bluuebunny/crossref_metadata_2025 huggingface dataset:
Flavan derivatives. XXI. Nuclear magnetic resonance spectra, configuration, and conformation of flavan derivatives
Authors: Clark-Lewis JW
Published: September 2010

Nuclear magnetic resonance
spectra of 80 compounds belonging to several classes of flavan
derivative have been analysed, and chemical shifts and coupling constants of
heterocyclic ring protons and aromatic protons are tabulated and discussed. Compounds
examined include flav-2-enes, flav-3-enes,
3-substituted flavanones and flavans, 2- and
4-substituted isoflavans, 3,4-disubstituted flavans,
and flavan-4-ols. The geometrical configurations of
substituents in the heterocyclic ring follow unequivocally
from the magnitudes of the vicinal coupling constants.
Infrared spectra of hydroxynaphthalenes
Authors: van Gemert JT
Published: September 2010

Infrared spectra of the two
naphthols and nine naphthalenediols
are presented in the region 4000-400 cm-1 for the solid state and
1600-900 cm-l for benzene, aqueous, and methanol solutions. By
comparisons of frequency shifts resulting from change in the state or solvent,
absorptions arising from the hydroxyl substituents have been located. As in
phenol, the OH in-plane deformation in naphthols
occurs near 1180 cm-l and is shifted to 1200 cm-l by
association. Other bands near 1380 and
1220 cm-1 can be classified as α- or ,β-type because of an
apparent correlation of their frequency with substituent position. Dissociation
of the compounds has been followed spectroscopically in methanol solutions.
Some features of the aqueous solution spectra of 1,3-dihydroxynaphthalene
are shown to be consistent with the previously established keto-enol tautomerism of the monoanion.
Chemical studies of the Proteaceae. II. Some further constituents of Grevillea robusta A. Cunn.; Experiments on the synthesis of 5-n-Tridecylresorcinol (grevillol) and related substances
Authors: Ridley DD , Ritchie E , Taylor WC
Published: September 2010

By mass spectrometry, gas
chromatography, and chemical degradation it was shown that crude grevillol from the wood of Grevillea robusta contains small amounts of 5-n-pentadecylresorcinol, 5-pentadec-8-enylresorcinol,
and 5-pentadec-10-enyl-resorcinol. The first of these
substances was synthesized; grevillol has been
synthesized by three new routes. Xethylation of
resorcinol derivatives by dimethyl sulphate-potassium
hydroxide-aqueous methanol resulted in some nuclear methylation as well as the
predominant O-methylation.
Flavan derivatives. XXIV. cis- and trans-3-Methoxyflavanones
Authors: Clark-Lewis JW , Jemison RW , Nair V
Published: September 2010

Oxidation of three 2,3-cia-3,4-cis-3-methoxyflavan-4-ols with active manganese
dioxide gave the corresponding 2,3-cis-3-methoxyflavanones which were equilibrated in
deuterochloroform containing trifluoroacetic acid to mixtures of cis- (c.33%) and trans-3-methoxyflavanones (c.67%). Tominaga's base-catalysed cyclization of 2'-hydroxy-α-methoxycha1cones to 3-methoxyflavanones
has been found to yield the 2,3-trans isomers. The higher stability of the 2,3-trans-configuration of 3-hydroxy-

flavanones (dihydroflavonols)
compared with 3-methoxyflavanones is attributed to
hydrogen bonding; no cis-isomer was
detected when acid-catalysed epimerization of a trans-3-hydroxyflavanone was attempted. M.m.r. data are reported for the compounds described.
Some studies in inorganic complexes. XXIII. Reactions of copper(II) with chelating heterocyclic bases
Authors: Nicholson AR , Sutton GJ
Published: September 2010

Studies have been made of
copper(II) complexes of the ligands 2- aminomethyl-pyridine,
2-methylaminomethylpyridine, 2-aminomethyl-6- methylpyridine, and
2-(2-aminoethyl)pyridine. Various hydrated and anhydrous copper(II) complexes
with the anions sulphate, nitrate, halide, and perchlorate were obtained with
copper(II) ion to ligand in stoicheiometric ratios of 1 : 1 and 1 : 2 and
several instances of water molecule and anion attachment to the coordination
sphere are reported. Certain sulphate complexes are considered to be of the
bridged type, others have sulphate coordinated to the� copper(II) atom by unidentate attachment, and
some of the halide complexes are thought most probably to be dimers based upon
double halogen to copper bridging. But there are no instances of bridging by
metal-metal bonding between adjacent copper atoms since all magnetic moment
values for the copper atoms in the complexes are either normal or only very
slightly lower than normal. Physical methods used in the elucidation of structures
included measurements of molecular conductances in suitable organic solvents,
solubility observations, infrared and visible absorption spectrophotometry, pyrolysis
methods, and measurements of magnetic susceptibility. Complex cations in
aqueous solution were characterized by visible spectrophotometry. ��� A majority of the solid complexes isolated
are described for the first time; where complexes have previously been recorded
additional physical investigations have been made.
Hydrolysis of amides. III. Dilute acid hydrolysis of amides of the type R-CH2-CONH2
Authors: Bolton PD , Jackson GL
Published: September 2010

Rate constants over a range
of temperature, enthalpies of activation, and entropies of activation are
reported for the dilute acid hydrolysis of n-valeramide, isovaleramide,
3,3-dimethylbutanamide, phenylacetamide, cyclohexylacetamide, methoxyacetamide,
bromoacetamide, and chloroacetamide. ��� The rate constants of the first six amides
together with those of two other alkyl-substituted acetamides taken from a
previous paper are almost perfectly correlated by the Taft linear steric energy
relationship. The enthalpies of activation, also, show a linear dependence on
the steric parameter, Es. The results obtained for the halogeno amides indicate
that the acid hydrolysis of amides may show a slight sensitivity to polar
effects.
The stereospecific solvation of non-polar organic solutes in liquid benzene
Authors: Le FFvre RJW , Murthy DSN , Stiles PJ
Published: September 2010

The molar Cotton-Mouton
constants of several non-polar and axially symmetric solutes have been measured
in both benzene and carbon tetrachloride. Differences between the Cotton-Mouton
constants of the same solute in these two solvents are largely attributable to
angular correlations between the solute and the benzene molecules.
Hexafluorobenzene and 1,3,5-trinitrobenzene reveal pronounced tendencies
towards parallel alignment of solute and neighbouring benzene molecules.
Sulphur-nitrogen chelating agents. VII. Five- and six-coordinate complexes of cobalt(II), nickel(II), and copper(II) with an S-N-S tridentate ligand
Authors: Livingstone SE , Nolan JD
Published: September 2010

Mono-ligand complexes of
the tridentate ligand N-(2-methylthiophenyl)- 2?-methylthiophenylmethyleneimine
(SNS) of the type MX2(SNS) (M = Co, Ni, Cu; X = Cl, Br, I, or FCS)
have been prepared. The electronic spectra indicate that the cobalt halide
complexes are five-coordinate, whereas the complex Co(NCS)2- (SNS)
and the nickel complexes are six- coordinate and polymeric. The copper complexes
CuX2(SNS) (X = Cl, Br) are possibly five-coordinate. ��� The bis-complexes of nickel [Ni(SNS)2]X2
(X = ClO4, BF4) are high- spin but the complex [Co(SNS)2](ClO4)2
appears to be a rare example of a low-spin octahedral complex of cobalt(II).
Octahedral cobalt(III) complexes of the chloropentammine type. XIX. The preparation, properties, and reactions of some Chlorobenzylaminebis-(ethylenediamine)cobalt(III) salts and related complexes
Authors: Chan SC , Lau OW
Published: September 2010

Salts of one isomeric
series of chlorobenzylaminebis(ethylenediamine)-
cobalt-(III) type of cations have been prepared using a variety of benzylamine
derivatives as ligands. They are tentatively assigned a cis-configuration on
the basis of their visible spectra. The first- order rate constants for their
solvolytic aquation have been measured. Both resonance contributions and steric
factors from the benzyl radical, as well as inductive effects of its
substituents, all have negligibly small influences on the rate of reaction. The
second-order rate constants for the hydrolysis of these cations by base have
also been determined. The labilizing powers of the benzylamine ligands in this
reaction are very similar to those of open-chain aliphatic amines, and significantly
different from those of aromatic amines. To see if reactivities depend on the
distance of separation between cobalt and the benzene ring, the experiments are
extended to the chloro(β- phenylethylamine)bis(ethylenediamine)cobalt(III)
type of complexes.
Structural investigation of the galactan component of the pectic substance from Carica papaya
Authors: Biswas AB , Rao CVN
Published: September 2010

A galactan was isolated in
98% purity from the pectic substance isolated from the unripe fruit of papaya (Carica papaya). Hydrolysis of the fully methylated galactan
gave 2,3,4-tri-, 2,3,6-tri-, and 2,3,4,6- tetra-O-methyl-D-galaotose in a mole
ratio of 18 : 38 : 1. The structure of galactan is discussed in the light of
the results of methylation and periodate oxidation studies.
Vibrational spectra of mercury(II) and methylmercury(II) thiocyanates
Authors: Cooney RPJ , Hall JR
Published: September 2010

The Raman spectra of
Hg(SCN)2 in both the solid state and in solution have been recorded
and interpreted in conjunction with the infrared spectra. For the solid state
the Raman shifts for Hg-S stretching, S-C stretching, and C-N stretching are 270,
721, and 2112 cm-1 respectively. In diglyme solution the
corresponding values are 278, 692, and 2139 cm- 1. The infrared
and Raman spectra of CH3HgSCN in the solid state do not contain any
coincidences which may indicate that the unit cell is centrosymmetric. The
Raman spectrum of CH3HgSCN in CH3OH solution shows
strong, sharp, polarized lines at 283, 540, 1186, and 2138 cm-1
which are attributed to Hg-S stretching, Hg-C stretching, CH3
deformation, and C-N stretching modes respectively.
Nitrophenols from exposed soils
Authors: Bear IJ , Kranz AH
Published: September 2010

A homologous series of
nitro-alkylphenols has been isolated from the odoriferous oil extracted from
rocks, clays, and silicate minerals, which have been exposed to the atmosphere.
A relatively large amount of another nitro-hydroxy compound, possibly a derivative
of diphenyl, is also present in the oil. The most likely origin of these
compounds, or their precursors, is alkylphenols liberated into the atmosphere
from plant material.
The photochemistry of α- and β-farnesenes
Authors: Courtney JL , McDonald S
Published: September 2010

The ultraviolet irradiation
of α- and β-farnesene with and without photosensitizers
is described, α-Farnesene simply undergoes cis-trans isomerization. The photosensitized
irradiation of β-farnesene yielded a mixture of bicyclohexanes, whereas
the direct irradiation of β- farnesene afforded the same bicyclohexanes
plus a substituted cyclobutene and a compound which may be cis-β-bergamotene.
Halogenated terpenoids. II. The 1,8-Dihalo-p-menthanes
Authors: Carman RM , Deeth HC
Published: September 2010

The low-melting
1,8-dichloro- and 1,8-dibromo-p-menthanes reported in the literature are shown
to be mixtures. Stereochemical assignments for the various
1,8-dihalo-p-menthanes have been revised.
Magnetism, electronic spectra, and structure of transition metal alkoxides. VIII. Nickel halo methoxides
Authors: Krueger AG , Winter G
Published: September 2010

The results of magnetic and spectral measurements of Ni(OMe)Cl and
its solvates are interpreted in terms of clusters of four nickel atoms
interacting ferromagnetically through 90� methoxy
bridges. It is proposed that these clusters associate through chlorine bridges
to form an infinite lattice. Solvation by methanol breaks only chlorine bridges
so that the magnetic clusters are preserved. Stepwise replacement of chlorine
by methoxyl resulted in the isolation of the expected compounds of composition Ni3(OMe)4Cl2
and Ni3(OMe)5Cl.
Here, the magnetic isolation of the clusters disturbed by antiferromagnetic intercluster exchange. Bromine and iodine bridges also
promote antiferromagnetic exchange but in contrast to the methoxy bridges, they
may be broken by solvation with methanol.
7-Phenylindolo[3,2,1-de]phenanthridin-13-one, the Vilsmeier-Haack reaction product of 1,4-diphenylcarbazole
Authors: Teitei T
Published: September 2010

Formylation of 1,4-diphenylcarbazole
(la) under the conditions of the Vilsmeier-Haack
reaction gave 7-phenylindolo[3,2,1-de]phenanthridin-13-one (2a), which brominated to give
6-bromo-7-phenylindolo[3,2,l-de]phenanthridin-13-one (2b). Treatment
of the compounds (2a) and (2b) with sodium hydride and alkyl iodides yields
l-(o-lkoxycarbonylphenyl)-9-alkyl-4-phenylcarbazoles (3a) and (3b) and the 3-bromo analogue
(3c), respectively. The parent compound, indolo[3,2,1-de]-
phenanthridin-13-one (2c), under the same reaction
conditions also gave the ring-opened compound 1-(0-methoxycarbonylphenyl)-9-methylcarbazole (3d).
Xanthates of titanium(III)
Authors: Coutts RSP , Wailes PC , Kingston JV
Published: September 2010

The first xanthates of titanium have been prepared from cp2TiCl (cp = π-cyclo-pentadienyl)
and NaS2COR (R = CH3, C2H2,
n-C3H7, n-C4H9, and n-C5H11)
in air-free water under inert atmosphere. The trivalent titanium complexes are
blue in colour, monomeric, and extremely sensitive to
oxygen, with one unpaired electron per titanium atom. They are believed to be
of the form

(See diagram in article)

with bidentate xanthato ligands, analogous to the corresponding dithiocarbamates.
Transition metal complexes of substituted alkynes. VI. Substituent arrangement in some bridging tris(alkyne)-cobalt complexes
Authors: Dickson RS , Fraser PJ
Published: September 2010

The new organocobalt
complex CO2(CO)4(CF3C2CF3)2(CF3C2H)
has been isolated from the reaction
of hexafluorobut-2-yne with p-trifluoropropyne-hexacarbonyldicobalt.
In addition, a second isomer of the known complex CO2(CO)4(CF3C2CF3)2(CF3C2H)2
has been isolated from the reaction of 3,3,3-tri-fluoropropyne
with p-hexafluorobut-2-yne-hexacarbonyldicobalt. A
detailed study of the 1H and 19F N.M.R. spectra of these
and the related complexes Co2(C0)4-
(CF3C2CF3)3 and CO2(CO)4(CF3C2H)3
has led to an assignment of the substituent arrangement in all of these
complexes.
The chemistry of pyrrolic compounds. X. A contribution to the chemistry of the oxyporphyrins
Authors: Clezy PS , Liepa AJ , Smythe GA
Published: September 2010

The preparation of a number
of new oxyporphyrins is described and the spectroscopic and
tautomeric properties of these tetrapyrroles and
their metal ohelates examined in terms of substituent
and steric effects. In selected cases oxyporphyrins
and their acetates can be prepared in fair yield by condensation of the
appropriate dipyrrylketone and diformyldipyrrylmethane
in the presence of acetic anhydride. The zinc
chelates of oxyporphyrins like the parent compounds
are paramagnetic. Phosphorus pentasulphide has been
shown to deoxygenate some oxyporphyrins.
Determination and comparison of the stability constants of some metal complexes of 8-hydroxyquinoline N-oxide and 8-hydroxyquinoline
Authors: Gupta RD , Manku GS , Bhat AN , Jain BD
Published: September 2010

The stability constants of
8-hydroxyquinoline N-oxide (or "oxine N-oxide") complexes with MnII,
Fell, CoII, Kill, CuII, ZnII,
CdII, UO211, AlIII, FeIII,
YIII, LaIII, CeIII, PrIII,
NdIII, SmIII,
GdIII, DyIII,
HoIII, ErIII,
TmIII, YbIII,
and LuIII, and oxine
complexes with LnIII and YIII
have been determined using pH-metric titrations in 50% v/v aqueous dioxan in the presence of 0.30M sodium perchlorate as the
constant ionic medium. With both the ligands, the "gadolinium break"
is observed in the case of the lanthanon complexes,
whereas the bivalent ion complexes follow the Irving-Williams order of
stability constants in the case of the oxine complexes. The stability
constants of the oxine complexes have been found to
be larger than those of the N-oxide
complexes, though the oxine anion is only five times
as basic as the N-oxide anion. A
possible explanation for the increased stability of the oxine
complexes in comparison with the corresponding N-oxide derivative is proposed.
Photolytic studies of cyclic unsaturated ketones. I. Irradiation products of 2-Methylcyclobutane-1,3-dione and its ethyl enol ether
Authors: Johns RB , Kriegler AB
Published: September 2010

The photochemical
rearrangement of 2-methylcyclobutane-1,3-dione and the ethyl ether of its enol
(4) have been shown to follow the expected pathway for an α, β-unsaturated
cyclobutenone. The enol ether, when irradiated in moist cyclohexane, forms
3-ethoxy-2-methyl-trans-crotonic acid
(8) which is photo-isomerized to the cis-isomer
(7). This latter isomer is the major product when the solvent is moist diethyl
ether. It is suggested that the necessary rotation about a carbon-carbon single
bond is solvent-dependent,
and occurs in a β,γ-unsaturated carboxylic acid formed as a reaction
intermediate.
A proton magnetic resonance and preparative study of trimethylenediamine complexes of cobalt(III)
Authors: Jonasson IR , Lincoln SF , Stranks DR
Published: September 2010

The preparation of trans-[Co(tn)2Cl2]Cl,3.5H2O and [Co(tn)3]Cl3,H2O (1,3-diaminopropane = tn) is shown to proceed more readily and with greater yields when methanol solvent is employed instead of water. The preparation of the new species [Co(tn)2PO4]4H2O, [Co(tn)2(ox)]Cl,H2O, trans-[Co(tn)2(OH)H2O]-(ClO4)2,2H2O, and trans-[Co(tn)2(NH3)2]AsO4,3H2O is reported together with a modified preparation of [Co(tn)2CO3]ClO4. These preparations are discussed in terms of reaction mechanism.
The p.m.r, spectra of the above species, trans-[Co(tn)2(NO2)2]NO2, cis-[Co(tn)2(H2O)HPO4]+, and cis-[Co(tn)2(H2O)2]3+ are reported in a range of solvents. The nature of the solvent markedly influences the observed chemical shifts and fine structure. The spectra are interpreted in terms of varying rates of conformational interchange of the tn ligands, and variation of solvent-solute interactions.
Polarization energies of molecular crystals
Authors: Batley M , Johnston LJ , Lyons LE
Published: September 2010

The electrostatic polarization energies have been calculated for 17 molecular crystals, including some of two-components. Comparison with photoelectric emission data confirms that the energies of ionized states in organic crystals can be described in terms of properties of the free molecule and classical electrostatic interaction energies.
The calculations were made in more detail and for a greater number of compounds than has been attempted previously; contributions from terms formerly neglected are significant especially for large molecules like pentacene.
The thermal decomposition of RDX at temperatures below the melting point. III. Towards the elucidation of the mechanism
Authors: Batten JJ
Published: September 2010

The rate of thermal
decomposition of RDX has been investigated in the presence of its decomposition
products and free radical traps. From the measurements, it is concluded that
formaldehyde and nitrogen dioxide, presumably ?encaged? in the sample, catalyse
the decomposition of RDX positively and negatively respectively. The
non-volatile residue also acts as a positive catalyst. The other products have
little or no effect on the rate, and the free radical traps did not reduce the
rate.
Polysaccharides of tropical pasture herbage. IV. A pectic acid from Townsville lucerne (Stylosanthes humilis)
Authors: Alam M , Richards GN
Published: September 2010

Pectic acid, extracted from
the stems of Townsville lucerne in 4% yield, has been fractionated by
precipitation with sodium acetate. The product contains two components as
revealed by electrophoresis in phosphate buffer, but the major structural
characteristics have been determined by partial hydrolysis. The pectic acid is
esterified to a very small extent (1% OCH3) and consists
predominantly of 1,4-a-linked D-galacturonic acid units with L-arabofuranose
units as the major neutral constituent.
Oxidation of aromatic secondary and tertiary amines by peroxydisulphate. A kinetic study
Authors: Sabesan A , Venkatasubramanian N
Published: September 2010

The kinetics of the
oxidation of aromatic secondary and tertiary amines by peroxydisulphate ion
under aqueous basic conditions have been investigated. The reaction is first
order in amine and first order in S2O82- ion.
The order of the reactivity is found to be: N-methylaniline > N,N-dimethylaniline
> aniline and N-ethylaniline > N,N-diethylaniline > aniline, and among
each class: N-methylaniline > N-ethylaniline and N,N-dimethylaniline > N,N-diethylaniline.
This reactivity is explained on the basis of a steric strain in the transition
state super- imposed over the usual polar effects.
Photochemical syntheses. II. The photo-addition of diphenylacetylene to some substituted naphthalenes
Authors: Sasse WHF , Collin PJ , Roberts DB , Sugowdz G
Published: September 2010

Twenty-one naphthalenes
substituted with alkyl, fluoro, chloro, and cyano groups form photo-adducts
with diphenylacetylene (dpa); eight naphthalenes with acyl, ammo, chloro, and
bromo substituents do not react. ��� These adducts are derivatives of the adduct
(1) as shown primarily by their p.m.r. and mass spectra. Except for 2-t-butylnaphthalene
and possibly 1-cyano-naphthalene, two isomeric adducts are formed from
naphthalene derivatives with non-equivalent rings, and addition to the more
highly substituted ring is favoured with all substituents. The overall yields
and the isomer ratios depend on the kind, number, and position of the
substituents, and on experimental conditions, particularly the solvent. The
results are discussed in terms of a mechanism previously considered for the
addition of dpa to naphthalene.
Chlorosulphonation of 2,4-dimethylacetanilide
Authors: Armarego WLF
Published: September 2010

The reaction of
chlorosulphonic acid with 2,4-dimethylacetanilide was described in two patents
the orientation of the sulphonyl group in the sulphonyl chloride formed (m.p.147�)
was not stated. This reaction was later repeated and was said to yield 5-acetamido-2,4-dimethylbenzenesulphonyl
chloride which had a lower melting point (133-134�). Because no rigorous proof
of the constitution of the product was given by these authors,
the reaction was reexamined and is reported here. The acetamidodimethylbenzenesulphonyl
chloride obtained in this work had m.p. 146.5-147�. It reacted with ammonia to
give 5-acetamido-2,4-dimethylbenzene-sulphonamide which was hydrolysed to
5-amino-2.4-dimethylbenzenesulphonamide. The constitution of these
products was established by diazotizing the latter compound and converting it
into 5-iodo-2,4-dimethylbenzenesulphonamide. The melting point of the iodo compound (188-188.5�) differed from the melting point
(176�) described in the literature for this compound which was prepared by sulphonation of

1-iodo-2,4-dimethylbenzene
followed by conversion into the sulphonyl chloride and then into the amide.
5-Iodo-2,4-dimethylbenzenesulphonamide was reduced with zinc and ammonia to
2,4-dimethylbenzenesulphonamide whose melting point was similar to the value in
the 1iterature it did not depress the melting point of an authentic sample made
in two steps from sodium 2,4-dimethylbenzenesulphonate, and its p.m.r. spectrum was consistent with its structure, i.e. H5
and H6 gave a quartet with a coupling of 9 Hz
characteristic of ortho benzene protons.
The rearrangement of heteroaryl nitrenes formed by pyrolysis of fused oxadiazolones at 600°C
Authors: Brown RFC , Smith RJ
Published: September 2010

Heteroaryl nitrenes were formed by pyrolysis of the
corresponding ring-fused oxadiazolones at
600�/0.1-0.5 mm with short contact times. 2-Pyridyl and 3-iso-quinolyl nitrenes
rearranged predominantly by ring contraction to give cyano-pyrroles
and 1-cyanoisoindole, respectively. 2-Quinolyl and 1-isoquinolyl nitrenes
underwent ring fission followed by rearrangements which led to O-cyanophenyl-acetonitrile
and 4-cyanoindole. 2-Benzo[f]quinolyl nitrene
rearranged predominantly by ring fission, but some ring contraction also
occurred. The rearrangement of
2-quinolyl nitrene has been investigated by using 14C and 15N
labelling. The dominance of ring contraction or ring fission reactions is
rationalized in terms of the effect on the whole π-system of the
localization of π-electrons in an electrocyclic
transition state for ring contraction.
Reactions in frozen aqueous solutions : The kinetics of the reaction of morpholine with Dihydrothiophen-2(3H)-one and with methyl formate
Authors: Oakenfull DG
Published: September 2010

The reactions of morpholine
with dihydrothiophen-2(3H)-one and with methyl formate
have been studied in frozen solution at -10�C. The rates for these reactions
are the same as those found when reaction is carried out at the same
temperature in simple solutions with concentrations equal to those present in
the equilibrium liquid phase of the partly frozen solution. These observations
show that the change in rate is a pure concentration effect. There is no need
to assume any change in order or mechanism of reaction in the frozen solution
as was claimed by Bruice and Butler.
Cyclization and cupric-ion oxidation of 4-(Cyclohex-1-enyl)butyl radical
Authors: Beckwith ALJ , Gream GE , Struble DL
Published: September 2010

4-(Cyclohex-1-enyl)butyl
radical (45), generated by thermolysis of the appropriate diaoyl peroxide (32), or by treatment of 4-(oyclohex-1-enyl)butyl
bromide (34) with tributylstannane, readily undergoes
intramolecular homolytic addition. The rate constants
for the 1,5- and 1,6-modes of oyclization in benzene
at 65� have been determined as 3.8 x 104 s-l and 3.2 x 104
s-l respectively. The mechanisms of homolytic
addition and of other processes leading to the formation of the observed
products are discussed.

Cuprio-ion oxidation of 4-(cyclohex-1-enyl)butyl radical
(45) affords mainly 4-(cyclohex-1-enyl)but-1-ene (43); the rate constant for
the reaction in benzene at 80� is estimated to be c. 4 x 108 1. mol-1
s-1. Evidence for the intermediacy of organo-copper
species in this and related oxidation reactions is presented.
Raman spectra of crystalline hydrolysis products of aqueous solutions of mercury(II) nitrate
Authors: Cooney RPJ , Hall JR
Published: September 2010

Raman spectra of the
crystalline polymeric compounds [HgOH]NO3,
[Hg3O2](NO3)2,
and [Hg3O2](NO3)2,H2O,
obtained by hydrolysis of aqueous solutions of mercury(11) nitrate, are
reported. For purposes of comparison with [HgOH]NO3,
the Raman spectrum of polymeric [HgNH2]Cl is also recorded. The two
most significant aspects of the Raman spectra of these hydrolysis products are
the dependence of the frequency of the most intense Hg-O stretching mode on the
number of mercury atoms bonded to a common oxygen in each compound and the
appearance of the nitrate spectrum, which suggests in each case that the ion
has symmetry lower than the free ion symmetry (D3h). The spectrum of
the solution from which the compound [HgOH]NO3
is isolated is notable for the intensity of the Hg-ONO2 stretching
mode and the magnitude of the splitting of the originally degenerate v3
frequency of the free ion.
The measurement of frequency separations in high resolution nuclear magnetic resonance spectra using a frequency modulated observing field
Authors: Moritz AG
Published: September 2010

A new method for the
measurement of frequency separations in high resolution nuclear magnetic
resonance spectra is presented. The method, which involves comparison of two
points on the line profile, is shown to be capable of an internal precision of
at least 2 mHz. Line separations measured in this way
are shown to give results consistent with those obtained using a double-lock
spectrometer and a nuclear double side-band oscillator.
Generation of Stable Cell Lines Expressing GFP-Tubulin and Photoactivatable-GFP-Tubulin and Characterization of Clones
Authors: Goodson Holly V. , Dzurisin Jill S. , Wadsworth Patricia
Published: September 2010

INTRODUCTION

A bicistronic expression vector can be used to generate stable cell lines expressing green fluorescent protein (GFP)-tubulin and photoactivatable (PA)-GFP-tubulin. This vector, pIRES (originally available from BD Biosciences/Clontech), expresses the gene of interest (GFP-tubulin) and a selection marker from the same promoter. The vector uses an internal ribosome entry site (IRES) derived from the encephalomyocarditis virus and translates two open-reading frames from one mRNA. The gene of interest is inserted immediately downstream from the pCMV IE promoter, and the selection marker is downstream from the IRES site. Selection is more efficient using this vector system, presumably because of the linked expression of both genes. IRES vectors have been used with neomycin- and hygromycin-resistance markers. Cell lines can also be generated for proteins cloned into standard vectors (i.e., pCMV).
Electrophysiological Recording from a ‘Model’ Cell
Authors: Zhang Bing , Stewart Bryan
Published: September 2010

INTRODUCTION

The Drosophila larval neuromuscular junction (NMJ) shares many structural and functional similarities to synapses in other animals, including humans. These include the basic feature of synaptic transmission, as well as the molecular mechanisms regulating the synaptic vesicle cycle. Because of its large size, easy accessibility, and the well-characterized genetics, the fly NMJ remains an excellent model system for dissecting the cellular and molecular mechanisms of synaptic transmission. This protocol describes the basics of setting up and conducting electrophysiological experiments using a model cell. For the novice, a model cell provides a way to learn the operation of electrophysiology equipment and software without the anxiety of damaging living cells. This protocol also illustrates passive membrane properties such as the input resistance, capacitance, and time constant.
Hidden Variability of Floral Homeotic B Genes in Solanaceae Provides a Molecular Basis for the Evolution of Novel Functions
Authors: Geuten Koen , Irish Vivian
Published: September 2010

B-class MADS box genes specify petal and stamen identities in several core eudicot species. Members of the Solanaceae possess duplicate copies of these genes, allowing for diversification of function. To examine the changing roles of such duplicate orthologs, we assessed the functions of B-class genes in Nicotiana benthamiana and tomato (Solanum lycopersicum) using virus-induced gene silencing and RNA interference approaches. Loss of function of individual duplicates can have distinct phenotypes, yet complete loss of B-class gene function results in extreme homeotic transformations of petal and stamen identities. We also show that these duplicate gene products have qualitatively different protein–protein interaction capabilities and different regulatory roles. Thus, compensatory changes in B-class MADS box gene duplicate function have occurred in the Solanaceae, in that individual gene roles are distinct, but their combined functions are equivalent. Furthermore, we show that species-specific differences in the stamen regulatory network are associated with differences in the expression of the microRNA miR169. Whereas there is considerable plasticity in individual B-class MADS box transcription factor function, there is overall conservation in the roles of the multimeric MADS box B-class protein complexes, providing robustness in the specification of petal and stamen identities. Such hidden variability in gene function as we observe for individual B-class genes can provide a molecular basis for the evolution of regulatory functions that result in novel morphologies.
The inhibitory effects of intravenous administration of rabbit immunoglobulin G on airway inflammation are dependent upon Fcγ receptor IIb on CD11c+ dendritic cells in a murine model
Authors: Yamamoto M , Kobayashi K , Ishikawa Y , Nakata K , Funada Y , Kotani Y , Masuda A , Takai T , Azuma T , Yoshida M , Nishimura Y
Published: September 2010

Immunoglobulins (Igs) play important immunomodulatory effects on allergic asthma. Among these, IgG has been reported to regulate allergic inflammation in previous studies about immunotherapy and intravenous immunoglobulin therapy. In this study, to examine the immunomodulatory mechanisms of IgG and FcRs we evaluated the effects of intravenous (i.v.) rabbit IgG administration (IVIgG) on allergic airway inflammation and lung antigen-presenting cells (APCs) in a murine model of ovalbumin (OVA) sensitization and challenge. In OVA-challenged mice, IVIgG attenuated airway eosinophilia, airway hyperresponsiveness and goblet cell hyperplasia and also inhibited the local T helper type (Th) 2 cytokine levels. Additionally, IVIgG attenuated the proliferation of OVA-specific CD4+ T cells transplanted into OVA-challenged mice. Ex vivo co-culture with OVA-specific CD4+ cells and lung CD11c+ APCs from mice with IVIgG revealed the attenuated transcription level of Th2 cytokines, suggesting an inhibitory effect of IVIgG on CD11c+ APCs to induce Th2 response. Next, to analyse the effects on Fcγ receptor IIb and dendritic cells (DCs), asthmatic features in Fcγ receptor IIb-deficient mice were analysed. IVIgG failed to attenuate airway eosinophilia, airway inflammation and goblet cell hyperplasia. However, the lacking effects of IVIgG on airway eosinophilia in Fcγ receptor IIb deficiency were restored by i.v. transplantation of wild-type bone marrow-derived CD11c+ DCs. These results demonstrate that IVIgG attenuates asthmatic features and the function of lung CD11c+ DCs via Fcγ receptor IIb in allergic airway inflammation. Targeting Fc portions of IgG and Fcγ receptor IIb on CD11c+ DCs in allergic asthma is a promising therapeutic strategy.
Systematic assessment of protein phenotypes characterizing high‐grade tumour budding in mismatch repair‐proficient colorectal cancer
Authors: Karamitopoulou Eva , Lugli Alessandro , Panayiotides Ioannis , Karakitsos Petros , Peros George , Rallis George , Patsouris Efstratios S , Terracciano Luigi , Zlobec Inti
Published: September 2010

Karamitopoulou E, Lugli A, Panayiotides I, Karakitsos P, Peros G, Rallis G, Patsouris E S, Terracciano L & Zlobec I (2010) Histopathology 57, 233–243 Systematic assessment of protein phenotypes characterizing high‐grade tumour budding in mismatch repair‐proficient colorectal cancer

Aims:  A tumour bud is defined as a single tumour cell or tumour cell cluster of up to five cells at the invasive tumour front. Significant differences in survival have been detected in colorectal cancer patients with low‐ compared to high‐grade budding. The aim of this study was to identify potential multi‐marker phenotypes characterizing low‐ and high‐grade budding in mismatch repair (MMR)‐proficient colorectal cancer.

Methods and results:  Established and promising prognostic proteins such as epidermal growth factor receptor (EGFR), pERK, RHAMM, RKIP, β‐catenin, E‐cadherin, pAKT, p16, p21, Ki67, Bcl‐2, vascular endothelial growth factor (VEGF), apoptotic protease activating factor‐1 (APAF‐1), MUC1, EphB2, matrix metalloproteinase 7, pSMAD2, CDX2, laminin5γ2 and MST1 were analysed on 208 MMR‐proficient colorectal cancers with complete clinicopathological data. The most accurate markers for predicting high‐grade budding (more than six tumour buds) were EphB2 (P < 0.001), Bcl‐2 (P < 0.001), RKIP (P < 0.001), E‐cadherin (P = 0.004), laminin5γ2 (P = 0.004) and APAF‐1 (P = 0.005). On multivariable analysis, only loss of Bcl‐2 (P < 0.001) and EphB2 (P < 0.001) were independent predictors of high‐grade budding. Bcl‐2−/EphB2− tumours were more frequently poorly differentiated (P < 0.001), of advanced pT stage (P = 0.002), lymph node positive (P = 0.023), presented vascular (P = 0.053) and lymphatic invasion (P = 0.005) and had a negative impact on patient survival (P = 0.012).

Conclusions:  The multi‐marker phenotype EphB2−/Bcl‐2− is an independent predictor of high‐grade budding and implies increased aggressive behaviour in MMR‐proficient colorectal cancer.
Metapopulation structure of Vibrionaceae among coastal marine invertebrates
Authors: Preheim Sarah P. , Boucher Yan , Wildschutte Hans , David Lawrence A. , Veneziano Daniele , Alm Eric J. , Polz Martin F.
Published: September 2010

Although animal‐associated microbial communities (microbiomes) are increasingly recognized to influence health, the extent to which animals represent highly selective habitats for microbes leading to predominance of high host specificity remains poorly understood. Here, we show that vibrios, which are well‐known commensals and opportunistic pathogens of marine animals, overall display little host preference, likely because of efficient dispersal‐colonization dynamics mediated by food items. We isolated 1753 strains from water and animal samples, which are linked in a food chain and display different degrees of similarity (respiratory and digestive tract of mussels and crabs, live and dead zooplankton, and whole water samples). Multilocus sequence data served as input for modelling and statistical analysis of spatiotemporal population structure. These data showed that the majority of populations occurred broadly within and among hosts, with the dominant population being a near perfect generalist with regard to seasons, host taxa and body regions. Zooplankton harboured the fewest and most specific populations, while crabs and mussels contained the highest diversity with little evidence for host preferences. Most mussel‐ and crab‐associated populations were detected in water samples at similar frequencies, particularly in filter‐feeding mussels where populations were also evenly distributed across host individuals. The higher variation among individuals observed in crabs and zooplankton is consistent with stochastic clonal expansions. These patterns suggest that evolution of a high degree of host specificity is surprisingly rare even though these animals represent long‐lived habitats, and vibrios are consistent members of their microbiome. Instead, many of the populations show stronger association with planktonic (micro)habitats while the microbiome may be a fairly open system for vibrios in which high rates of immigration can outpace selection for specialization.
State Regulatory Enforcement and Nursing Home Termination from the Medicare and Medicaid Programs
Authors: Li Yue , Harrington Charlene , Spector William D. , Mukamel Dana B.
Published: September 2010

Objectives. Nursing homes certified by the Medicare and/or Medicaid program are subject to federally mandated and state‐enforced quality and safety standards. We examined the relationship between state quality enforcement and nursing home terminations from the two programs.

Study Design. Using data from a survey of state licensure and certification agencies and other secondary databases, we performed bivariate and multivariate analyses on the strength of state quality regulation in 2005, and nursing home voluntary terminations (decisions made by the facility) or involuntary terminations (imposed by the state) in 2006–2007.

Principal Findings. Involuntary terminations were rarely imposed by state regulators, while voluntary terminations were relatively more common (2.16 percent in 2006–2007) and varied considerably across states. After controlling for facility, market, and state covariates, nursing homes in states implementing stronger quality enforcement were more likely to voluntarily terminate from the Medicare and Medicaid programs (odds ratio=1.53, p=.018).

Conclusions. Although involuntary nursing home terminations occurred rarely in most states, nursing homes in states with stronger quality regulations tend to voluntarily exit the publicly financed market. Because of the consequences of voluntary terminations on patient care and access, state regulators need to consider the effects of increased enforcement on both enhanced quality and the costs of termination.
Linear Childhood Discoid Lupus Erythematosus Following the Lines of Blaschko: Successfully Treated with Topical Tacrolimus
Authors: KAWACHI YASUHIRO , TAGUCHI SHIJIMA , FUJISAWA YASUHIRO , FURUTA JUNICHI , NAKAMURA YASUHIRO , ISHII YOSHIYUKI , OTSUKA FUJIO
Published: September 2010

Abstract:  The linear arrangement of discoid lupus erythematosus is uncommon. Here, we report a 6‐year‐old Japanese girl with linear discoid lupus erythematosus following the lines of Blaschko on her face and neck. Topical tacrolimus treatment improved the eruptions. The present case also indicated the important role of epidermal and dermal cells as well as immune cells in the pathogenesis of cutaneous lupus erythematodes.
Analysis of the Phase Transition and the Domain Structure in K0.5Bi0.5TiO3 Perovskite Ceramics by In Situ XRD and TEM
Authors: Otoničar Mojca , Škapin Srečo D. , Jančar Boštjan , Ubic Rick , Suvorov Danilo
Published: September 2010

The local crystal and domain structures of K0.5Bi0.5TiO3 ceramics were investigated by transmission electron microscopy (TEM) and selected‐area electron diffraction (SAED). The individual grains showed a lamellar domain structure, and on the basis of spot splitting along the characteristic crystallographic directions, 90°a–a‐ and 90°a–c‐type domains were identified. Furthermore, lamellar features within the 90° domains were observed, which we presumed were 180° domains; however, in the case of P4mm structures they cannot be distinguished by SAED. The 90° domain boundaries were (011) and (101) twin planes, typical for tetragonal perovskites. The domains could be designated as rotation twins, where the symmetry element describing the relationship between two twin domains is a twofold twin axis [011]/[101] and the symmetry operation is a 180° rotation. In order to determine the dynamics and the temperature of the phase transformation from the tetragonal to the cubic structures, high‐temperature XRD and in situ heating TEM analyses were performed. The results showed a gradual phase transformation in the temperature range from ∼280° to ∼450°C, where some grains lost their polar domains at a lower temperature than others. These findings confirmed the existence of a binary stability field in which the cubic and tetragonal structures coexist.
Effects of the Re-Entrant Bowl Geometry on a DI Turbocharged Diesel Engine Performance and Emissions—A CFD Approach
Authors: Venkateswaran S. Pasupathy , Nagarajan G.
Published: September 2010

The purpose of this study is to investigate the influence of re-entrant bowl geometry on both engine performance and combustion efficiency in a direct injection (DI), turbocharged diesel engine for heavy-duty applications. The piston bowl design is one of the most important factors that affect the air–fuel mixing and the subsequent combustion and pollutant formation processes in a DI diesel engine. The bowl geometry and dimensions, such as the pip region, bowl lip area, and toroidal radius, are all known to have an effect on the in-cylinder mixing and combustion processes. Based on the idea of enhancing diffusion combustion at the later stage of the combustion period, three different bowl geometries, namely, bowl 1 (baseline), bowl 2, and bowl 3 were selected and investigated. All the other relevant parameters, namely, compression ratio, maximum diameter of the bowl, squish clearance and injection rate were kept constant. A commercial CFD code STAR-CD was used to model the in-cylinder flows and combustion process, and experimental results of the baseline bowl were used to validate the numerical model. The simulation results show that, bowl 3 enhance the turbulence and hence results in better air-fuel mixing among all three bowls in a DI diesel engine. As a result, the indicated specific fuel consumption and soot emission reduced although the NOx emission is increased owing to better mixing and a faster combustion process. Globally, since the reduction in soot is larger (−46% as regards baseline) than the increase in NOx (+15% as regards baseline), it can be concluded that bowl 3 is the best trade-off between performance and emissions.
Measurement Selection for Engine Transients by Parameter Signatures
Authors: McCusker James R. , Danai Kourosh
Published: September 2010

A method of measurement selection is introduced that relies on parameter signatures to assess the identifiability of dynamic model parameters by different outputs. A parameter signature is a region in the time-scale plane wherein the sensitivity of the output with respect to one model parameter is much larger than the rest of the output sensitivities. Since a parameter signature can be extracted when the corresponding output sensitivity is independent of the others, the ability to extract parameter signatures is indicative of parameter identifiability by the output and used here for output/measurement selection. The purpose of this paper is to introduce a strategy for measurement selection by parameter signatures and to demonstrate its applicability to the transient decks of turbojet engines. The validity of the selected outputs in providing observability to all the engine model parameters is independently verified by successful estimation of parameters by nonlinear least-squares estimation.
Immune Regulators: Not Just for Type 1 Diabetes Anymore?
Authors: Bremer Andrew A.
Published: September 2010

Stimulation of 4-1BB with an agonistic antibody reduces adiposity and body weight, modulates inflammatory cytokine levels, improves glucose/lipid metabolism, and increases energy expenditure, suggesting a role for 4-1BB in the management of obesity and metabolic disorders.
SORTing Out Lipids
Authors: Damani Samir
Published: September 2010

A gene encoding a protein that helps to sort and clear cellular proteins is the most common genetic contributor to plasma LDL concentrations.
Phylogenetic studies on nuclear large subunit ribosomal DNA sequences of smut fungi and related taxa
Authors: Begerow Dominik , Bauer Robert , Oberwinkler Franz
Published: September 2010

To show phylogenetic relationships among the smut fungi and their relatives, we sequenced a part of the nuclear LSU rDNA from 43 different species of smut fungi and related taxa. Our data were combined with the existing sequences of seven further smut fungi and 17 other basidiomycetes. Two sets of sequences were analyzed. The first set with a representative number of simple septate basidiomycetes, complex septate basidiomycetes, and smut fungi was analyzed with the neighbor-joining method to estimate the general topology of the basidiomycetes phylogeny and the positions of the smut fungi. The tripartite subclassification of the basidiomycetes into the Urediniomycetes, Ustilaginomycetes, and Hymenomycetes was confirmed and two groups of smut fungi appeared. The smut genera Aurantiosporium, Microbotryum, Fulvisporium, and Ustilentyloma are members of the Urediniomycetes, whereas the other smut species tested are members of the Ustilaginomycetes with Entorrhiza as a basal taxon. The second set of 46 Ustilaginomycetes was analyzed using the neighbor-joining and the maximum parsimony methods to show the inner topology of the Ustilaginomycetes. The results indicated three major lineages among Ustilaginomycetes corresponding to the Entorrhizomycetidae, Exobasidiomycetidae, and Ustilaginomycetidae. The Entorrhizomycetidae are represented by Entorrhiza species. The Ustilaginomycetidae contain at least two groups, the Urocystales and Ustilaginales. The Exobasidiomycetidae include five orders, i.e., Doassansiales, Entylomatales, Exobasidiales, Georgefischeriales, and Tilletiales, and Graphiola phoenicis and Microstroma juglandis. Our results support a classification mainly based on ultrastructure. The description of the Glomosporiaceae is emended. The Doassansiopsaceae, Melanotaeniaceae, and Urocystaceae are proposed as new taxa. Key words: basidiomycete systematics, LSU rDNA, Microbotryales, molecular phylogeny, smut fungi, Ustilaginomycetes.