bluuebunny/crossref_metadata_2025 huggingface dataset:
Δ5‐Steroids and provitamins d with branched side chains, II. The reduction of Δ5‐keto‐steroids via their mercaptals
Authors: Louw D. F. , Strating J. , Backer H. J.
Published: September 2010

The Δ5‐keto‐steroids described in our previous paper 1) were made to react with dithioglycol. Mercaptals could only be obtained from C24 ketones; they were reductively desulphurised to the Δ5‐androstene derivatives by boiling with Raney nickel in dioxan. LiAlH4 did not attack the carbon‐sulphur bond of the mercaptals. All C22 ketones were found to be subject to steric hindrance at the formation of mercaptals.
Thermal decomposition of higher sulphonylalkylnitrosamides: Vth communication on sulphonylnitrosamides
Authors: Hey D. H. , de Boer Th. J.
Published: September 2010

Sulphonylnitrosamides ArSO2N(NO)R with RC2H5, n‐C3H7, i‐C3H7 and n‐C4H9 undergo two types of decomposition in inert solvents at 95°, yielding

nitrogen and alkyl arylsulphonate

nitrogen, arylsulphonic acid and olefin.

The rate of gas evolution is strictly first order. This is compatible with a nitroso‐azo rearrangement as the rate‐determining step. The resulting diazosulphonate decomposes quickly into the products of either a or b.

Under the influence of acid arising from b, denitrosation becomes appreciable towards the end of reaction. Such denitrosation is not observed when RCH3, no acid (and olefin) being produced.
Investigation of the structure of the compounds TeCl4 · AlCl3 and SeCl4 · AlCl3 by means of the Raman effect
Authors: Gerding H. , Houtgraaf H.
Published: September 2010

Raman spectra of the addition compounds TeCl4 · AlCl3 and SeCl4 · AlCl3 in the liquid as well as in the solid state show, besides other lines, three more or less characteristic strong lines, for which in the case of liquid Tecl4. AlCl3 some information has been obtained with regard to their polarization state. The frequencies of these lines are compared with those of the component parts and of the AlCl4−; ion.

The findings point to an ionic structure for both compounds (TeCl3+ · AlCl4− and SeCl3+ · AlCl4−). The assigned frequency values for TeCl3+ and SeCl3+ in these compounds are somewhat higher than the corresponding lines in TeCl4 and SeCl4. This makes it probable that the interaction between TeCl3+ (and SeCl3+) and its surrounding anions (Cl− and AlCl4− respectively) is stronger in the compound TeCl4 (and SeCl4) than in the corresponding addition compound. Force constants have been calculated for TeCl3+ in the compound TeCl4 · AlCl3.
Notes on the extraction of nickeldimethylglyoxime by chloroform and on the photometric determination of nickel by the glyoxime method
Authors: Claassen A. , Bastings L.
Published: September 2010

The extraction of nickeldimethylglyoxime by chloroform has been investigated as a function of pH. In pure nickel solutions extraction is complete in the pH range 4.7‐10; in tartrate solutions in the range 4.8‐12 and in citrate solutions in the range 7.2‐12. Interferences by copper and cobalt are discussed.

For the photometric determination of the extracted nickel as the oxidized nickeldimethylglyoxime complex an improved procedure has been developed resulting in a colour system of great stability.
On the accuracy of moving‐bomb calorimetry: II. Equilibration of carbon dioxide between the gaseous and the liquid phase in the bomb
Authors: Bjellerup L. , Sunner S.
Published: September 2010

The rate of absorption of carbon dioxide in the liquid phase in a calorimetric bomb has been determined under conditions prevailing in rotating‐bomb calorimetry for compounds containing C, H, O, halogen or C, H, O, S. In order to ensure complete equilibration during the time of rotation, the following procedure is suggested for rotation of the bomb:

The bomb should be rotated end‐over‐end at a speed of 10‐12 rpm. During the rotation period the bomb should also make at least three complete axial turns, either continuously or intermittently. The length of the rotation period depends on the amount of bomb liquid. With approximately 10 ml of bomb liquid the rotation period should preferably be 3 minutes, although 2 minutes will be sufficient in most cases. With 30 ml of bomb liquid the rotation period should be at least 3 minutes and preferably 4.5 minutes.
The interaction of free radicals with aromatics: II. Reaction of 9‐substituted anthracenes with 2‐cyano‐2‐propyl radicals
Authors: Engelsma J. W. , Farenhorst E. , Kooyman E. C.
Published: September 2010

2‐Cyano‐2‐propyl radicals (R.) add on to 9‐substituted anthracenes (A) at the 10‐position, yielding radicals R‐A. having their free valence mainly at the 9‐position. These combine with R. to form substituted dihydro‐anthracenes R‐A‐R in high yield. Unlike the reactions of anthracene1), products R‐A‐A‐R are not formed and only a single isomer R‐A‐R is obtained. This difference is interpreted on the basis of model considerations, which lead to conclusions as regards the conformations of the products R‐A‐R.
Formation of 1‐phenyl‐2‐bromo‐indone‐3 by bromination of 2‐acetobenzophenone
Authors: Harms A. F. , Nauta W. Th.
Published: September 2010

In the course of synthetic work in the benzophenone series we undertook to brominate 2‐aceto‐benzophenone. Under the circumstances of the reaction, however, ring closure occurred, and instead of the expected ω‐bromo compound a substituted indone was obtained.
Some remarks on the Raman spectrum of solid phosphorus pentachloride
Authors: Gerding H. , Houtgraaf H.
Published: September 2010

Powell c.s. deduced from an X‐ray study that solid PCl5 has to be considered as [PCl4+] [PCl6−]. From the distances between P and Cl in PCl4+ and in PCl6− given by the authors, force constants fPCl4+ and fPCl6− have been calculated using Badger's rule. From these f values and by a comparison with the results of a similar calculation for SiCl4 it follows that the strongest lines of the Raman spectrum of PCl5, namely 358(15) and 451 (7), belong to v1(PCl6−) and v1(PCl4+) respectively. With these frequencies known, it is possible to make an estimate of the frequencies to be expected for the other Raman‐active vibrations of both ions. A probable assignment of Raman shifts to vibrations of PCl4+ and PCl6− is given. Force constants have been calculated for both ions, using formulae based on Nath's force field and on the orbital valence force field introduced by Heath and Linnett, Probable frequency values: PCl4+ 173, 244, 451, 627; PCl6− 244, 285, 358.
The Raman spectrum of liquid and solid AlCl3·NH3
Authors: Gerding H. , Houtgraaf H.
Published: September 2010

The Raman spectra (inclusive of polarization measurements) of liquid and solid AlCl3. NH3 have been taken.

An assignment of frequency shifts to vibrations of AlCl3. NH3 (symmetry C3v ) ‐ somewhat different from that assumed by Goubeau and Siebert ‐ has been given. Force constants have been calculated from these frequencies with Wagner's formulae.

To the symmetrical stretching vibration of N‐H in Cl3Al. NH3 a frequency has been assigned by us (liquid 3247 cm−1; solid 3259 cm−1), which is higher than the one assumed by Goubeau and Siebert (2900 cm−1). Our value shows a rather small difference from the corresponding one in free NH3.
Kinetics of the formation of azobilirubin
Authors: Overbeek J. Th. G. , Vink C. L. J. , Deenstra H.
Published: September 2010

The coupling reaction between bilirubin and p‐diazobenzenesulphonic acid has been carried out in a mixture of ethanol, chloroform, and water, in which all the components of the reaction are soluble. One molecule of bilirubin reacts with two molecules of the diazonium salt to give two molecules of azobilirubin. The yield of the reaction, as determined colorimetrically, is close to 100%. A kinetic analysis of the reaction has shown that it consists of two consecutive steps: bilirubin + p‐diazobenzenesulphonic acid → azobilirubin + + hydroxypyrromethene carbinol, hydroxypyrromethene carbinol + p‐diazobenzenesulphonic acid → → azobilirubin + CH2O.

At 20° C, in a medium of 60% by volume of ethanol, 30% of chloroform, and 10% of water, and containing 0.006 mole of HCl per litre, the first reaction constant k1 = 8.1 × 103 mole−1 1 min−1 and the second constant k2 = 1.2 × 103 mole−1 1 min−1.

In the coupling of bilirubin with 2,4,6‐tribromobenzene diazonium salt the main reaction is similar to that with p‐diazobenzenesulphonic acid. The corresponding tribromoazobilirubin has been isolated with a yield of 78%. It has been analysed, and its molecular weight has been determined by ebullioscopy in acetone. These data confirmed that the azodye formed contains only one‐half of the bilirubin molecule. A side‐reaction leads to a few per cent of a coupling product between one molecule of bilirubin and one molecule of the diazonium salt.
Application of the prins reaction to trans‐cinnamic acid and transformation of the reaction product into dl‐erythro‐1 ‐phenyl‐1,3 ‐dihydroxy‐2‐aminopropane (dl‐erythro‐phenylserinol)
Authors: Brugman F. W. , Arens J. F.
Published: September 2010

The reaction of trans‐cinnamic acid (I) with formaldehyde in acetic‐sulphuric acid solution yielded 4‐phenyl‐5‐carboxy‐1,3‐dioxane (II). Degradation of the carboxyl group according to the methods of Hofmann or Curtius yielded 4‐phenyl‐5‐amino‐1,3‐dioxane (III). The 1,3‐dioxane ring could be opened by means of phloroglucinol and hydrochloric acid. Acetylation of the product of the latter reaction yielded the triacetate of dl‐erythro‐1‐phenyl‐1,3‐dihydroxy‐2‐aminopropane (IV).
The application of radioactive iodine in the diagnosis of thyroid disease
Authors: Skanse Bengt
Published: September 2010

A review is given of the various radioactive iodine tests used for the evaluation of the thyroid function. The different quantitative tests are discussed chiefly from a fundamental point of view. The comparative merits and shortcomings of the various tests are reviewed. It is concluded that at present the thyroidal accumulation of radioactive iodine after a short interval is the most practical screening procedure. The determination of the protein‐bound radioactive iodine in the plasma or the measurement of the thyroidal iodide clearance are probably the best indices of the thyroid function.
Isotopes in body electrolyte measurements
Authors: Veall N.
Published: September 2010

The use of radioactive isotopes for measurements of body electrolyte content and turnover rate is briefly reviewed. Some of the more useful radioactivity measuring techniques are discussed including methods for double traces investigations and for the direct measurement of whole body radioactivity content.
The determination of isotope ratios by infrared gas analysis
Authors: Kluyver J. C.
Published: September 2010

A new method is described for the determination of the abundance ratios of stable isotopes. The method is based on the difference in the infrared absorption spectra of isotopic molecules. The infrared isotope analyzer developed is a relatively simple instrument and succeeds in the measurement of the C13 abundance in 20 mg of CO2 with an error of 0.005 at % C13N15 abundance in 8 mg of NNO with an error of 0.015 at % N15 in the neighbourhood of the natural abundances of C13 and N15 respectively.
Experiences with an I131 excretion test, using small radioactive doses
Authors: Stöa K. F.
Published: September 2010

A method for measuring small amounts of excreted radioactive iodine in the urine after oral administation is described. Extremely small doses (about 8 μ C ) have been used.

It is concluded that the I131 test is of great value in the diagnosis of thyroid diseases.
Emploi de I131 pour la recherche et le dosage de l'excretion thyreotrope urinaire
Authors: Henry R.
Published: September 2010

Utilisant l'augmentation de fixation de I131 dans la thyroide du cobaye, nous avons étudié les conditions dans lesquelles l'hormone thyréotrope ajoutée à de l'urine pouvait être récuperée.

Dans ces conditions, la recherche de l'élimination thyréotrope dans les urines de sujets normoux est le plus souvent négative.

Avec la technique plus sensible de Querido et des extraits suffisamment détoxiqués, il semble que la présence de l'hormone thyréotrope dans les urines normales soit constante.
Functions thyroidiennes et radioactivité du sang après administration de radioiode
Authors: de Visscher M.
Published: September 2010

L'auteur expose la méthode employée dans son laboratoire pour explorer le fonctionnement thyroïdien dans les cas complexes: après administration d'une dose‐test de radioiode, la radioactivité des fractions du plasma et celle des urines est mesurée. Les courbes d'iode hormonal marqué et d'iodure marqué du plasma, apportent un élément de valeur diagnostique plus considérable que la simple mesure du pouvoir de captation. Diverses applications sont données, notamment pour le diagnostic différentiel entre le myxoedème primitif et l'hypothyroïdie secondaire.

La valeur de la méthode a été contrôlée par des expériences similaires sur lapins ayant subi soit une thyroïdectomie soit une hypophysectomie, soit des injections d'hormone thyréotrope.
The use of I131 protein in intestinal absorption studies in man
Authors: Frazer A. C. , McWeeny D. J. , Pover W. F. R. , Ross Constance A. C. , Sammons H. G.
Published: September 2010

Balance studies in man are complicated by secretion into the intestine and modification of intestinal contents by micro‐organisms. To overcome some of these difficulties the absorption of I131 labelled protein has been used and the results are recorded and discussed in this paper. Studies have been made in normal children, children with coeliac disease and those with pancreatic insufficiency.

It is concluded that for the quantitative assessment of absorption the method is preferable to the nitrogen balance technique. It does not appear to be adequate as a test for pancreatic function, as marked proteolysis occurs even in the absence of pancreatic proteinases.
A propos de l'inclusion de carbone radioactif dans les protéines tissulaires au cours de certaines avitaminoses
Authors: Orekhovitch V.
Published: September 2010

Des données concernant des protéines nommées par nous procollagènes ont été présentées par nous et par nos collaborateurs. Les procollagènes existent dans la peau de tous les vertébrés; la teneur en ces protéines varie avec l'âge et avec l'état dans lequel se trouvent les animaux. C'est ainsi par exemple que nous avons pu démontrer que la teneur en procollagènes de la peau de cobayes diminue avec l'augmentation de l'age de ees animaux. La peau de cobayes n'ayant pas dépassé les 6 mois en contient de 7 à 10 fois plus que celle de cobayes de 8 mois et plus. En outre, nous avons constaté que chez les cobayes scorbutiques la quantité de collagène dans la peau est de moitié plus petite que chez les animaux sains. Ces observations nous ont permis de formuler l'hypothèse que l'inhibition pendant le scorbut des processus de la formation du collagène, signalée par de nombreux chercheurs, se trouve en rapport avec l'inhibition de la synthèse des procollagènes que selon nous précèdent le collagène dans l'organisme.
Repartition tissulaire du radiosodium dans l'organisme jeune et adulte
Authors: Lambrechts A. , Delava S. , Govaerts J.
Published: September 2010

Le sodium Na22, en quantité proportionnelle au poids, est injecté sous la peau à des rats jeunes (30‐40 g) et adultes (150‐170 g) qui sont sacrifiés 15 à 20 minutes après l'injection. Confirmant les résultats obtenus pour le foie chez la souris et le rat par Delava nous avons montré une répartition de radiosodium très différente chez l'adulte et le jeune animal dans les divers tissus et organes (serum, foie, reins, poumons, coeur, os, peau, muscle squelettique). L'activité spécifique trouvée dans les tissus de l'animal jeune est environ 5 fois plus élevée que chez l'adulte. Il n'y a pratiquement pas de différence entre la quantité de Na stable par unité de poids chez l'animal jeune et l'adulte.
Photometric estimation of calcium
Authors: Baker R. W. R.
Published: September 2010

Results obtained with a flame photometer developed for the determination of calcium in serum are presented, and details of a spray with micrometer control are given.
Potentiometric titration of chlorides in biological fluids
Authors: Jordan Arthur
Published: September 2010

The object of the work was to develop a method for the direct titration of chlorides in biological fluids using silver nitrate, the end‐point being detected by means of a direct‐reading potentiometer. This has been achieved.
The estimation of some different kinds of human haemoglobin
Authors: van der Schaaf P. C. , Huisman T. H. J.
Published: September 2010

The estimation of the amount of abnormal haemoglobins in the blood (in this case the foetal and sickle cell haemoglobin) can be carried out by different methods. It will be outlined that only by combination of some of these methods it is possible to detect the presence of small amounts of the foetal haemoglobin.
Spectrophotometric determination of hemoglobin oxygen saturation
Authors: Klungsöyr L. , Stöa K. F.
Published: September 2010

A rapid and accurate method for spectrophotometric determination of oxygen saturation in slightly diluted, hemolyzed blood is described. This method proved to be as accurate as the manometric method (van Slyke‐Neill) 1), but to take much less time.
Recherches électrophorétiques du sérum sanguin humain dans différentes solutions tampons
Authors: Heyndrickx G. V. , de Vleeschauwer A.
Published: September 2010

Des diagrammes obtenus lors des recherches électrophorétiques de sérum sanguin d'après Tisélius avec différentes solutions tampons, il apparaît qu'une bonne séparation entre l'albumine et la globuline α1 est déterminée par le pH, qui doit être de 8,6 à 8,9. Il apparaît également qu'une bonne séparation entre la globuline γ2 et le delta, dépend de la concentration en ions à mobilité réduite. Dans la pratique on donnera la préférence soit au tampon modifié de Michaêlis, soit au tampon de Longsworth d'après notre modification (Tableau I ‐ Solutions 3 et 5). Lors de l'emploi du tampon original de Longsworth (Tableau I ‐ Solution 4) on obtient également une bonne séparation de la globuline α1 et du delta, mais les électrodes doivent être couvertes d'une solution de chlorure de sodium, ce qui occasionne certains désavantages.
Methodes spéciales par contre‐courant pour l'analyse de mélanges de porphyrines
Authors: de la Gandara J. Otero , Torres J. Tamarit
Published: September 2010

La mélange de deux porphyrines, de K connu, est résous au moyen d'une formule, qui donne le K du mélange en fonction du pourcentage de chaque composant; pour cela une distribution en 4 transports suffit.

Le mélange de trois porphyrines, dont les K sont inconnus, mais significativement différents, est résous par une distribution en 8 transports. En caractérisant les courbes des substances extrêmes dans la distribution, on peut trouver le troisième composant.
Soluble uricase in the determination of uric acid
Authors: Holmberg Carl G.
Published: September 2010

In the following will be described the preparation of a highly purified and soluble uricase, which is very suitable for the determination of uric acid in serum and urine, using the principle employed by Kalckar
Zur Beurteilung der Serumlipoiduntersuchungen
Authors: Schulze Günter
Published: September 2010

Phosphatide, Cholesterol‐Ester und Neutralfette des Blutserums stehen zu einander in einem quantitativen Verhältnis. Zur Beurteilung von Serumlipoidwerten ist es notwendig, diese quantitativen Mischungsverhältnisse und ihre Grenzwerte im Normalen zu kennen. Die Beziehungen der genannten Stoffe untereinander wurden untersucht und Regulationsgleichgewichte wurden gefunden.
The measurement of the glomerular transference rate in man
Authors: Owen J. A. , Robson J. S. , Scandrett F. J. , Stewart C. P.
Published: September 2010

It is commonly but not unanimously held that the renal clearance of inulin measures the glomerular filtration rate in man, and that creatinine is partly excreted by the renal tubules.

Results obtained from infusion experiments indicate that both substances are excreted at rates proportional to the respective plasma concentrations. The creatinine/inulin clearance ratio is never less than 1.0 and tends to decrease when the concentrations of creatine and inulin are high, sometimes as a result of slight increases in the inulin clearance and more commonly due to slight decreases in the creatinine clearance

The interpretation of these findings is discussed in relation to the problem of the measurement of the glomerular filtration rate in man. It is concluded that there is at present no conclusive evidence in favour of the acceptance of the use of either substance.
Dérivés de l'acide β‐résorcylique a intérêt biologique
Authors: Buu‐HoOï Ng. Ph. , Xuong N. D. , Lavit Mlle D.
Published: September 2010

On décrit la préparation et les propriétés d'une série de composés nouveaux dérivés de l'acide β‐résorcylique, et pouvant présenter un intérêt pharmacologique: hydrazides, hydrazones, 1‐acyl‐4‐arylthiosemicarbazides, β‐résorcylate de quinine.
Acid anilides: I. Preliminary communication on the chromatography of acid anilides
Authors: de Jonge A. P.
Published: September 2010

A new method for the separation of fatty acids by means of the paper‐chromatography of the fatty acid anilides is described.

Paper‐chromatography of the lower fatty acids as such is difficult due to the volatility of the acids in question. To get round this difficulty two ways are open:

a) to make use of the salts 1); and

b) to subject the derivatives (hydroxamic acids 2), acid hydrazides 3), or ethyl esters 4)) to paper‐chromatography.

In the literature no mention is made of the application of the acid anilides. It is true that in a recent publication by Green 5) the paper‐chromatography of saccharinic acid anilides is discussed, but this investigator has not exploited the possibilities of the anilides.
An improved histochemical benzidine‐blue peroxidase method and a note on the composition of the blue reaction product
Authors: van Duijn P.
Published: September 2010

Starting from the observation that at a high salt concentration the blue intermediate in the reaction between peroxidase, hydrogen peroxide, and benzidine precipitates in the form of stable blue crystals, a histochemical method for peroxidases was developed. In this method 5% of NH4Cl is added to the benzidine‐H2O2 mixture. The blue crystals, prepared by adding a milk‐peroxidase concentrate to this mixture, have a minimum formula of C24H24N4Cl. 2 H2O. The formation of a semiquinone‐like odd (C12H12N2) +X−ion during oxidation of benzidine in an aqueous medium has been postulated by Weis, though such an intermediate was hitherto isolated from a nonaqueous medium only by Milligan, The blue reaction product, formed during enzymatic oxidation of benzidine in an aqueous medium, formally is in a state of reduction intermediate between benzidine and the odd ion. Such intermediates, though found by Kuhn in the flavine series, have not yet been reported in the “Wurster” series.
Photooxidation of ascorbic acid by isolated chloroplasts
Authors: Wessels J. S. C.
Published: September 2010

The photooxidation of ascorbic acid by chloroplasts in the presence of various quinones and dyes was investigated. The kinetics of the reaction were studied, using 2,6‐dichlorophenol‐indophenol as dye mediator. Inhibitors of the Hill reaction did not affect the photooxidation rate. It is postulated that the reaction is photosensitized by chlorophyll. Evidence for this assumption was obtained by bringing about quite the same reaction in alcoholic solution, the chloroplasts being replaced by chlorophyll a. A possible rôle of this photooxidation in the back‐oxidation of reduced Hill‐reaction oxidants is discussed.
Note on the electrical conductivity of solid I2Cl6
Authors: Vonk C. G. , Boswijk K. H. , Wiebenga E. H.
Published: September 2010

In contradistinction to the results of previous investigations 1), the electrical conductivity of I2Cl6 was found to show a discontinuity at the melting point.
Synthesis of β‐phenyl‐ethylamine derivatives. III bronchodilators
Authors: Moed H. D. , van Dijk J. , Niewind H.
Published: September 2010

The synthesis is described of a number of β‐(m,p‐dihydroxyphenyl)‐β‐hydroxy‐N‐aralkyl‐ethylamine derivatives,

magnified image

which were screened for their bronchodilator effect against acetylcholine‐induced bronchoconstriction in the guinea pig, and for their cardiovascular action.

The influence of the side‐chainmagnified imagepharmacological activity of the basic structure,

magnified image

was investigated. For comparison, a number of N‐alkylarterenols were prepared and examined.

At the same time attention was paid to the bronchodilator activity of adrenalone,magnified image, and some N‐alkyl and N‐aralkyl derivatives of noradrenalone.

The U.V. absorption spectra of these sympathomimetics, aminoalcohols as well as aminoketones, were measured.

The results are discussed.
Raman spectra of aliphatic chlorine compounds: II. Chloroethenes and chloropropenes
Authors: Gerding H. , Haring H. G.
Published: September 2010

Complete Raman spectra, inclusive of depolarization factors, are given for sixteen out of the thirty‐one possible chlorine derivatives of propene, ten of which have been prepared especially for this purpose.

Examination of the Raman results shows that the “specific group frequencies” derived for groups such as CH2, CH2Cl, CHCl2, and CCl3 from the Raman spectra of chloroethanes and chloropropanes largely retain their values in the chloropropenes.

From a comparative study of the Raman spectra of chloroethenes and ‐propenes an additional number of specific group frequencies is deduced, characterizing the configurations CH2, CH, CHCl, and CCl2.

The carboncarbon double‐bond frequency proper shows a decreasing value with an increasing degree of substitution of chlorine for hydrogen in the molecule.
Viscosimetric investigation into the influence of pH and ionic strength on molecular shape of a structural muscle protein
Authors: Wassermann Albert
Published: September 2010

An attempt to explain some viscosity properties of actomyosin in terms of a reversible polymerisation reaction can not be reconciled with experimental results described in this paper. A consistent explanation of these experiments can be given if it is postulated, that actomyosin, in dilute solution, is composed of flexible chains, the shape of which depends on pH and ionic strength of the solvent. The order of magnitude of the average distance between the chain ends of actomyosin molecules is estimated.
The oxidation of phenols with copper‐amine catalysts and its relation to the mode of action of tyrosinase V. Reaction mechanisms
Authors: Brackman W. , Havinga E.
Published: September 2010

The kinetic peculiarities of the conversion of monohydric phenols into orthobenzoquinone derivatives with oxygen as an oxidant and copper‐morpholine complex as a catalyst may be explained, at least in a qualitative sense, by assuming the following mechanism (see Fig. 1).

The primary reaction consists in the introduction of a hydroxyl group into phenol. This reaction occurs within a complex of copper with morpholine, phenol and hydrogen peroxide. The catechol formed is oxidized further, either by oxygen or by a cupric‐morpholine complex, to give ortho‐benzoquinone. This takes up morpholine to give the morpholinocatechol, which is subject to a rapid autoxidation to morpholino‐ortho‐benzoquinone. The addition of a second morpholine molecule followed by another autoxidation gives rise to the main reaction product: dimorpholino‐ortho‐benzoquinone.

The hydrogen peroxide necessary for the primary attack upon the phenol, originates from the autoxidation of the catechols formed.

The primary reaction occuring in the hypothetical copper‐morpholine‐phenol‐hydrogen peroxide complex explains the specific ortho‐oxidation as well as the exclusive activity of copper in these catalytic oxidations.

The overlap of the non‐hybridized 4 p orbital of the Cu atom with the electron system of the phenol and with the lone pairs of the hydrogen peroxide might have a diminishing effect upon the activation energy of the reduction‐oxidation reaction in the complex.
The crystal structure of P4S3
Authors: van Houten S. , Vos Aafje , Wiegers G. A.
Published: September 2010

The crystal structure of P4S3 has been determined by X‐ray diffraction. Space‐group Pnma, 8 molecules per unit cell. The crystal consists of P4S3 molecules having the same structure as that derived by Hassel and Pettersen 1) from an electron‐diffraction study of gaseous P4S3. The average P‐S and P‐P distances are 2.10 Å and 2.24 Å respectively.
Investigation of plant wound hormones
Authors: Haagen‐Smit A. J. , Viglierchio D. R.
Published: September 2010

Laurie, linolenic, and linoleic acids have been shown to cause a considerable growth response in the Wehnelt bean test. The action of these acids is enhanced in the presence of coenzyme A, cytochrome C, and ascorbic acid. The growth response to lemon peel infusion and pressed orange oil is attributed in part to the presence of these substances.
Direct oxidation of L‐gulono‐γ‐lactone to vitamin C
Authors: Berends W. , Konings J.
Published: September 2010

It is demonstrated that direct oxidation of L‐gulono‐γ‐lactone by Fenton's reagent gives rise to a reducing substance, which, according to all the reactions used, is identical with L‐ascorbic acid.
Synthetic neuromuscular‐ and ganglion‐blocking agents. N‐Alkylated bipyridyls, bipiperidyls, and their methylene and ethylene “homologues”
Authors: Beyerman H. C. , Bontekoe J. S.
Published: September 2010

The synthesis is reported of N.N′‐alkylated α,α′‐, β,β′ and γ,γ′‐bipyridylium diiodides (Type I), and of N,N′‐alkylated α, α′‐, β,β′‐ and γ,γ′‐bipiperidylium diiodides (Type II) listed in Table I. It was found thatwhen the bipyridyls were hydrogenated in absolute methanolic or ethanolic solution in the presence of a nickel catalyst not only reduction of the pyridine rings took place, but also N‐alkylation by the alcohols. This nickel‐catalyzed “hydrogenation‐alkylation” gave satisfactory yields.

In table II some N‐alkylated di‐(α‐pyridylium) and di‐(α‐piperidylium)‐methane and ethane diiodides of the Types III and IV are summarized.

Syntheses are described of di‐(α‐pyridyl)‐methane and 1,2‐di‐(α‐pyridyl)‐ethane, which compounds were needed as intermediates for the preparation of III and IV.

The compounds listed in the Tables I and II were prepared because of their possible neuromuscular‐ and ganglion‐blocking activity.
Raman spectra of aliphatic chlorine compounds: IV. Chloroketones and chloroacid chlorides
Authors: Gerding H. , Haring H. G.
Published: September 2010

The chloroacetones CH2Cl. CO. CH3, CHCl2CO. CH3, CH2Cl. CO. CH2CL CHCl2CO. CH2Cl, and CHCl2CO. CHCl2 have been prepared. Their Raman spectra as well as those of several other chloroketones and chloroacid chlorides have been determined. A comparative study of these spectra reveals that the specific bending frequencies for the groups CH3 and CH2Cl, as deduced for the chloropropanes, show a characteristic shift to lower values if these groups are directly attached to the carbonyl group; the “CCl3 frequency” is shifted to a higher value. An intense Raman line at 350 cm−1, which has been found in the spectra of several chloropropanes and chloropropenes containing a CHCl2 group, is particularly strong and characteristic in carbonyl compounds possessing the configuration CHCl2CO. ‐ or CHCl2CHCl. CO.‐. The carbonyl group frequency shows highly different values for groups of compounds such as saturated ketones (1730‐1760 cm−1), unsaturated ketones (1710‐1720 cm−1), and acid chlorides (1780‐1820 cm−1). v(CO) gradually Increases with an increasing substitution of chlorine for hydrogen in the molecule of saturated ketones. In unsaturated ketones, in which C  O and CC are conjugated, v(CO) and v(CC) are lowered and their Intensity is enhanced.
p‐Chloro‐o‐Sulphobenzaldehyde. Influence of BF3 in the case of oxidation with CrO3
Authors: van der Zanden J. M. , de Vries G.
Published: September 2010

For an investigation into the physiological activity of certain compounds we required I as starting material. We prepared it by the method described below.
Some thermodynamic properties of the system benzene ‐ 1,2‐dichloroethane. Part II: The excess molar heat capacities
Authors: Ruiter L. H.
Published: September 2010

A calorimeter similar to the one used in the heat‐of‐mixing experiments has served for the determination of the excess molar heat capacities of the system benzene‐1,2‐dichloroethane at 7.73° C, 20.46° C, and 35.66° C. At 7.73° C and 20.46° C the agreement between the directly measured excess molar heat capacities and those derived from the heat‐of‐mixing experiments is excellent. At 35.66° C the agreement is reasonable.
Some thermodynamic properties of the system benzene ‐ 1,2‐dichloroethane. Part III: The excess molar volumes
Authors: Ruiter L. H.
Published: September 2010

The excess molar volumes on mixing benzene and 1,2‐dichloroethane have been measured at 20.00°C, 30.10°C, and 50.00°C. It appears that the excess molar volumes are of the order of 0.25 ml/mole at equimolar concentrations. A small temperature dependency has been observed.

Finally some conclusions concerning this sytem have been drawn.
Studies on halogenated esters. Part I.‐ Esters of tertiary trichlorobutanol with some aromatic monocarboxylic acids
Authors: Gupta (Vaishwanar) Indu , Srivastava N. P.
Published: September 2010

Trichlorotertiary butanol has been condensed with benzoic, ortho‐, meta‐, and para‐chlorobenzoic, ortho‐, meta‐ and para‐toluic, para‐nitrobenzoic and acetic acids. The esters so obtained have been examined and analysed. Antiseptic and insecticidal properties of these compounds will be examined and reported separately.
Freezing‐point curves for binary systems of ϵ‐caprolactam with carboxylic acids
Authors: van Velden P. F.
Published: September 2010

Freezing‐point curves have been determined, by an approximately static method, in the temperature range 20‐90°C for binary systems of ϵ‐caprolactam with palmitic, benzoic, adipic and pimelic acid. The molecular compound formation, shown to occur from the diagrams, points to specific interaction between one carboxyl group and one caprolactam‐amide group.
Applications, limitations and the mechanism of amide formation from acids and urea
Authors: Rahman Aziz‐Ur
Published: September 2010

The formation of amide by interaction of urea and carboxylic acids according to the method of Cherbuliez and Landolt

E.Cherbuliez and F. Landolt, Helv. Chim. Acta 29, 1438 (1946).

) has been examined for its application and limitations. On the one hand, the method has been successfully extended to include a group of simple aliphatic, aryl‐aliphatic, and dibasic acids; on the other hand the fact, illustrated by numerous literature references, that this method fails in the case of those acids which contain functional groups in α‐ or β‐position is pointed out.

The mechanism of amide formation from acid and urea, based on the interaction of carboxylic acid and cyanic acid ‐ the latter being formed by decomposition of urea ‐, is suggested and discussed. The formation of cyanuric acid, isolated and identified in some experiments, is discussed in conjunction with some literature citations supporting the proposed mechanism.
The U.V. absorption spectra of p‐amino‐salicylic acid and some related compounds: II. Discussion of the U.V. absorption spectrum of p.amino‐salicylic acid)
Authors: Rekker R. F. , Nauta W. Th.
Published: September 2010

The U.V. absorption spectrum of p.amino‐salicylic acid was measured in water at various pH‐values ranging from 0‐12 and in methanol, ethanol, n.propanol. Attempts were made to give a satisfactory interpretation for the three observed absorption bands.

In buffer‐solutions containing borate a typical shift of the absorption bands could be observed.
An electron‐diffraction investigation of the molecular structures of acetone, 2‐butanone, and 3‐pentanone
Authors: Romers C. , Creutzberg J. E. G.
Published: September 2010

A description is given of a new electron‐diffraction apparatus. The dis‐fraction patterns of the vapours of acetone, 2‐butanone, and 3‐pentanone were analyzed. The carbonyl bond (1.24 Å) is coplanar with a planar zigzag cham of carbon atoms. The C‐C and C‐H distances are found to be 1.525 Å and 1.09 Å, respectively; ∠ C‐C‐C ∠ 109.5° and ∠ O‐C‐C ∠ 118.5°. The molecules show restricted rotation on the central C‐C bonds.
Potentiometric determination of arsenic by potassium permanganate in alkaline solutions
Authors: Issa I. M. , Elsherif I. M.
Published: September 2010

The oxidation of trivalent arsenic by potassium permanganate in alkaline solutions has been studied potentiometrically. The end points are largely affected by the concentration of the reactants and the alkalinity of the reaction medium. It is found that, provided the proper alkalinity is chosen, good results could be obtained. At alkalinities as low as 0.1NNaOH, dilute solutions could be titrated, so that the method can be applied for the determination of micro‐quantities of arsenic.
Phosphatidic acids and derivatives VI: Phosphatidic acids derived from batyl alcohol
Authors: Stegerhoek L. J. , Verkade P. E.
Published: September 2010

The synthesis of a number of phosphatidic acids derived from batyl alcohol and of the two batyl alcohol phosphoric acids is described.

Some properties of these substances are discussed.
The chemistry of acetylenic ethers XVI. Acetylenic thioethers
Authors: Arens J. F. , Doornbos T.
Published: September 2010

The preparations of ethylthio‐ and of tertiary butylthio‐acetylene are described. See scheme in the following text.
Thermodynamics of n‐alkanes
Authors: Schaerer A. A. , Baylé G. G. , Mazee W. M.
Published: September 2010

The properties of the crystalline Sβ‐modifications of n‐alkanes show alternation: this alternation effect is the basis of all alternation effects occurring in the general behaviour of n‐alkanes, also when other states of matter (liquid state or Sα‐modification) are involved. The properties of the latter states do not show alternation themselves.

Quantitative experimental evidence by means of thermodynamic data has now been obtained. In terms of enthalpy the magnitude of the alternation effect is about 600 cal/mole, in terms of entropy and free enthalpy the magnitudes are about 1.5 cal/mole °C and 80 cal/mole, respectively. Generally the Sβ‐phases of n‐alkanes with an even number of carbon atoms show relatively lower values for the absolute thermodynamic quantities as compared with the n‐alkanes with an odd number of carbon atoms.
Some complex fluorides of ruthenium
Authors: Peacock R. D.
Published: September 2010

Until recently few fluorine complexes of the platinum metals were known, and the only ruthenium‐fluorine compound reported was the binary pentafluoride RuF5.

Complex fluorides of pentavalent Ru have now been prepared from the reaction between bromine tri‐fluoride BrF3, ruthenium metal, and appropriate metallic bromide, e.g. KRuF6 is formed from BrF3, Ru and KBr. In aqueous solution these compounds yield complexes of tetravalent Ru; e.g. KRuF6 yields K2RuF6. The hexafluororuthenateIV ion RuF6 = is fairly stable towards water, but in the presence of hydrochloric acid chlororuthenate ion RuCl6 = is formed quantitatively.

Attempts are now being made to prepare these and other fluorine complexes of ruthenium by other methods.
Resolution and synthesis of an optically active fluoro complex
Authors: Matoush William R. , Basolo Fred
Published: September 2010

An optically active complex containing coordinated fluoride ion has been resolved for the first time. Salts of the new complex ions, cis and trans [Co en2NO2F]+ were prepared. Rates of aquation and racemization were measured for the complex [Co en2F2]+. It was of interest to find that the aquation of this complex is catalyzed by acid.
Contribution to complex formation with polyvalent chlorides and oxychlorides
Authors: Groeneveld W. L.
Published: September 2010

It is already well known that in a number of cases polyvalent chlorides and oxychlorides are able to form quite stable complexes. It was, however, not clear what influences determine the formation of these complexes, and we therefore made a number of investigations for the purpose of getting some insight into the properties of these chlorides and the reaction mechanism of complex formation. It is thought that polyvalent chlorides and oxychlorides behave in fundamentally different ways, the former forming complexes by a Cl− ion donor mechanism, the latter predominantly by dipole interaction.
Phosphoryl‐metal halide complexes
Authors: Payne D. S.
Published: September 2010

Molecular compound formation between metal halides and oxygencontaining compounds has often been considered as a consequence of metal to oxygen bonding.

The complexes SnCl4 · 2 POCl3 and TiCl4 · 2 POCl3 have been investigated. Data are presented which suggest complete dissociation of these compounds in the vapour phase. Equilibrium data on the dissociation of these molecules are discussed along with data on the molar volumes and other physical properties. It is concluded that metal to oxygen bonding cannot be held responsible for the formation of the complexes under consideration.
Crystal field theory of complex formation by ions in the first transition series ‐ experimental thermodynamic data (ΔH and ΔS)
Authors: George Philip
Published: September 2010

A correlation is established between the variation in bonding energy throughout a series of transition element complexes of the same composition, CaLn2+ …. MnLn2+ …. ZnLn2+, and the extra stabilization arising from the splitting of the d‐orbital into two sets of different energy in the field of the ligand groups. Quantitative data for eighteen ligands are discussed in terms of ΔHL for the reaction

equation image

and two derived quantities, Em and Er, the “maximum stabilization energy” and “transition series contraction energy”. To a first approximation, Em and Er fall into classes depending on the number and nature of the atoms directly bonded to the metal.
Directing effects in inorganic substitution reactions
Authors: Chatt J. , Duncanson L. A. , Venanzi L. M.
Published: September 2010

Substitution in square planar platinous complexes is similar in many respects to benzene substitution. Ammonia and amines already present in a complex direct incoming groups into cis‐positions whereas ethylene, tends to direct incoming groups into the trans‐position. An infra‐red spectroscopic investigation of a series of complex compounds of the type trans‐[L, am PtCl2] (am = piperidine and p‐toluidine) where L = RnM (M = P, As, Sb, S, Se, Te), P(OR)3 and C2H4, indicates that the trans‐directing effect does not operate by trans‐bond weakening as hitherto supposed. The donor capacity of the above donor atoms are found to lie roughly in order of their electronegativities. It appears probable that when a ligand withholds or withdraws the bonding electrons in the ligand‐to‐metal o‐bond, it directs substitution into the cis‐positions to itself.

On the other hand when the ligand‐to‐metal bond has some double bond character and electron withdrawal occurs in the π‐type bond substitution takes place in the trans‐position.
Komplexe in Wässeriger Lösung
Authors: Schwarzenbach G.
Published: September 2010

Es wird ein kurzer Ueberblick gegeben über die Lösungsstabilität von Metallkomplexen. Die Kationen mit Edelgaskonfiguration verhalten sich bei der Komplexbildung etwa so, wie man es bei der Annahme rein elektrostatischer Kräfte zwischen Zentralatom und Ligand erwarten würde. Bei den Kationen mit einer 18‐er Aussenschale oder mit einer anderen nicht‐Edelgaskonfiguration sind die Verhältnisse prinzipiell anders. Hier spielt die Gegensätzlichkeit zwischen Zentral‐ und Ligandatom in Bezug auf die Elektronegativität die Hauptrolle. Die Elektronegativität der Metalle beurteilt man dabei am besten an Hand ihrer Ionisationspotentiale. Chelatkomplexe sind besonders stabil und es wird gezeigt, wie man das Verhalten von Atomen und Atomgruppen als Koordinationspartner dadurch untersuchen kann, dass man dieselben als Substituenten von Chelatkomplexbildnern benutzt.
The mechanism of thorium IV and uranium IV hydrolysis
Authors: Hietanen Sirkka
Published: September 2010

The hydrolysis of Th4+ has been studied in a 1 M perchlorate medium at 25°C by electrometric titrations. The hydrogen ion concentration was measured with quinhydrone or hydrogen electrodes. It can be deduced from the equilibrium data that a series of complexes Th((OH)3Th)n or rather magnified image are formed with n = 1, 2, 3 etc. No upper limit for n was found and it was concluded that there must be complexes in the solutions with n values greater than 6. To a good approximation the data may be interpreted by the assumption that the equilibrium constants for all successive steps

are the same, k = 10−7.50 (mechanism IIIa with ko = 1, Acta Chem Scand. 8, 318‐335 (1954). The data agree well with thos published by Kraus and Holmberg (1954), although the conclusions differ somewhat.

The hydrolysis of U4+ has been studied in a 3 M perchlorate medium at the same temperature. Hydrogen and glass electrodes were used for the pH measurements. The data indicate that complexes magnified image are formed first with n = 1; at higher degrees of hydrolysis, larger complexes are formed, some with n > 3.
The application of solvent extraction to the study of chelate complexes of thorium
Authors: Dyrssen Margareta
Published: September 2010

The extraction method is very useful for studies of the complex formation of metal ions MN+ with chelating agents. These reagents are very often organic acids HA which form uncharged complexes MAN of very low solubility in water but of appreciable solubility in organic solvents. The distribution ratio, q, of the metal M between the two liquid phases is measured as a function of the concenrtation [A−] of free ligand. Mathemathical treatment of the function log q (log [A−]) very often enables the calculation of at least two parameters a and b for the complex formation. These parameters are defined by the equations

Moreover we can determine the distribution constant of the uncharged complex
On the properties of binary mixtures: II. A method for testing the assumption of compound formation
Authors: Högfeldt Erik
Published: September 2010

Positive and negative deviations from ideal behaviour in binary mixtures are discussed in relation to the formation of compounds with a stoechiometric composition AuBv. The results are applied to metallic mixtures.
The structure of the complex ions AgI2− and Ag4I6−−
Authors: Dallinga G. , Mackor E. L.
Published: September 2010

The presence of the complex ions AgI2− and Ag4I6− in solutions of AgI in water‐acetone mixtures, to which KI is added, has been demonstrated. The arguments leading to the assumption that these ions are formed are summarized and their structures, as determined from X‐ray analysis of the solutions, are discussed.
Mercuric complexes in aqueous solution
Authors: van Panthaleon van Eck C. L. , Wolters H. B. M. , Jaspers W. J. M.
Published: September 2010

An analysis of thermodynamic data on the Cu(NH2)n++ complexes reported in the literature shows that the heat and entropy of formation for every bond is constant within experimental error for 1 ≤ n ≤ 4; it is believed that this result indicates that all complexes involved have the same structure. Data on the stability of Hg++ complexes have led us to investigate the structure of these complexes. X‐ray measurements on complexes in aqueous solution are in agreement with a tetrahedral configuration for the HgCln complexes in the cases where n = 4 (HgCl4=) and n = 1 (HgCl(H2O)3+). According to these measurements HgCl2 is almost certainly a linear molecule and the only reasonable structure for the hydrated mercuric ion appears to be a regular octahedron, Hg(H2O)6++.

These results help to make it clear why a close relationship between the stabilities of the HgCl+, HgCl3− and HgCl4= ions has been observed, and why HgCl2 does not fit into this pattern.