-2-ONE
Authors: Edward J. T. , Ferland J.-M.
Published: May 2006

9-Methylhydrindan-1-one was obtained as a mixture (80% trans, 20% cis) in four steps from 10-methyl-Δ1,9-octal-2-one. In the presence of alkali it epimerized to cis-9-methylhydrindan-1-one containing less than 1% of the trans isomer. Oxidation of this cis ketone with peroxytrifluoroacetic acid gave cis-1-oxa-10-methyldecal-2-one.
KINETICS OF THE ABSTRACTION OF HYDROGEN ATOMS FROM HYDROGEN SULFIDE BY TRIFLUOROMETHYL RADICALS
Authors: Arthur N. L. , Bell T. N.
Published: May 2006

Trifluoromethyl radicals generated from the photolysis of hexafluoroacetone abstract hydrogen atoms from hydrogen sulphide.[Formula: see text]The rate constant of this reaction measured by comparing the rate with that for the recombination of trifluoromethyl radicals (k = 2.3 × 1013 cc mole−1 s−1) is given by,[Formula: see text]
RARE-EARTH PICOLINATE AND PICOLINATE-N-OXIDE COMPLEXES
Authors: Manning P. G.
Published: May 2006

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THE SIGN, TEMPERATURE, AND SOLVENT DEPENDENCE OF THE PROTON COUPLING CONSTANT AND CHEMICAL SHIFT IN α-CHLOROACRYLONITRILE
Authors: McLauchlan K. A. , Reeves L. W. , Schaefer T.
Published: May 2006

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COMPLEXES OF ALKYL AND ARYL CYANIDES. PART III. THE FAR-INFRARED SPECTRA (500–200 CM−1) AND ASSIGNMENT OF THE METAL-NITROGEN STRETCHING FREQUENCY IN COMPLEXES WITH PALLADIUM (II), PLATINUM (II), AND RHODIUM (III) HALIDES
Authors: Walton R. A.
Published: May 2006

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REACTIONS OF SUGAR CHLOROSULFATES: VII. SOME CONFORMATIONAL ASPECTS
Authors: Cottrell A. G. , Buncel E. , Jones J. K. N.
Published: May 2006

The reaction of sulfuryl chloride with several 1,6-anhydro-hexosans has yielded crystalline, fully chlorosulfated derivatives. Replacement of the chlorosulfate moieties by chlorodeoxy groups could not be achieved under the reaction conditions employed. This non-reactivity is discussed in terms of steric interactions in the transition state for substitution.An examination of some chloro-substituted sugar chlorosulfates confirmed that an axial chlorodeoxy group in a glycopyranoside deactivates a neighboring equatorial chlorosulfate group and thus prevents further chlorodeoxy groups being introduced into such positions. Methyl α-D-altropyranoside, methyl α-L-rhamnopyranoside, methyl α-D-lyxopyranoside, L-rhamnose, and D-lyxose were reacted with sulfuryl chloride. The resulting products were those expected if these sugars reacted primarily in the C1 conformation.
THE REACTION OF n-BUTYLAMINE AND BENZYLAMINE WITH SOME β-NITROSTYRENES, DIETHYL BENZALMALONATES, AND CINNAMALMALONONITRILES
Authors: Lough C. E. , Currie D. J.
Published: May 2006

The relative rates of reaction of n-butylamine with 27 β-nitrostyrenes, 36 β-nitropropenylbenzenes, 20 β-nitrobutenylbenzenes and 7 related compounds, 11 diethyl benzalmalonates, and 4 cinnamalmalononitriles were measured in dioxane solution at 25 °C. In addition, the slower rates of reaction of benzylamine with 15 of these compounds were measured under identical conditions. The pseudo first order rate constants, koverall, for all the reactions were adequately represented by the expression[Formula: see text]where A and B are constants which, in general, could be correlated with Hammett sigma constants. A nitro group substituted in the ortho position or chlorines substituted in both ortho positions gave anomalous rate constants in some series but not in others. A mechanism is proposed for the amine additions.
BORON SULFIDE AS A SOURCE OF ACYLOXYBORANE
Authors: Lalancette J. M. , Bessette F. , Cliche J. M.
Published: May 2006

Triacyloxyboranes ((RCO2)3B) are obtained in good yields by the action of organic acids on boron sulfide or on o-thioboric acid esters.
THE OCCURRENCE OF 2,3-DIBROMOBENZYL ALCOHOL 4,5-DISULFATE, DIPOTASSIUM SALT, IN POLYSIPHONIA LANOSA
Authors: Hodgkin J. H. , Craigie J. S. , McInnes A. G.
Published: May 2006

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PHOTOLYSIS OF SOLID CARBONYL SELENIDE AND CARBON DISELENIDE
Authors: Stiles D. A. , Tyerman W. J. R. , Strausz O. P. , Gunning H. E.
Published: May 2006

Samples of COSe and CSe2 were photolyzed at 77 °K, either pure or in matrices of Xe or trans-2-butene. Observed electron spin resonance spectra are assigned to Se(43P), to Se2, and to chains of selenium atoms, •Se(Se)nSe•. The selenium chains exhibit metallic behavior intermediate between that of sulfur and tellurium. It is suggested that polymeric chains of CSe are formed on warming photolyzed samples containing CSe2. The ultraviolet absorption spectrum of COSe vapor is reported.
INFRARED SPECTRUM AND STRUCTURE OF LIQUID WATER
Authors: Falk Michael , Ford T. A.
Published: May 2006

The infrared spectrum of HDO at low concentrations in H2O and in D2O was studied between 0° and 130° by a double-beam technique. Each of the three fundamentals of HDO shows nearly Gaussian contours, complete absence of shoulders, and a single maximum at a frequency intermediate between those of HDO in ice and in vapor. Increase of temperature causes a gradual shift of each band in the direction of the frequency in vapor. These observations fully support the "continuum" models of the structure of liquid water and present strong evidence against the "mixture" models. It is concluded that hydrogen bonds in liquid water have a broad, smooth, single-peaked distribution of strengths which gradually shifts with temperature. The hydrogen bonds at one end of this distribution have strengths comparable to those in ice, whereas those at the other end are very weak. These extremes do not correspond to distinct molecular species. Every description of liquid water in terms of "broken" and "unbroken" bonds, or "monomers" and "clusters", is therefore arbitrary.