bluuebunny/crossref_metadata_2025 huggingface dataset:
Electric tempest in a teacup: The tea leaf analogy to microfluidic blood plasma separation
Authors: Yeo Leslie Y. , Friend James R. , Arifin Dian R.
Published: September 2006

In a similar fashion to Einstein’s tea leaf paradox, the rotational liquid flow induced by ionic wind above a liquid surface can trap suspended microparticles by a helical motion, spinning them down towards a bottom stagnation point. The motion is similar to Batchelor [Q. J. Mech. Appl. Math. 4, 29 (1951)] flows occurring between stationary and rotating disks and arises due to a combination of the primary azimuthal and secondary bulk meridional recirculation that produces a centrifugal and enhanced inward radial force near the chamber bottom. The technology is thus useful for microfluidic particle trapping/concentration; the authors demonstrate its potential for rapid erythrocyte/blood plasma separation for miniaturized medical diagnostic kits.
Some Properties of Compressional Waves in Lennard-Jones and Devonshire Liquids. I. Weak Sound Waves
Authors: David HG , Hamann SD
Published: September 2006

The present paper describes some
calculations of the speed of sound u in a theoretical Lennard-Jones and
Devonshire liquid. It is found that u decreases as the temperature is raised,
but increases if the liquid is compressed. When quantum effects are considered
it is found that u decreases as the value of de Boer's quanta1 parameter Λ*
is increased. All these effects have been observed in experiments on real
liquids.
Diffusion across a Liquid-Liquid Interface
Authors: Watts JA
Published: September 2006

The rate of diffusion of iodine across the
liquid-liquid interface between potassium iodide solution and carbon
tetrachloride has been investigated. The initial rate of diffusion depends only
on the concentration of free iodine in the solution and is not influenced by
the iodine combined as I3-. There is no initial
interfacial resistance to diffusion. me as that for the subsequent reaction.
The Thermal Decomposition of Silver(II) Oxide
Authors: Allen JA
Published: September 2006

The thermal decomposition of silver(II)
oxide in a vacuum has been studied over the range 83-134 OC. The
rates are quantitatively accounted for by the Polanyi-Wigner equation, the
values of the vibration frequency at all stages being within a power of 10 of
the expected theoretical value. Changes in the rate at different stages of the
reaction are interpreted in terms of diffuseness of the reaction interface.
This conclusion is supported by X-ray and surface area studies. The activation
energy is 30 kcal.

The activation energy associated with the
removal of oxygen from the first layer has been shown to be the same as that
for the subsequent reaction.
Studies on Esters of Sulphuric Acid. I. Positions of Bond Fission during Hydrolysis of Dialkyl Sulyhates in Oxygen-18 Water
Authors: Lauder I , Wilson IR , Zerner B
Published: September 2006

The positions of bond fission during the
first stage hydrolysis of dimethyl, diethyl, and di-isopropyl sulphates under
acidic and alkaline conditions between 0 and 50 �C have been determined by the
use of 18O-enriched water. Isotopic analysis by the two independent
methods, namely, mass-spectrometry and micropyknometric density determination,
agreed within experimental error.

Each ester showed almost 100% alkyl-oxygen
fission. R-i-O.SO2.OR, under all conditions used. The present work
establishes with reasonable certainty that the results of similar work by
Kursanov and Kudryavtsev (1956) on dimethyl sulphate and of Anbar et al. (1954)
on diethyl sulphate are in error.
The Chemical Constituents of Australian Flindersia Species. XIV. The Constituents of Flindersia pubescens Bail. and F. schottiana F. Muell
Authors: Hollis AF , Prager RH , Ritchie E , Taylor WC
Published: September 2006

The alkaloids and other constituents of Flindersia pubescens Bail. and F. schottiana
F. Muell. have been isolated. From F. schottiana has been obtained osthol hydro-
ohloride and chemical work on its genesis is described. Several substances related
to osthol are reported for the first time.
The Chemistry of Ants. V. Structure and Reactions of Dolichodial
Authors: Cavill GWK , Hinterberger H
Published: September 2006

Dolichodial, isolated from Dolichoderus
acanthoclinea Clarki (Wheeler), is shown to be α-(2-formyl-3-methylcyclopentylacraldehyde
(I). The conversion of dolichodial into iridodial (II), and independently, into
isoiridomyrmecin (X), establishes further relationships in the cyclopentanoid
monoterpenes.
The α-Hydroxyacids of Sheep Brain
Authors: Downing DT
Published: September 2006

The α-hydroxyacids of sheep brain are
shown to consist of a series of straight-chain compounds having 14 to 26 carbon
atoms. The acids were isolated from the total lipids of sheep brain and a gas
chromatographic analysis was made of the isopropylidene derivatives of the
diols obtained on reduction of the α-hydroxyacids. Analyses were also
carried out on the mixture of hydrocarbons obtained on reduction of the diols.
Some complex anions containing rhenium
Authors: Colton R
Published: September 2006

Rhenium pentachloride dissolves in 12M
hydrochloric acid to give a reddish brown solution from which salts such as Cs2ReOCl5
may be isolated. Oxidation of the rhenium occurs if the solution is allowed to
stand exposed to the air and salts such as (K,Cs)2ReOCl6
may be isolated. These salts of rhenium(VI) have also been isolated by treating
a solution of rhenium pentachloride in a thionyl chloride/iodine monochloride
mixture with caesium chloride. The
complex acid thought to be HReI5, separated by ether extraction of a
solution of potassium hexaiodorhenate(IV) in 20% sulphuric acid, has been shown
to be in fact H2(ReI5OH) by isolating salts using cations
soluble in organic solvents.
Oxide halides of molybdenum and tungsten. I. Preparations
Authors: Colton R , Tomkins IB
Published: September 2006

New preparations of molybdenum oxide
tetrachloride, MoOCl4; tungsten oxide tetrachloride, WOCl4;
molybdenum oxide trichloride, MoOCl3; molybdenum dioxide dibromide,
MoO2Br2; and molybdenum oxide tribromide, MoOBr3,
have been developed. It has been shown that all previous preparations of
molybdenum pentachloride apparently contained some oxide tetrachloride. The
magnetic susceptibility of pure molybdenum pentachloride has been measured over
a temperature range.
Octahedral cobalt(III) complexes in dipolar aprotic solvents. I. The substitution of thiocyanate into the cis-Chlorodimethylsulphoxidobisethylenediaminecobalt(III) ion in anhydrous dimethylsulphoxide and NN-dimethylformamide
Authors: Chin LF , Millen WA , Watts DW
Published: September 2006

The substitution of thiocyanate ion into
the cis-chlorodimethylsulphoxidobisethylenediaminecobalt(III) ion, cis-(Coen2(DMSO)Cl)2+,
has been studied in the solvents dimethylsulphoxide (DMSO) and
NN-dimethylformamide (DMF). In DMSO the reaction shows second-order
characteristics which are accounted for by an ion-pair dissociative mechanism (SNIIP). The activation energy
is 30.1 kcal mole-1.

In DMF the entry is first-order, the rate
determining step being solvolysis to the intermediate cis-(Coen2(DMF)Cl)2+
which has been isolated as the nitrate. In high thiocyanate concentrations the
rate shows some thiocyanate dependence due to the competition of ion-paired
thiocyanate with the DMF solvent for coordination following the DMSO
dissociation. The activation energy for this substitution is 17.5 kcal mole-1.
Electronic conduction in polymers. V. Aromatic semiconducting polymers
Authors: Bolto BA , Weiss DE , Willis D
Published: September 2006

Electronically conducting polymers have
been prepared by treating hexa- chlorobenzene with sodium at 300�, using sodium
chloride as a diluent. The products, presumably polybenzenes, have
resistivities of 0.2-25 ohm cm depending on the amount of sodium used; less
crosslinked polymers similarly prepared from 1,2,4-tri-chlorobenzene have resistivities
some thousand times greater.

It has been confirmed that the reaction of
sulphur with anthracene at 400� yields conducting polymers whose resistivity decreases
with increasing sulphur content. A product containing 54% sulphur had a
resistivity of 330 ohm cm.

The data presented show that good
conductors can be obtained without the presence of hetero atoms within the
aromatic network of the macromolecules.
Complexes of cobalt(II) halides with 4-methylpyridine and 2-methylpyridine
Authors: Graddon DP , Watton EC
Published: September 2006

Complexes of CoCl2,
CoBr2, CoI2,
and Co(NCS)2 with two and four molecules of 4-methylpyridine and two
molecules of 2-methylpyridine have been prepared. Their magnetic properties,
conductivities, and reflectance and absorption spectra in the visible region
show that all the compounds of the type CoX2B2 are
tetrahedral except Co(NCS)2(4-mepy)2,
which is an octahedral polymer like its pyridine analogue. Infrared spectra in
the 3-15 μ region lend no support to the suggestion that there may be
differences in the extent of π-bonding between the metal and the base or
the metal and NCS- in tetrahedral and octahedral complexes.

It is suggested that the position of the
ligands in the spectrochemical series and the relative stabilities of the
compounds CoX2B2 with respect to dissociation into CoX2B4
and free base can be explained in terms of repulsion effects between the
non-bonding electron pairs on the ligands and metal dє-orbitals
on the one hand and the non-bonding electron pairs of neighbouring ligands on
the other.
Simple pyrimidines. VIII. The fine structure of isocytosine, thiocytosine, and some isomers
Authors: Brown DJ , Teitei T
Published: September 2006

The fine structures of 4-amino-6-hydroxy-,
4-amino-6-mercapto-, 4-amino-2-mercapto-, 2-amino-4-hydroxy-, and
2-amino-4-mercapto-pyrimidine are revealed by comparing their ultraviolet
spectra and ionization constants with those of their S- and 0-, or N- and
S-methyl derivatives. On the evidence here presented they appear to exist
largely in aqueous solution as the tautomers containing an amino group, namely:
4-amino-1,6-dihydro-6-oxopyrimidine, 4-amino-1,6-dihydro-6-thiopyrimidine,
4-amino-1,2(and 2,3)-dihydro-2-thiopyrimidine, 2-amino-1,4(and
3,4)-dihydro-4-oxopyrimidine, and 2-amino-1,6-dihydro-6-thiopyrimidine,
respectively. Syntheses of hitherto unknown methyl derivatives are recorded.
Nickel(II) complexes of some o-hydroxyarylcarbonyl compounds
Authors: Gaddon DP , Mockler GM
Published: September 2006

Nickel complexes of o-hydroxyarylcarbonyl compounds, (RCOC6H4O)2Ni (R = H, CH3, C2H5,
C6H5, OCH3, OC2H5), have
been studied in the solid state and in solution. Their six-coordinate adducts
(RCOC6H4O)2NiB2
(B = H2O or 4- methylpyridine) are unstable in solution in
hydrocarbon solvents and break down to (RCOC6H4O)2Ni. In solution these anhydrous compounds are
monomeric, paramagnetic (μeff 3.0-3.5), and have absorption
spectra characteristic of octahedral nickel(II). It is concluded that they are
probably examples of high-spin, square-planar complexes of nickel(II), though
possibly polymeric and octahedral in the solid state.
Octahedral chromium(III) complexes in dipolar aprotic solvents. I. The isomerization of cis- and trans-Dichlorobisethylenediamine-chromium (III) ions in anhydrous NN-dimethylformamide
Authors: Palmer DA , Watts DW
Published: September 2006

The kinetics and mechanism
of the isomerization of cis- and trans- dichloro- bisethylenediaminechromium(III)
ions, cis- and trans-[CrCl2 en2]+, have been investigated in
anhydrous NN-dimethylformamide (DNF). The complex cis- chlorodimethylformamidebisethylenediaminechromium-
(III), cis-[CrCl(DMF) en2]2+,
is found to be a necessary intermediate and to remain a significant part of the
system at equilibrium.

The equilibria are found to depend on the
concentration of free chloride ion as has been found in the comparable cobalt
system.��� Activation parameters have been determined for
isomerization reactions using both the cis- and trans-(CrCl2
en2)+ ions as starting
materials and for the chloride entry reaction into the cis-[CrCl(DMF)
en2]2+ ion which has been
isolated as cis-[CrCl(DMF) en2](ClO4)2,R2O.
Flavan derivatives. XV. Reinvestigation of the supposed enediol diacetate derived from dihydroquercetin 5,7,3',4'-tetramethyl ether: Novel ringfission of dihydroquercetin 5,7,3',4'-tetramethyl ether to α,2'-diacetoxy-3,4,4',6'-tetramethoxychalcone
Authors: Clark-Lewis JW , Jemison RW
Published: September 2006

Boiling acetic anhydride
and sodium acetate is shown to convert (�)- dihydro-quercetin tetramethyl ether
into (α,2?-diacetoxy-3,4,4?,6?- tetramethoxychalcone, the first chalcone
derivative to be isolated from base-catalysed ring fission of a dihydro-flavonol.
7,3?,4?- Trimethoxydihydroflavonol under similar
conditions gave the 3-acetate as the only characterizable product, so that a
methoxylated phloroglucinol-type A ring appears necessary for fission of a
dihydroflavonol to the corresponding chalcone diacetate. The dihydrochalcone
obtained by hydrogenation of α,2?-diacetoxy-3,4,4?,6?- tetramethoxychalcone
was also prepared by unambiguous synthesis in nine stages from phloroglucinol
(33% over-all yield), and was converted in low yield by N-bromosuccinimide into
α,2?-diacetoxy-3?(or 5?)-bromo- 3,4,4?,6?-tetramethoxychalcone. Infrared
and nuclear magnetic resonance data are recorded for the compounds described.
Tunnel model for quantum liquids
Authors: Oden L , Henderson D
Published: September 2006

In the tunnel model, a
fluid is regarded as being composed of lines of molecules which move almost
one-dimensionally in lines or tunnels, the walls of which are formed by
neighbouring lines of molecules. This model has been used, with good success,
to describe the properties of classical hard spheres and classical simple
liquids. For quantum fluids the energy levels of a one-dimensional line of
molecules must be calculated. This has been done only for a system of hard
spheres. For more complicated systems the energy levels must be approximated.
In this paper the tunnel model is applied to liquid 4He
at absolute zero and to liquid H2. The lowest energy level has been
approximated and the hard-sphere energy levels are used to estimate the higher
energy levels. The agreement with experiment is generally good except in the
critical region.
Inorganic coordination complexes of manganese(II) phthalimide with primary and secondary aliphatic amines
Authors: Narain G , Shukla P
Published: September 2006

A series of complexes of
manganese(II) phthalimide with aliphatic amines has been prepared. The general
formula Mn(C8H4O2N)2(amine)4
is indicated by the analytical data. Conductivity measurements in nitrobenzene
indicate the complexes to be non-electrolytes. Infrared and visible absorption
spectrophotometric measurements have been made and a possible interpretation of
the data has been presented.
Photochemical reactions of azo compounds. IX. Further studies related to the photochemical reactions of bisazo compounds
Authors: Jamieson NC , Lewis GE
Published: September 2006

The photochemical reactions
of 4,4?-bis(phenylazo)biphenyl and 4- phenyl-azoazobenzene in 98% sulphuric
acid have been examined, for comparison with the corresponding reactions in 22N
acid. Photochemical cyclodehydrogenation of 4-phenylazoazobenzene to two benzo[c]cinnoline derivatives
has thereby been effected for the first time. The observed course of the latter
reaction has led, in turn, to studies of the benzidine
rearrangement of 2-(2-phenylhydrazino)benzo[c]-
cinnoline, of the photochemical cyclodehydrogenation
of 3-phenylazobenzene, and of the photochemical
reaction of 2-phenylazobenzo[c]cinnoline. The results
of these investigations are now recorded and discussed.
Synthesis of D-(+)-tecostidine and related actinidine derivatives
Authors: Cavill GWK , Zeitlins A
Published: September 2006

6-, 8-, and
11-Hydroxyactinidine have been synthesized. D-(+)-11- Hydroxy-actinidine is
shown to be the enantiomer of tecostidine, thus defining the absolute
configuration of the natural product. Reduction of (+)-11-hydroxyactinidine has
given a mixture of the stereoisomeric tecostanines.
The reaction of some indoles with selenium dioxide
Authors: Wilshire JFK
Published: September 2006

The reaction of selenium
dioxide with indole in benzene gives 3,3?- diindolyl selenide. In separate
experiments but with similar reaction conditions, 2-methyl-indole gave complex
mixtures from which either 3,3?-di(2-methylindolyl)
diselenide or the corresponding triselenide was isolated in low yield.
1,2-Dimethylindole gave 3,3?-di(1,2- dimethylindolyl) triselenide, also in low yield.
Peptide syntheses with the 2,4,6-trimethylbenzyl esters of L-asparagine and L-glutamine
Authors: Stewart FHC
Published: September 2006

The 2,4,6-trimethylbenzyl
esters of L-asparagine and L-glutamine have been obtained as the crystalline
hydrochlorides by treatment of the o- nitrophenylsulphenyl amino acid esters
with methanolic hydrogen chloride. These hydrochlorides were used in the synthesis
of several benzyloxycarbonyl peptide 2,4,6-trimethylbenzyl esters, which were
converted into the corresponding free peptides by the action of hydrogen
bromide in acetic acid under mild conditions.
The adsorption of ethylene on silver(I) oxide. II. Adsorption equilibria
Authors: Allen JA , Scaife PH
Published: September 2006

The adsorption of ethylene
on silver(I) oxide in the temperature range 190-363�K has been studied by
volumetric and gas chromatographic methods. A reversible adsorption process
characterized by an isosteric heat of 8.4 kcal mole-1 extends over
the whole range of temperature and coverage, and coexists at temperatures
greater than 250�K with an activated adsorption process described in the
preceding paper.
The polarographic and chronopotentiometric reduction of nickel(II) complexes
Authors: Woodburn SI , Magee RJ
Published: September 2006

A comparison of Ep
reduction potentials with the absorption spectra and transition times of the
complexes has proved valuable in the investigation of the reduction of
nickel(II) complexes.

From the work it can be stated that as the
ligand in the complex becomes stronger (in the spectrochemical sense), the
complex becomes more stable towards the mercury drop in that higher negative
potentials are required for reduction and the chronopotentiometric
rate of reduction becomes greater.
The hydrolysis of some acidic metal cations in acetonitrile containing traces of water
Authors: Shirvington PJ
Published: September 2006

Acetonitrile is a solvent
in which the halogen acids are highly associated. The strongly polarizing Al3+ and Ti4+
ions, when present in acetonitrile with comparable concentrations of water,
form very stable hydroxy complexes. These two factors bring about the formation
of halogen acids when the metal ions are dissolved in solvent containing halide
ions. The results show (at least for aluminium) that it is the dissociation of
water rather than of solvent molecules which is involved.

Values obtained by polarography for the
degrees of hydrolysis of Al3+
and Ti4+ in 25mM
H2O and 0.1M tetrapropylammonium chloride
were 0.82 and 0.18 respectively. In 0.1M perchlorate media the values for AlCl3 and TiCl4
were 0.45 and 0.40 respectively, indicating that the hydrolysis of Ti4+ is limited as a result of
complexing by competing chloride ions.

Potentiometric titrations, conductance
measurements, and u.v. spectra (for TiCl4)
support the polarographic results. No significant hydrolysis could be detected
for Mg2+, So3+,
Ga3+, and Sn4+
in halide solutions of acetonitrile.
New imidazole alkaloids from a Glochidion species (family Euphorbiaceae)
Authors: Johns SR , Lamberton JA
Published: September 2006

The leaves of a Glochidion
species, probably Glochidion philippicum (Cav.) C. B. Rob., of the family Euphorbiaceae,
contain three new interrelated imidazole alkaloids, glochidine (I),
glochidicine (II), and Nα-4?-oxodecanoylhistamine
(III), together with the known alkaloid Nα-cinnamoylhistamine.
The bark of this species contains only glochidicine and Nα-cinnamoylhistamine.
The chemical constituents of Australian Zanthoxylum species. III. The constituents of Z. parviflorum Benth.; The structure of parvifloral; Some observations on the biogenesis of furoquinoline alkaloids
Authors: Diment JA , Ritchie E , Taylor WC
Published: September 2006

The leaves of Zanthoxylum parviflorum Benth.
yielded lupeol, sitosterol, and skimmianine; the bark gave sucrose, hesperidin,
lupeol, skimmianine, chelerythrine chloride, (-)-α-canadine
methiodide, and magnoflorine iodide. From the wood there were isolated hesperidin,
sitosterol, dictamnine, skimmianine, platydesmine, and a new phenolic aldehyde,
parvifloral.

Spectroscopic data and biogenetic
considerations suggested that parvifloral was 5-prenylconiferaldehyde, and the
assignment of structure was confirmed by a rational synthesis.

Oxidation of platydesmine with iodine/lead
tetraacetate gave dictamnine. The significance of this result to the biogenesis
of furoquinoline alkaloids is discussed.
The interface between a liquid and its vapour
Authors: Lane JE , Johnson CHJ
Published: September 2006

The concentration profile
in a multilayer model of a system containing two immiscible fluid phases is
given by the solution of a non-linear, second-order difference equation. The
surface excess thermodynamic functions of the system can be evaluated only if
this solution is known. Assuming that the solution is symmetric, attempts to
obtain an exact solution using a method described by Ono were unsuccessful, but
a numerical method is described which enables approximate solutions of any
desired accuracy to be obtained. The possible existence of asymmetric solutions
has been examined. Symmetric solutions have also been obtained by methods that
do not require any explicit assumption of symmetry.
Dielectric relaxation: Some phenols, anisoles, and acetylbenzenes as solutes
Authors: Le Fevre RJW , Radford DV , Sullivan EPA
Published: September 2006

Dielectric relaxation measurements
on 2,4,6-tri-t-butylphenol, 2,4,6- tri-bromophenol, 2,4,6-trichloroanisole,
2,4,6-tribromoanisole, acetophenone, 2,4,6-trimethylacetophenone,
2,4,6-trimethyl-1,3- diacetylbenzene, and 1,4-diacetyldurene, as solutes in benzene
or carbon tetrachloride, are reconcilable with the average conformations
deduced previously1-3 for those
molecules from experimental molar Kerr constants and dipole moments.
Chemical and spectroscopic studies in metal β-diketonates. I. Preparation and study of halogenate metal acetylacetonates
Authors: Singh PR , Sahai R
Published: September 2006

Introduction of chlorine,
bromine, and iodine into the rings of acetylacetonates of CuII,
NiII, AlIII,
CrIII, FeIII,
CoIII, and VOIV has been
effected by direct halogenation under varied but carefully controlled
electrophilic substitution reaction conditions (usually applicable to aromatic
systems) such as with chlorine, N-chlorosuccinimide (NCS), bromine,
N-bromosuccinimide (NBS), or iodine monochloride in chloroform, acetic acid, or
methanol solvent. Infrared and ultraviolet spectroscopic data on the metal
chelates and their halogen derivatives have been obtained with a view to
studying possible changes brought about by such substitution in the acetylacetonate
rings of different metals. The v(C=C) and v(C=O) values were both found to show
a linear relationship with the mass numbers of the substituents as also with
the third ionization potential of trivalent metals. The halogenation of these
chelates apparently results in an extension of conjugation.
Substitution reactions of some Bis(2,2'-bipyridine) and mixed 2,2'-bipyridine, 2,2',2'-terpyridine complexes of ruthenium(II)
Authors: Davies NR , Mullins TL
Published: September 2006

Substitution reactions of
the complex ions [RuIIX bipy trpy]+ and [RuIIX2
bipy2]0, where X = Cl, Br, I; bipy = 2,2?-bipyridine; trpy
= 2,2?2?- terpyridine, take place in aqueous solution via extremely rapid
formation of the aquoammines. The rates of substitution of the aquo groups by
NO-2 and N-3 occur by measurably
slow processes at room temperature and are not base catalysed. The aquo
complexes are immediately converted by OH- into hydroxo complexes.
The pKa values of the aquo complexes are shown to be 10.0 for [RuII(H2O) bipy trpy]2+
and about 9-10 for [RuII(H2O)2
bipy2]2+, the latter being an
estimate since oxidation to ruthenium(III) in alkaline solution could not be
avoided. The visible and ultraviolet spectra are reported.
Synthesis and infrared spectra of some transition metal complexes of α-amino acid esters
Authors: Hay RW , Porter LJ
Published: September 2006

A variety of transition
metal complexes of a-amino acid esters have been synthesized, and characterized
by analysis, conductivity measurements, and infrared spectra. The complexes can
be broadly divided into two groups: (a) complexes in which only a metal-nitrogen
bond occurs with the α-amino group of the ester, and (b) complexes in
which chelate ring formation occurs via secondary donor groups on the ligand.
These latter complexes are found with methyl L-histidinate, methyl γ-glutamate,
and methyl L-cysteinate. With the exception of a methyl tryptophanate complex,
the infrared spectra show that there is no interaction between the carbonyl
group of the ester and the metal ion.

The visible spectra of aqueous solutions
of the esters and copper(II) at a ligand/metal ratio of 5 : 1 have maxima in
the 600-650 mμ range at pH 7 consistent with
copper-nitrogen bonding only.
Structural changes of flavylium salts. I. Polarographic and spectrometric examination of 7,4'-Dihydroxyflavylium perchlorate
Authors: Harper KA , Chandler BV
Published: September 2006

From polarographic and
spectrometric studies a sequence of molecular changes is proposed for 7,4?-dihydroxyflavylium
perchlorate in solutions of increasing pH in the absence of oxygen. Below pH 2
the flavylium ion is stable. Between pH 2 and 7.5 the chalcone is formed, the
reaction occurring rapidly and completely in less than 1 hr between pH 4 and 6.
This transformation involves the anhydrobase, the ionized form of which is
stable from pH 7.5 to 10. Further increase in pH causes ring opening to the
ionized chalcone, which is almost instantaneously formed at pH 13. Electrode
reactions are proposed and diffusion coefficients calculated for the various
forms.
Shock-initiated exothermic reactions. II. The oxidation of ammonia
Authors: Drummond LJ , Hiscock SW
Published: September 2006

Reflected shocks have been
used to initiate reactions in mixtures of ammonia with oxygen, nitrous oxide,
and nitric oxide which were diluted with argon. Final pressures were between 3
and 6 atm and temperatures before reaction were between 1460� and 2360�K.
Speeds of the reflected shocks were measured and compared with the theoretical
results for the cases of no reaction and of instantaneous conversion into
equilibrium products behind the shock. The measurements confirm that certain
difficulties exist when using the reflected shock technique with strongly
exothermic reactions. Absorption spectroscopy on OH, NH, and N2O
permits reasonable deductions on important mechanisms in the ammonia oxidation
processes.
Mössbauer effect in the system Ca2Fe2O5-Ca2FeAlO5
Authors: Whitfield HJ
Published: September 2006

Mossbauer spectra were
measured on Ca2Fe2O5,
Ca2Fe1.5Al0.5O5,
Ca2FeAlO5, and Ca2Fe0.67Al1.33O5
at temperatures from 95�K to above the Neel points.
The Mossbauer spectrum of Ca2Fe2O5
below its Neel point shows lines which were assigned
to tetrahedral and octahedral site ferric ions on the basis of the observed
isomer shifts and hyperfine splittings. The Mossbauer spectra of the
aluminium-substituted calcium ferrites give unequivocal evidence that the
aluminium goes preferentially into tetrahedral sites. A four-sublattice magnetic
structure is suggested for Ca2Fe2O5.
The preparation of halogenotrimolybdate(II) compounds
Authors: Allison GB , Anderson IR , Sheldon JC
Published: September 2006

The preparation of halogenotrimolybdate(II) compounds containing the
staphylonuclear groups, (Mo3Cl13)7-,
(Mo3Br13)7-, (Mo3Cl12)6-,(Mo3Cl11)5-, (Mo3Br11)5-, (Mo3Br11)5- has been thoroughly
examined and 11 new compounds are reported. No iodomolybdate(II)
compounds were observed. When
(NH4)7Mo3Cl13,H2O
is heated in vacuum, ammonium chloride is evolved but the final product is
never MoCl2. This chloromolybdate(II)
undergoes rapid reaction with refluxing acetic acid to give an approximately two-thirds
yield of molybdenum(II) acetate. This suggests the cleaving of an Mo3 group to give Mo2(CH3CO2)4.

Crystalline [Co en3]3Mo3Cl15,6H2O
undergoes spontaneous intramolecular redox reaction which is stimulated by
light, or moisture, but not oxygen.
The hydrolysis of halogenopentamminechromium(III) complexes
Authors: Chan SC , Hui KY
Published: September 2006

The Croup Replacement
Factors (G.R.F.) of halogens in nucleophilic substitutions of halogenopentamminechromium(III) complexes both by solvent
water and by hydroxide ion have been compared with the corresponding data
available for the analogous cobalt(III) cations. Although reactions in the
latter system are typical SN2 processes with concurrent bond
formation and fission, the mechanism of substitutions in halogenopentamminechromium(III)
complexes depends on the nature of the halogen, being bimolecular for the
fluoro and unimolecular for the other halogeno cations. The kinetic results are
discussed partly along lines similar to those employed for the interpretation
of organic nucleophilic substitutions.
Solvent isotope effects in the enolization of acetaldehyde, acetone, and ethyl methyl ketone at high acidities
Authors: McTigue PT , Sime JM
Published: September 2006

Measurements of enolization
rates in D2O-D2SO4 mixtures and H2O-H2SO4
mixtures at high acidities yield data which support low (c. -7) values for the
pKa values of the protonated forms of acetaldehyde, acetone, and
ethyl methyl ketone.
Micromelin, a new coumarin from Micromelum minutum (Forst. f.) Seem (family Rutaceae)
Authors: Lamberton JA , Price JR , Redcliffe AH
Published: September 2006

A new coumarin from the rutaceous species Micromelum
minutum (Forst. f.) Seem has been shown to be (I).
The chemical constituents of Galbulimima species. VIII. The structures of the ester alkaloids
Authors: Guise GB , Mander LN , Prager RH , Rasmussen M , Ritchie E , Taylor WC
Published: September 2006

By means of spectroscopic
and chemical correlations the structures of the remaining 13 ester alkaloids
from Galbulimima species were assigned.

Together with himandridine and himbosine
these alkaloids form a new family.
Thio derivatives of β-diketones and their metal chelates. VI. Metal chelates of 3-Mercapto-1,3-diphenylprop-2-en-1-one and their infrared spectra
Authors: Chaton SHH , Livingstone SE
Published: September 2006

Complexes of
3-mercapto-1,3-diphenylprop-2-en-1-one, PhC(SH)=CHCOPh, with iron(III), cobalt(III), rhodium(III),
nickel(II), palladium(II), platinum(II), copper(II), silver(I), zinc(II), cadmium(II), and
mercury(II) have been prepared and characterized. Complexes of 4- mercaptopent-3-en-2-one, MeC(SH)=CHCOMe, with cobalt(III) and cadmium(II) and of ethyl
thioacetoacetate, MeC(SH)=CHCOOEt,
with cobalt(III) and copper(I) are also reported.

The infrared spectra of the complexes of
3-mercapto-1,3- diphenylprop-2-en-1-one are discussed. The similarity of the
spectra of the silver(I), cadmium(II),
and mercury(II) complexes to those of the free ligand and its S-methyl
derivative, PhC(SMe)=CHCOPh, indicate that in these three complexes the carbonyl
oxygen of the ligand is not, or is at most weakly, coordinated to the metal
ion. The assignments of the principal bands in the other metal complexes of
this ligand are: 1550- 1525 cm-1, v(C-C); 1480-1458 cm-1,
v(C=O); 1438-1412 cm-1, v(C=O)+δ(C-H); 1270-1260 cm-1,
v(C--S); 498-437 cm-1, v(M-O); 399-376 cm-1, v(M-S).
Sucrose crystal growth. I. Rate of crystal growth in pure solutions
Authors: Smythe BM
Published: September 2006

A method is described for
the measurement of rate of growth of sucrose crystals from aqueous solutions
under controlled conditions of temperature, super-saturation, and relative
velocity of the solution with respect to the crystal.

The effects of these parameters on sucrose
crystal growth rates in pure sucrose solutions are reported. The results can be
explained qualitatively in terms of a two-step rate process, the two steps of
which are interdependent and neither solely rate-controlling under the conditions
studied.
Catalysis by hydrogen halides in the gas phase. XIII. Isopropanol and hydrogen iodide
Authors: Failes RL , Stimson VR
Published: September 2006

Hydrogen iodide catalyses
the decomposition of isopropanol into propene and water at 356 to 457�, viz. �������������������������� i-C3H7OH+HI
→ C3H6+H2O+HI

This is followed by the
faster reactions

�������������������������� C3H6+HI
→ i-C3H7I

����� ��������������������i-C3H7I+HI
→ C3H8+I2������������������������ i-C3H7OH+I2
→ (CH3)2CO+2HI

The rates of the initial
reaction fit the Arrhenius equation

����������������� k2 = 1012.24
exp(-31900/RT) sec-1 ml mole-1

and it is believed to be
homogeneous and molecular. It is faster than the corresponding reactions with
hydrogen chloride and hydrogen bromide in the ratios 100 : 1 and 5 : 1,
respectively. For the overall reaction the amounts of the products formed to
70% reaction, computed with the use of rate constants of the individual
reactions, agree well with the amounts found by analysis.
Proton chemical shifts and electron densities in aromatic and heteroaromatic molecules. I. Procedure and chemical shift corrections; Applications to azines
Authors: Black PJ , Brown RD , Heffernan ML
Published: September 2006

In this series, the
observed proton chemical shifts of heteroaromatic compounds are used to obtain
estimates of the electron distribution in these systems. These estimates are
deduced from the measured shifts after applying corrections for the shielding contributions
arising from ring currents, magnetic anisotropy of neighbouring atoms, and the
electric field from the lone-pair dipoles on heteroatoms, in a manner closely
related to that of Gil and Murrell. The corrected chemical shifts are then used
to deduce an ?experimental? π-electron distribution via the electric field
dependence of the proton shifts on the excess charge at all ring positions.
However, in most cases, there are not enough experimental shifts to determine
uniquely the excess charge at each ring atom, and it is necessary to assume
that some inaccessible charges are close to values obtained from theoretical
calculations. With these limitations, a comparison is made between the excess
charges deduced in the above fashion from chemical shift data on mono- and
poly-cyclic azines and diazines and those obtained by theoretical calculations
using the BJ VESCF method.

It is emphasized that this interpretation
is tentative and that the extent of σ-electron polarization is not well
understood at present.
Proton chemical shifts and electron densities in aromatic and heteroaromatic molecules. II. Derivatives of pyrrole and furan
Authors: Black PJ , Brown RD , Heffernan ML
Published: September 2006

In this paper, the methods
outlined in Part I are used to estimate the electron distribution from the
proton chemical shifts in a series of five-membered ring heteroaromatic
compounds. The systems studied are pyrrole and furan, their benzo and dibenzo
derivatives, indazole, indolizine, the azaindolizines, and purine. It is found
that the estimated excess charges are not as closely represented by the BJ
VESCF method as was the case for the azine derivatives and that the role of the
σ-electrons is in urgent need of closer investigation.
Mass spectra of spermatheridine alkaloids. The structure of moschatoline
Authors: Bick IRC , Bowie JH , Douglas GK
Published: September 2006

The mass spectra of a
series of alkaloids of the spermatheridine group, together with those of their
alkoxy derivatives, are reported and discussed. The characteristic
fragmentation processes, substantiated by appropriate metastable peaks, exact
mass measurements, and in some cases by deuterium labelling, facilitate the
location of substituents in the tetracyclic system. A structure for
moschatoline is deduced from a consideration of the mass spectra of its
derivatives.
The formation of aromatic hydrocarbons at high temperatures. XXVIII. Pyrolysis of n-[α-14C]propylbenzene
Authors: Badger GM , Jolad SD , Spotswood TM
Published: September 2006

The pyrolysis of n-[σ-14C]propylbenzene
at 700� has given a tar from which nine compounds have been isolated in
sufficient quantity and purity for radio- chemical analysis; four of these have
been degraded to determine the distribution of the radioactivity. Evidence is
presented that there is an effective partial interchange of α and β
carbon atoms in the formation of styrene, and probable mechanisms of formation
for this, and other, compounds are discussed.
Photochemical reactions of azo compounds. XI. Formation and characterization of 2-Dimethylaminobenzo[c]cinnoline
Authors: Lewis GE , Reiss JA
Published: September 2006

2-Dimethylaminobenzo[c]cinnoline
is formed when 4-dimethylaminoazo benzene N-oxide is
irradiated in 22N sulphuric acid. The same product arises in good yield when
2-chlorobenzo[c]cinnoline is heated with dimethylamine in a sealed tube at
160-170�. A compound formerly described in the literature as 2-dimethyl-aminobenzo[c]cinnoline
has now been shown to be 4,4?-bis(4-dimethylaminophenylazo)biphenyl.
Antirhine, a new indole alkaloid from Antirhea putaminosa (F. Muell.) Bail. (family Rubiaceae)
Authors: Johns SR , Lamberton JA , Occolowitz JL
Published: September 2006

Antirhine, the major
alkaloid of Antirhea putaminosa
(F. Muell.) Bail., has been shown to be (III).
Synthesis of the cis and trans isomers of 4-Chloro-L-proline, 4-Bromo-L-proline, and 4-Amino-L-proline
Authors: Andreatta RH , Nair V , Robertson AV , Simpson WRJ
Published: September 2006

cis- and trans-4-Chloro-
and 4-bromo-L-prolines have been synthesized stereospecifically, the key step
being SN2 displacement of a free or substituted 4-hydroxyl group in
suitably protected 4-hydroxy-L- prolines. Similar displacements with azide ion
followed by reduction provide convenient routes to cis- and trans-
4-amino-L-proline. A less satisfactory pathway to cis-4-aminoproline is
reduction of a 4- oximinoproline derivative. In the course of the syntheses,
which involve a variety of protecting groups, 45 new L-proline derivatives have
been prepared. Unexpected side reactions were the formation of cis-4-hydroxyprolinamide by the action of ammonia on trans-4- bromoproline,
and the reduction by sodium borohydride of N- benzyloxycarbonyl-4-oximinoproline
methyl ester to N-benzyloxycar- bonyl-4-oximinoprolinol.
The reactions of 3,4-dehydroproline with substituted isatins
Authors: Hudson CB , Robertson AV
Published: September 2006

Substituted isatins having
a free NH group react with 3,4- dehydroproline, like isatin itself, to give
3-(1-pyrrolyl)oxindoles. Analysis of the N.M.R. spectra of the 5-nitro and
5,7-dibromo analogues confirms that the isatins condense at their 3- and not their
2-carbonyl groups. N-Alkylisatins form similar
products which, depending on the conditions, may react with a further molecule
of the isatin to give unstable di-adducts whose structures have been
determined.
Electron impact studies. XI. Mass spectra of aromatic azoxy compounds. Skeletal rearrangement upon electron impact
Authors: Bowie JH , Cooks RG , Lewis GE
Published: September 2006

The mass spectra of 15
aromatic azoxy compounds are reported and discussed. The spectra exhibit
pronounced molecular ions, and fragmentation modes which are produced by both
simple cleavage and complex skeletal reorganization processes.
Electron impact studies. XII. Mass spectra of substituted imidazoles
Authors: Bowie JH , Cooks RG , Lawesson S , Schroll G
Published: September 2006

The mass spectra of 37
imidazoles are reported and discussed. The spectra exhibit pronounced molecular
ions and characteristic fragmentation patterns. The fragmentation modes have
been substantiated by deuterium labelling, exact mass measurements, and appropriate
metastable ions. Skeletal rearrangement fragments are rare in these spectra;
consequently mass spectrometry is useful for structure elucidation of
imidazoles.
Oxidative cyclizations. I. The mechanism of the oxidation of ortho-substituted anilines with phenyliodoso acetate
Authors: Dyall LK , Kemp JE
Published: September 2006

A comparison has been made
of the types of ortho substituents which can be incorporated into a new
heterocyclic ring by pyrolysis of aryl azides or during oxidation of anilines
with phenyliodoso acetate. The results enable a new mechanism to be proposed for
the amine oxidation. In its key step, the ortho substituent displaces
iodobenzene from an intermediate iodoso ester to form the cyclic oxidation
product. A competing reaction path involves homolysis of this iodoso ester to
yield the free-radical precursors of azo compounds.
The synthesis of 1,4-epimino[18]annulene 7,10:13,16-disulphide
Authors: Badger GM , Lewis GE , Singh UP
Published: September 2006

1,4-Epimino[18]annulene
7,10:13,16-disulphide has been synthesized. It has been found to be a stable
non-aromatic system in which the three five-membered heterocyclic rings are
linked by three essentially olefinic vinylene groups.
The preparation of 2-Fluoro-5-nitrobenzonitrile and the proton magnetic resonance spectra of some compounds containing the N-(2-Cyano-4-nitrophenyl) group
Authors: Wilshire JFK
Published: September 2006

2-Fluoro-5-nitrobenzonitrile,
an analogue of 1-fluoro-2,4- dinitrobenzene, in which the 2-nitro group has
been replaced by a cyano group, has been prepared and made to react with
several amines, amino acids, and NH-heteroaromatic compounds. The proton magnetic
resonance spectra of some of the resultant N-(2-cyano-4-nitrophenyl)
derivatives were compared with the spectra of the corresponding N-(2,4- dinitrophenyl)
derivatives and furnish further evidence that the ortho nitro group of the
latter derivatives is rotated out of the plane of the aromatic nucleus.
Photochemistry of a-diketones. I. Some photochemical reactions of 1,1,4,4-Tetramethyl-2,3-dioxotetralin
Authors: Gream GE , Paice JC , Ramsay CCR
Published: September 2006

The photochemical reactions
(at λ > 3000 A) of the non-enolizable α- diketone (XIV) have been
investigated in the solvents methanol, isopropanol. cyclohexane, toluene, n-butyraldehyde,
methyl formate, acetic acid, dioxan, and benzene. In general, selective 1,2-addition
of solvent to one carbonyl group to give a-hydroxy ketones is the predominant
reaction. Competing reactions include reduction to the acyloin (XXI) and loss
of carbon monoxide to give 1,1,3,3- tetramethylindanone
(XVII). In methanol, two isomeric diols (XXIII) and (XXIV) were unexpectedly
formed.
Carbon Capture and the Aluminium Industry: Preliminary Studies
Authors: Jones Graham , Joshi Gargi , Clark Malcolm , McConchie David
Published: September 2006

Environmental Context. Carbon dioxide concentrations in the atmosphere are rising every year by 1.5–3.0 ppm and there is now a general acceptance that increased efforts must be made to reduce industrial sources of this greenhouse gas. Carbonation of red mud wastes produced by aluminium refineries has been carried out to study the capacity of these wastes to capture carbon dioxide. Removal is very rapid, with the added carbon dioxide recorded as a large increase in bicarbonate alkalinity. Although these results can only be considered preliminary, the experiments indicate that these wastes can potentially remove up to 15 million tonnes of carbon dioxide produced in Australia per annum. Furthermore, the carbonated waste can be used in other industrial processes to add further value to these waste materials.
Abstract. Carbonation of raw red mud produced by aluminium refineries and a chemically and physically neutralized red mud (Bauxsol™) has been carried out to study the capacity of these wastes to capture carbon dioxide. After only 5 min of carbonation of raw red mud, total alkalinity dropped 85%. Hydroxide alkalinity was almost totally consumed, carbonate alkalinity dropped by 88%, and bicarbonate alkalinity increased to 728 mg L–1. After 24 min carbonation, the bicarbonate alkalinity reached its maximum value of 2377 mg L–1, and hydroxide and carbonate alkalinity were virtually absent. After 30 and 60 min carbonation, bicarbonate alkalinity started to decrease slightly as the pH of the slurry increased. After 5 min carbonation of Bauxsol™, total and bicarbonate alkalinity dropped 89% and 9%, respectively. After 20 min carbonation, bicarbonate alkalinity dropped another 11%, but after 30 min carbonation bicarbonate alkalinity increased 26% to levels found in the original Bauxsol material, and pH was stable. Based on these experiments, a calculation of the amount of carbon dioxide that could be removed annually at aluminium refineries in Australia is potentially 15 million tonnes, and suggests that further studies are necessary to maximize this carbon removal process. Furthermore, carbonation produces a product, which can potentially be used in other industrial and agricultural activities to remove toxic metals and nutrients.
Complexation of Lead in Model Solutions of Humic Acid: Heterogeneity and Effects of Competition with Copper, Nickel, and Zinc
Authors: Fasfous Ismail I. , Chakrabarti C. L. , Murimboh John , Yapici Tahir
Published: September 2006

Environmental Context. Metal bioavailability and toxicity are often related to free metal concentration rather than total metal concentration. Humic substances are chemically and physically heterogeneous complexants for metals in natural waters, and play an important role in trace metal transport, fate, and bioavailability. Metal bioavailability, which depends on chemical speciation of metals, is greatly influenced by the presence of other trace metals and major cations in natural waters. In this work, the effects of heterogeneity of humic substances, and of competition of trace metals on lead speciation in model solutions have been studied to gain a better understanding of these effects on complexation of trace metal lead and its bioavailability.
Abstract. Physicochemical heterogeneity of a well characterized humic acid (HA) in its complexation with a trace metal lead in model solutions was investigated using pseudo-polarography at a stationary mercury drop electrode, and the differential equilibrium function (DEF) of Pb(ii)–HA complexes was determined. The complexation of Pb(ii) by HA was determined by taking into account the dependence of the strength of the binding on the metal (Pb) loading. Also investigated were the effects of competition of the trace metals copper, nickel, and zinc on the DEF of Pb(ii)–HA complexes in model solutions. The results showed that these trace metals competed with trace metal lead for binding by HA even when present at the same concentrations as that of lead.