bluuebunny/crossref_metadata_2025 huggingface dataset:
Bryotoxins B and C, Toxic Bufadienolide Orthoacetates From the Flowers of Bryophyllum Tubiflorum (Crassulaceae)
Authors: Capon RJ , Macleod JK , Oelrichs PB
Published: November 2018

A mixture of bryotoxins B and C, two new toxins from the flowers of Bryophyllum tubiflorum, was resolved after acetylation and semipreparative silica h.p.l.c . Spectroscopic analysis of the isolated acetates resulted in identification of the toxins as the bufadienolide orthoacetates (3) and (4).
Heterocyclic Synthesis With Azides. II. The Reaction of Azide With Ethoxymethylenemalonate
Authors: Donkor A , Prager RH , Taylor MR , Thompson MJ
Published: November 2018

Sodium azide reacts with diethyl ethoxymethylenemalonate in dimethylsulfoxide to give diethyl 2,4-diethoxycarbonylpent-2-enedioate (12%) and diethyl 5-hydroxypyrrole-2,4-dicarboxyiate (60%). The structure of the latter was determined by X-ray crystal structure analysis at 150 K, and both compounds have been independently synthesized.
Cyclopent[a]iondene (Benzopentalene) and Pentalene: Pyrolytic Formation From 3-Phenyl- and 3-Vinyl-phthalic Anhydrides
Authors: Brown RFC , Choi N , Eastwood FW
Published: November 2018

Pyrolysis of 3-phenylphthalic anhydride at 900°/0.02mm gives cyclopent [a]indene, characterized by 1H n.m.r. at -70° and by formation of a cyclopentadiene adduct and of a dimer at room temperature. Pyrolysis of 3,4-, 3,5- and 3,6-diphenylphthalic anhydrides also gives much cyclopent [a]indene by loss of the additional phenyl group. 3,4-Diphenylphthalic anhydride forms triphenylene as the major product. The pyrolysate from 3-vinylphthalic anhydride contains the known dimer of pentalene , and phenylacetylene. Pyrolyses of 3-(1-naphthyl) phthalic anhydride and of 4-phenylphenanthrene-2,3-dicarboxylic anhydride are described.
Maleimide-Fused Cyclobutadienes and Dewar Furans: Trapping With Dienes as a Route to Propellane Photosubstrates With Potential for Oxiren Production
Authors: Warrener RN , Elsey GM , Pitt IG , Russell RA
Published: November 2018

N-Methylmaleimide-fused cyclobutadiene (15) and its 1,2-dimethyl derivative (41) have been generated by zinc/titanium tetrachloride treatment of the vicinal dibromide (39) and (24) respectively. Prior epoxidations of (24) and (39) produce mixtures of dibromo epoxides which yield the related N-methylmaleimide-fused Dewar furans (16) and (17) upon similar debromination (Zn/TiCl4). None of these reactive intermediates is sufficiently stable for direct observation, but each was trapped in adduct form by Diels-Alder reaction with furan. Attempts to form fused Dewar furan (17) by flash vacuum pyrolysis of the furan adduct (34) led to the production of the isomeric furo [3,4-c] pyrrole (43), the structure of which was confirmed by separate synthesis. Stereochemical assignments have been made to most adducts, and AM1 calculations have been used to predict the stereoselectivities and facial selectivities in these cycloaddition reactions. Reaction of these Dewar furans with cyclopentadienones produced propellanes which were decarbonylated to their respective cyclohexadienes and used as photosubstrates for the generation of oxiren or dimethyloxiren . Attempts to trap oxiren, generated by photolysis of propellane (12), with isobenzofuran were unsuccessful.
Hydrogenolysis and One-Electron Reduction of Alkoxy Sulfones
Authors: Julia M , Uguen D , Zhang D
Published: November 2018

The readily available 1-t-butoxyalkyl sulfones were converted by hydride reduction into alkyl t-butyl ethers. Reductive coupling with sodium metal or amalgam in an aprotic solvent led to glycol bis-1,2-O-t-butyl ethers. Polyethers such as 18-crown-6 can be synthesized by this procedure.
Synthesis and Structural Systematics of Nitrogen Base Adducts of Group 2 Salts. V. Some Complexes With 3-Azapentane-1,5-diamine
Authors: Waters AF , White AH
Published: November 2018

Syntheses and room-temperature single-crystal X-ray structural characterizations are recorded for an array of adducts of H2N(CN2)2NH(CH2)2NH2, ' dien ', with salts of Group 2 elements, MX2.n( dien ).[Mg( dien )2] Cl2 (1) is monoclinic, P 21/c, a 11.326(6), b 10.928(5), c 12.636(6) Ǻ, β 92.74(4)°, Z = 4 f.u .; R was 0.047 for No 1726 independent 'observed' (I > 3σ(I)) diffractometer reflections. [Mg( dien )2] Br2 (2) is monoclinic, P 21/c, a 9.541(7), b 14.55(1), c 11.894(8) Ǻ, β 100.42(5)°, Z = 4 f.u ., R 0.054 for No 1778. [Mg( dien )2] I2 (3) is isomorphous , a 9.969(2), b 14.907(2), c 12.300(3) Ǻ, β 100.02(2)°, R 0.039 for No 3180. In all three complexes, the two tridentate ligands are disposed mer in a six-coordinate MgN6 environment, the trans Mg-N(central) distances being somewhat shorter (2.161 (4)-2.181(9)Ǻ) than Mg-N(distal) (2.215(8)-2.249(4)Ǻ). [Ba(dien)3] Cl2 (4a) is orthorhombic, Pnaa , a 19.309(2), b 13.545(2), c 8.872(2)Ǻ, Z = 4 f.u ., R 0.055 for No 1070; the methanol disolvate (4b) is monoclinic, P 21/c, a 16.807(8), b 8.764(5), c 19.493(4) Ǻ, β 102.39(3)°, Z = 4 f.u ., R 0.11 for No 2613. A family of derivative structures (5)-(8), [M( dien )3] X2, M, X = Sr , Br (5), Sr , I(6), Ba , Br (7), Ba , I(8), have cells of half the volume (a ≈ 13.8, b ≈ 9, c ≈ 9.8 Ǻ), probable space group P21212, R 0.050, 0.061, 0.034, 0.037 for No 549, 914, 1044, 1801 respectively, with the cations disposed about crystallographic 2 axes with one disordered ligand . [ Ba( dien )3](ClO4)2 (9) is rhombohedral , R3c, a 10.240(2), c 45.19(1) Ǻ (hexagonal setting), Z = 6 f.u ., R 0.054 for No 508. Like (4)-(8), the barium environment is nine-coordinate with the three tridentate ligands here� disposed about a 3 axis through the metal.
Dimers of Podocarpic Acid Derivatives
Authors: Cambie RC , Craw PA , Murray DK , Rutledge PS , Schwerdtfeger PA , Seth M , Woodgate PD
Published: November 2018

Treatment of methyl 12-hydroxypodocarpa-8,11,13-trien-19-oate (5) with a commercial sample of thallium(III) trifluoroacetate gave a low yield (5%) of a non-symmetric ether-linked dimer (15). Use of freshly prepared thallium(III) trifluoroacetate gave a 28% yield of the symmetrical biaryl dimer (16). The dimethyl ether (17) was prepared in low yield (10%) by treatment of methyl 12-methoxypodocarpa-8,11,13-trien-19-oate (4) with the latter reagent.
Calixcrown Binding to Alkali Metal Cations—Comparison of Two 1,3-Alternate Calix[4]arenebiscrown-5 Ligands
Authors: Abidi R , Asfari Z , Harrowfield JM , Sobolev AN , Vicens J
Published: November 2018

While determination of the crystal structure of 1,3;2,4-biscrown-5-calix[4] arene (chloroform solvate, triclinic. space group Pī, a 11.151(4), b 16.832(6), c 21.929(8) Ǻ, α 98.78(3), β 92.02(3), γ 92.12(3)°, Z = 4 f.u ., conventional R on |F| 0.085 for 4699 'observed', I > 2σ(I), reflections) shows that this ligand has a closely similar solid state conformation to that of its previously characterized, substituted analogue, 1,3;2,4-biscrown-5-p-t-butylcalix[4] arene, the two ligands do differ significantly in their interactions with alkali metal picrates in chloroform solution. Most obviously, the t-butyl substituents of the latter ligand appear to inhibit caesium binding. changing the nature of the interactions to a form similar to that of both ligands with Li+ and Na+, for which 1H n.m.r. spectroscopy indicates weak exocyclic binding to some of the polyether oxygen atoms. 1H n.m.r. spectroscopy also provides evidence of picrate binding to the metals in isomeric forms.
Synthesis of Aromatic Spiroacetals
Authors: Brimble MA , Horner GM , Stevenson RJ
Published: November 2018

The synthesis of aromatic spiroacetal ring systems related to the papulacandins is reported. ortho-Metalation of diisopropylbenzamide, followed by reaction with the electrophiles δ- valerolactone, γ- butyrolactone and γ-valerolactone, provided the keto alcohol adducts (10),(16) and (21) respectively. Reduction of the ketone followed by treatment with acid afforded phthalides (12),(18) and (23). Finally oxidative cyclization with iodobenzene diacetate provided the spiroacetals (7),(14) and (19).
The Stereochemistry of Organometallic Compounds. XLIII. Rhodium-Catalysed Reactions of 2-(Alkenyloxy)benzylamines and 2-(N-Allyl-N-benzylamino)benzylamine
Authors: Campi EM , Jackson WR , Mccubbin QJ , Trnacek AE
Published: November 2018

Reactions of 2-( allyloxy ) benzylamines with H2/CO in the presence of rhodium catalysts give 1,3-benzoxazines, and 2-(N- allyl-N-benzylamino ) benzylamine gives a quinazoline . These reactions have been shown to involve allylic cleavage followed by regioselective carbonylation at the internal carbon atom as demonstrated by crossover experiments. Reactions of longer chain ( alkenyloxy ) benzylamines under similar conditions give polymeric material.
A Novel Cyclopropanation
Authors: Bostick TM , Christie SD , Connolly TJ , Copp S , Langler RF , Reid DL , Zaworotko M
Published: November 2018

Reaction between benzaldehyde and methyl α- benzylsulfonylacetate furnishes methyl (E)-α- benzylsulfonyl-β-phenylacrylate as the exclusive Knoevenagel adduct. The related condensations between α-benzylsulfonylacetonitrile and paraformaldehyde furnish trans-1-benzylsulfonyl-2-phenylcyclopropane-1-carbonitrile in modest yields. These product structures are established by X-ray crystallographic analysis. Phenylsulfene is ruled out as an intermediate in the formation of the cyclopropane.
Synthesis of Gibberellin Ga(53) and Its (17,17-D-2)Derivative
Authors: Mander LN , Owen DJ , Twitchin B
Published: November 2018

Gibberellin GA53 (1) has been prepared by a modified Wolff- Kishner reduction of gibberellin
GA19 protected as its 13-methoxymethyl ether (11). Careful regulation of the
temperature at c. 174� is necessary, otherwise migration of the 16-ene function
into the endocyclic 15-ene position occurs to an increasing
extent at higher temperatures. The methodology was also extended to the
preparation of the (17,17-D2)derivative (20).
Decomposition of Some Skarn-Rock Samples in Neutral and Basic Molten Potassium Nitrate for the Extraction and Determination of Iron
Authors: Mujumba JK , James BD , Tariq SA
Published: November 2018

Five skarn -rock samples were heated with KNO3 and with a solution of 5% KOH in KNO3 for 2 h at 450°C. The decomposed samples were cooled, dissolved in water and filtered. Iron was extracted from each residue as well as from the original samples by hot conc. HCl , and determined by atomic absorption spectroscopy. These results were compared with the known (X-ray fluorescence) total iron content of the original samples. The amount of iron extracted with HCl from the skarn samples was 3-11% lower, while that extracted after heating with KNO3 alone was 2-4% lower, than the amount present according to the X-ray fluorescence results. However, the amount of iron extracted from the samples treated with a solution of KOH in KNO3 was comparable to that determined by X-ray fluorescence.
Fused Isoquinoline Systems From Reactions of an Iminoisocoumarin With Nitrogen Nucleophiles
Authors: Deady LW , Loria PM , Quazi NH
Published: November 2018

Some reactions of 1-acetylimino-3-methyl-1H-2-benzopyran-4-carbonitrile with nitrogen nucleophiles are reported. This is a versatile intermediate and leads to isoquino [1,2-b] quinazoline (with methyl anthranilate ), [1,2,4] triazolo [5,1-a] isoquinoline (with hydrazine), imidazo [2,1-a] isoquinoline (with glycine ethyl ester), benzimidazo [2,1-a] isoqinoline (with o-phenylenediamine) and 1,3,5-triacine (with acetamidine ) systems.
The Structure of Dissectic Acid, a β-Orcinol meta-Depside From the Lichen Heterodermia dissecta
Authors: Elix JA , Wardlaw JH
Published: November 2018

The depside dissectic acid [methyl 3-(3′-formyl-2′,4′-dihydroxy-6′-methylbenzoyloxy)-4,6-dihydroxy-2,5-dimethylbenzoate] (2) has been isolated from the lichen Heterodermia dissecta together with atranorin (1). The structure of the compound (2) followed from a combination of spectroscopic data and was confirmed by synthesis.
Selectivity in Radical Reactions of Alanylglycine Anhydride Derivatives
Authors: Chai CLL , Hay DB , King AR
Published: November 2018

Functionalization of N,N′- disubstituted alanylglycine anhydrides under radical conditions is described. The radical (7), generated ( i ) from reactions of N,N'- disubstituted alanylglycine anhydrides with N- bromosuccinimide , and (ii) from related bromo compounds by reaction with tributyltin deuteride , undergoes carbon-bromine and carbon-deuterium bond formation with moderate to high diastereoselectivities depending on the N- substituents present.
Deoxyspongiaquinones: New Sesquiterpene Quinones and Hydroquinones From a Southern Australian Marine Sponge Euryspongia sp.
Authors: Urban S , Capon RJ
Published: November 2018

Chemical investigation of a marine sponge, Euryspongia sp., collected from the Great Australian Bight, Australia, resulted in the isolation of two new sesquiterpene quinones , deoxyspongiaquinone (4) and (E)-chlorodeoxyspongiaquinone (5), as well as two sesquiterpene hydroquinones, deoxyspongiaquinol (6) and (E)-chlorodeoxyspongiaquinol (7). The structures for (4)-(7) were determined by detailed spectroscopic analysis, as well as chemical interconversion and degradation.
Synthesis of the Androgen-Receptor Antagonists (±)-Ws9761 A and B
Authors: Cameron DW , Skene CE
Published: November 2018

The non-steroidal androgen-receptor antagonists WS9761 A (1,6,10-trihydroxy-2,8,10-trimethylanthrone) and WS9761 B (1,6,10-trihydroxy-2-hydroxymethyl-8,10-dimethylanthrone) were synthesized for the first time in racemic form by using Diels-Alder methodology followed by regioselective Grignard addition.
A Caveat Concerning Anionic Oxy-cope Rearrangements Within Bicyclo[2.2.2]octenyl Frameworks
Authors: Banwell MG , Dupuche JR , Gable RW
Published: November 2018

Compounds (10), (15) and
(16) all react with potassium hydride at 0°C to give, via retro- Diels-Alder reaction, 1-methylnaphthalene (12) in 60-67% yield. No evidence could be obtained for the formation of a product derived from the anionic oxy-Cope rearrangement of substrate (16).
New Sesquiterpenes From Eremophila spectabilis
Authors: Syah YM , Ghisalberti EL , Skelton BW , White AH
Published: November 2018

Two new eudesmane sesquiterpenes have been isolated from Eremophila spectabilis subsp. brevis. The structures of 6β-hydroxy-7α(H)-eudesm-4-en-3-one (1) and α(H)-eudesm-4(15)-ene-3α,6β-diol (2) were elucidated by spectroscopic studies, and that of (1) was confirmed by a single-crystal room-temperature X-ray study. Crystals of (1) are monoclinic, P21, a 11.302(6), b 9.99(1), c 13.487(6) Ǻ, β 108.45(4), Z = 4; R was 0.052 for 2340 independent 'observed' (I > 3σ(I)) diffractometer reflections.
Lamellarin-S: a New Aromatic Metabolite From an Australian Tunicate, Didemnum sp.
Authors: Urban S , Capon RJ
Published: November 2018

An Australian tunicate Didemnum sp. has yielded a new alkaloid lamellarin-S (1) along with the known compound lamellarin-K (12). Of this structure class, lamellarin-S (1) is the first example that demonstrates atropisomerism , and its structure was secured by spectroscopic analysis.
Synthesis and Structure of N,N'N"-Tris(2-hydroxyethyl)-N,N,N',N',N',N'-hexamethyl-2,2',2'-nitrilotris(ethylammonium) Trichloride
Authors: Koh TS , Fallon GD , Baklien A , Hearn MTW , Jackson WR
Published: November 2018

The synthesis of N,N′,N″- tris(2-hydroxyethyl)-N,N,N′,N′,N″,N″-hexamethyl-2,2′,2″-nitrilotris( ethylammonium ) trichloride, a potential monomer for the preparation of polyurethane-based ion exchangers, is described and its structure reported based on X-ray diffraction data.
Experiments Directed Towards the Synthesis of Anthracyclinones. XXIX. Fluoro-Substituted Tetracycles
Authors: Cambie RC , Higgs KC , Rustenhoven JJ , Rutledge PS
Published: November 2018

Diastereoselective formation of 9-fluoro-9-methylanthracyclinones has been achieved by treating ortho-methallyl-substituted anthraquinonyl homochiral dioxans with boron trifluoride etherate . The demethoxy anthraquinonyl dioxan (16) underwent slow reaction to give exclusively the (7S,9R) fluoro tetracycle (21) in 58% yield. The dimethoxy anthraquinonyl dioxan (15) was less reactive, allowing other reactions to compete, but boron trifluoride -acetic acid complex effected rapid cyclization of (15) with high diastereoselectivity. Short reaction times with this reagent circumvented the formation of the alkenes (25) and the naphthacenedione (9). Boron trifluoride-nitromethane gave the (7S,9R) fluoro tetracycle (19) in 36% yield. Although the yields of the fluoro tetracycles were modest, they compare favourably with a 4% yield reported for the fluorination of daunomycinone. The 6-demethoxy tetracycle (21) has been shown to exist in the expected half-chair conformation, with the bulky C7 side chain in a pseudo-equatorial position. In contrast, the 6,11-dimethoxy fluoro tetracycle (19) exists in a significantly perturbed half-chair conformation with a pseudo-axial side chain.
A Composite Modulated Structure Versus Superstructure Approach to the Refinement of >Zr108N98F138
Authors: Schmid S , Withers RL
Published: November 2018

Zr108N98F138 is an x = 2.185 member of a wide range non- stoichiometric solid solution Zr (N,O,F)x, 2.12 ≤ x ≤ 2.25, in the zirconium nitride oxide fluoride system. The structure is rerefined as a composite modulated structure composed of two mutually incommensurable Q and H substructures with overall superspace group symmetry Acmm (0,0,1.185..)0s0. The Q substructure has lattice parameters a = 5.186, b = 5.368 and cQ = 5.374 Ǻ, and substructure superspace group symmetry Acmm (0,0,1.185..)0s0. The H substructure has lattice parameters a = 5.186, bH = 1/2b = 2.684 and CH = 4.534 Ǻ, and substructure superspace group symmetry Pmcm (0,±,0.844...)s00. While employing almost an order of magnitude fewer positional parameters than the previous study, refinement on 956 unique reflections converged to R = 0.057 instead of R = 0.113.
The Crystal Chemistry of Moganite and Amethyst
Authors: Hyde B , Mclaren A
Published: November 2018

The crystal structure of moganite , SiO2, is described, analysed, and shown to be (mimetic) Brazil-twinned α-quartz: it consists of {1101} layers of the latter, one tetrahedron thick, coherently joined at composition planes, with left- and right-handed quartz layers alternating. The structure of the region immediately adjacent to a composition plane is identical to that found in macroscopically twinned quartz, e.g. in amethyst. Thus the 'defect' structure in the latter is the total structure of the former-a classic example of Wadsley's idea that, in crystals, 'defects' are stable structural entities.
Marcasite and Pyrite (FeS2)
Authors: Hyde B , Okeeffe M
Published: November 2018

We first describe the structures of FeS2-marcasite and FeS2-pyrite, and the way in which they are related. It is then explained how this relationship can successfully account for several phenomena: pyrite- marcasite intergrowths, the reported anisotropy of (nominally cubic, and therefore isotropic) FeS2-pyrite, stacking and deformation faults in pyrite parallel to {100}, and the observed structure of the pararammelsbergite polymorph of NiAs2.
The Effects of Doping on the Selectivity and Response Time of Fluoride Ion-Selective Electrodes
Authors: Wang XD , Shen W , Cattrall RW , Nyberg GL , Liesegang J
Published: November 2018

We report the effect of doping on the response time and hydroxide ion interference of fluoride ion-selective electrodes made by using membranes consisting of single crystals of CeF3, LaF3 and NdF3, both undoped and doped with divalent cations , and of mixed crystals of neodymium and samarium fluorides (Nd0.95Sm0.05F3 and Nd0.86Sm0.14F3). Doping not only increases the bulk conductivity of the membrane, but also reduces both the response time and the hydroxide ion interference of the electrode. This behaviour is due to an increase in the number of Frenkel defects in the crystal membrane, an effect which increases the mobility of the fluoride ion. It has also been established that doped single crystals of either LaF3 or NdF3 offer the best performance in terms of selectivity.
The X-Ray Crystallographic Structure of a 1,2-Dibromo-4,8-epoxy-p-menthane
Authors: Carman RM , Edwards RA , Rayner AC , Robinson WT
Published: November 2018

The crystalline dibromo epoxide obtained from (R)-α- terpineol is shown by X-ray crystallography to have the (1S,2S,4S)-1,2-dibromo-4,8-epoxy-p-menthane structure (3).
On the Bonding Behaviour of Transition Metal Ions in Inorganic Solids—Optical and Epr Spectroscopic Studies on Anhydrous Phosphates and Phosphate-Silicates of Ti3+
Authors: Glaum R , Hitchman MA
Published: November 2018

TiPO4 (green), Ti4P6Si2O25 (purple-red) and TiP3O9 (blue) show a remarkable variety of colours . We compare the results of optical and e.p.r. spectroscopic measurements on these compounds with d-electron energy levels for Ti3+ obtained by using the angular-overlap model. Thus, a unified set of angular-overlap model bonding parameters for the description of the spectroscopic behaviour of Ti3+ in anhydrous phosphates can be derived. The σ-interaction was assumed to depend on the nth power of the Ti-O bond distance, and it was found that optimum agreement with experiment occurred with n = -4.5. For the correct reproduction of the experimentally observed ground-state splittings it is necessary to allow for anisotropic π-bonding interactions between titanium and the oxygen ligands linking Ti-O coordination polyhedra.
The Structure of a Human Metabolite of Pholcodine
Authors: Gore J , Kasum B , Holman MA , Scharfbillig IM , Ward AD
Published: November 2018

The structure of a metabolite of pholcodine produced by humans is shown, by spectroscopic and synthetic data, to be a morpholin-3-one (amide) derivative rather than the alternative morpholin-2-one ( lactone ) isomer. Acylation of diethanolamine leads to an N,O- diacyl product even when only 1 equiv. of acylating agent is used. A mechanism is proposed to account for this observation. The appropriately substituted diacyl product can be cyclized to give a morpholin-3-one derivative which can be coupled to morphine by using caesium carbonate to give the metabolite. Suitable morpholin-2-one systems were coupled with morphine in basic conditions to give the alternative metabolite structure whose lactone group hydrolysed on standing to form a hydroxy acid derivative.
Growth and phosphorus uptake of faba bean and cotton are related to Colwell-P concentrations in the subsoil of Vertosols
Authors: McLaren T. I. , Bell M. J. , Rochester I. J. , Guppy C. N. , Tighe M. K. , Flavel R. J.
Published: November 2018

Recent studies report low and variable phosphorus (P) fertiliser use efficiency (PUE) for cotton in the northern grains region (NGR) of eastern Australia. This may be due to cotton accessing P pools that are not currently tested for in the subsoil (10–30 cm) or variation in response to P source and placement strategy. Two glasshouse studies were used to investigate this, incorporating two soil P tests to assess readily and slowly available P pools (Colwell, and a dilute acid colloquially referred to as the BSES extractant), and five different P fertiliser placement strategies in the subsoil. Eighteen Vertosols were collected across southern to central Queensland in the NGR, and then used to grow faba bean (Vicia faba L.) and cotton (Gossypium hirsutum L.) sequentially in the same 28-L pot. Readily available P pools assessed by Colwell-P were of major importance for faba bean and cotton dry matter, as well as for tissue P concentrations. Cotton was less responsive to extractable subsoil P concentrations than faba bean, suggesting either greater internal PUE or improved ability to accumulate P under conditions of limited availability. We recommend that subsoil P fertilisation should occur before sowing faba bean to maximise PUE in a cotton–faba bean rotation. Faba bean and cotton both recovered more P when the subsoil was fertilised, but no individual P fertiliser placement strategy was superior. Phosphorus extracted using the BSES method was not correlated with faba bean or cotton dry matter or tissue P concentration over the single crop cycle. We also recommend that Colwell-P be measured in the topsoil and subsoil to understand the quantity of plant-available P in Vertosols of the NGR, and that further research is needed to describe the resupply of the readily available P pool from slowly available P pools during a single crop cycle.
Survey of Barley yellow dwarf virus incidence in winter cereal crops, and assessment of wheat and barley resistance to the virus
Authors: Beoni Eva , Chrpová Jana , Jarošová Jana , Kundu Jiban Kumar
Published: November 2018

A survey of Barley yellow dwarf virus (BYDV) incidence in cereal crops in the Czech Republic over 4 years showed, on average, 13.3% BYDV-positive, randomly tested wheat and barley samples. The cultivated wheat and barley cultivars had different levels of susceptibility to BYDV infection. Field trials were performed with different barley and wheat breeding lines and cultivars, and resistance traits were evaluated after artificial inculcation by the viruliferous aphid vector Rhopalosiphum padi L. with BYDV-PAV. Our results showed high variability of visual symptom score (VSS) and reduction in grain weight per spike (GWS-R) in trials within the tested lines and cultivars. The barley line (WBON 96-123) and cultivars (Wysor, Travira) that contained RYd2 differed significantly from other cultivars in VSS. Line WBON 96-123 and cvv. Wysor and Yatzi showed the lowest GWS-R. Wheat line PSR 3628 and cvv. Altigo, Elan, Sparta, Aladin and Hewit showed significant difference from other cultivars in VSS. PSR 3628, Sparta, and Elan showed the lowest GWS-R. Similar results were obtained from BYDV titre analysis by RT-qPCR corresponding to the VSS and GWS-R traits. A low virus titre corresponded to low VSS and GWS-R. Hence, our results suggest that laborious and time-consuming GWS-R analysis could be replaced in some cases by qPCR-based BYDV titre analysis and, together with VSS evaluation, could enhance the efficiency of resistance assessment.
The cost of immunising at the general practice level
Authors: Turner Nikki , Rouse Paul , Airey Stacey , Petousis-Harris Helen
Published: November 2018

INTRODUCTION: Childhood immunisation is one of the most cost-effective activities in health care. However, New Zealand (NZ) has failed to achieve national coverage targets. NZ general practice is the primary site of service delivery and is funded on a fee-for-service basis for delivery of immunisation events. AIM: To determine the average cost to a general practice of delivering childhood immunisation events and to develop a cost model for the typical practice. METHODS: A purposeful selection of 24 diverse practices provided data via questionnaires and a daily log over a week. Costs were modelled using activity-based costing. RESULTS: The mean time spent on an immunisation activity was 23.8 minutes, with 90.7% of all staff time provided by practice nurses. Only 2% of the total time recorded was spent on childhood immunisation opportunistic activities. Practice nurses spent 15% of their total work time on immunisation activity. The mean estimated cost per vaccination event was $25.90; however, there was considerable variability across practices. A ‘typical practice’ model was developed to better understand costs at different levels of activity. CONCLUSIONS: The current level of immunisation benefit subsidy is considerably lower than the cost of a standard vaccination event, although there is wide variability across practices. The costs of delivery exceeding the subsidy may be one reason why there is an apparently small amount of time spent on extra opportunistic activities and a barrier to increasing efforts to raise immunisation rates. KEYWORDS: Immunisation; vaccination; patient care management; cost analysis; cost allocation
Do invitations to attend Well Man Checks result in increased male health screening in primary health care?
Authors: Barwell Pete
Published: November 2018

BACKGROUND AND CONTEXT: Male health outcomes lag behind those of women in many areas. Male utilisation of primary health care and uptake of preventative health care is relatively lower. Our question was: will inviting males who have not received recent health screening nor attended the practice frequently result in a higher rate of male health checks? ASSESSMENT OF PROBLEM: An auditable uniform classification ‘Well Man Check’ was established and education sessions on the importance of increasing male health care were held for all clinical staff. Recording of Well Man Check was audited for time periods prior to and after mailing out invitations to attend a Well Man Check. Thirty cases were reviewed to see if previously unrecognised health risks or symptomatic problems were detected. RESULTS: Bottom line: inviting males to attend for a Well Man Check almost triples the number of recorded Well Man Checks, and does not reduce the number of opportunistic Well Man Checks carried out. A range of problems and health risks requiring intervention or follow-up were detected. STRATEGIES FOR IMPROVEMENT: Further mail-outs to wider age ranges and ongoing discussion of results to stimulate ongoing interest amongst clinical staff is planned. LESSONS: Mail-out invitations do increase recorded Well Man Checks both within the age group mailed to, and also for males outside that age group. KEYWORDS: Male health; Well Man Check; primary health care
The calculation of transcript flux ratios reveals single regulatory mechanisms capable of activation and repression
Authors: Galburt Eric A.
Published: November 2018

Significance

Cells adapt to their environment by modulating the amount of RNA transcripts produced in a gene-specific manner. While some transcription factors are recruited via DNA sequence motifs, other factors bind directly to RNA polymerase to modulate the rate constants underlying the initiation process. Here, I describe a freely available web-based tool to quantitatively evaluate how factor-induced changes in the rate constants connecting initiation intermediates combine to regulate the amount of RNA produced per time. I use these calculations to show that multifaceted kinetic mechanisms may lead to differential and promoter-specific regulation. Finally, I explore the mechanisms of two factors essential for the response of bacteria to stress. The insights provided help to understand the logic of bacterial gene regulation.
Jump rope vortex in liquid metal convection
Authors: Vogt Tobias , Horn Susanne , Grannan Alexander M. , Aurnou Jonathan M.
Published: November 2018

Significance

The large-scale circulation (LSC) is the key dynamical feature of turbulent thermal convection. It is the underlying structure that shapes the appearance of geo- and astrophysical systems, such as the solar granulation or cloud streets, and the cornerstone of theoretical models. Our laboratory-numerical experiments reveal that the LSC can perform a fully 3D motion resembling a twirling jump rope. The discovery of this LSC mode implies that the currently accepted paradigm of a quasi-planar oscillating LSC needs to be augmented. Moreover, it provides an important link between studies in confined geometries used in experiments and simulations and the effectively unconfined fluid layers in natural settings where an agglomeration of LSCs forms larger patterns.
RT States: systematic annotation of the human genome using cell type-specific replication timing programs
Authors: Poulet Axel , Li Ben , Dubos Tristan , Rivera-Mulia Juan Carlos , Gilbert David M , Qin Zhaohui S
Published: November 2018

Motivation

The replication timing (RT) program has been linked to many key biological processes including cell fate commitment, 3D chromatin organization and transcription regulation. Significant technology progress now allows to characterize the RT program in the entire human genome in a high-throughput and high-resolution fashion. These experiments suggest that RT changes dynamically during development in coordination with gene activity. Since RT is such a fundamental biological process, we believe that an effective quantitative profile of the local RT program from a diverse set of cell types in various developmental stages and lineages can provide crucial biological insights for a genomic locus.

Results

In this study, we explored recurrent and spatially coherent combinatorial profiles from 42 RT programs collected from multiple lineages at diverse differentiation states. We found that a Hidden Markov Model with 15 hidden states provide a good model to describe these genome-wide RT profiling data. Each of the hidden state represents a unique combination of RT profiles across different cell types which we refer to as ‘RT states’. To understand the biological properties of these RT states, we inspected their relationship with chromatin states, gene expression, functional annotation and 3D chromosomal organization. We found that the newly defined RT states possess interesting genome-wide functional properties that add complementary information to the existing annotation of the human genome.

Availability and implementation

R scripts for inferring HMM models and Perl scripts for further analysis are available https://github.com/PouletAxel/script_HMM_Replication_timing.

Supplementary information

Supplementary data are available at Bioinformatics online.
Reorganization of Higher-Order Somatosensory Cortex After Sensory Loss from Hand in Squirrel Monkeys
Authors: Qi Hui-Xin , Liao Chia-Chi , Reed Jamie L , Kaas Jon H
Published: November 2018

Unilateral dorsal column lesions (DCL) at the cervical spinal cord deprive the hand regions of somatosensory cortex of tactile activation. However, considerable cortical reactivation occurs over weeks to months of recovery. While most studies focused on the reactivation of primary somatosensory area 3b, here, for the first time, we address how the higher-order somatosensory cortex reactivates in the same monkeys after DCL that vary across cases in completeness, post-lesion recovery times, and types of treatments. We recorded neural responses to tactile stimulation in areas 3a, 3b, 1, secondary somatosensory cortex (S2), parietal ventral (PV), and occasionally areas 2/5. Our analysis emphasized comparisons of the responsiveness, somatotopy, and receptive field size between areas 3b, 1, and S2/PV across DCL conditions and recovery times. The results indicate that the extents of the reactivation in higher-order somatosensory areas 1 and S2/PV closely reflect the reactivation in primary somatosensory cortex. Responses in higher-order areas S2 and PV can be stronger than those in area 3b, thus suggesting converging or alternative sources of inputs. The results also provide evidence that both primary and higher-order fields are effectively activated after long recovery times as well as after behavioral and electrocutaneous stimulation interventions.
A subcutaneous fluid collection after the Bentall procedure in a female patient with giant cell arteritis
Authors: Guimaron Samantha , Heautot Jean-François , Cador-Rousseau Bérangère , Verhoye Jean-Philippe
Published: November 2018

We report a 61-year-old woman with a history of untreated inflammatory symptoms, who underwent a Bentall procedure for a rapidly evolving aneurysm. Postoperatively, she presented with a sub-sternal pulsatile mass communicating with a periaortic collection. After excluding surgical and infectious complications, an inflammatory seroma due to an uncontrolled vasculitis was suspected. We proposed a non-surgical approach involving immunosuppressive therapy.
Obstinate nature
Authors: Cury Philippe
Published: November 2018

Resolving ecological patterns is challenging but fascinating as it generates new ways of looking at nature. I recapitulate here four independent scientific ideas that I developed throughout my career and that have contributed to a better understanding of the functioning of marine ecosystems. The optimal environmental window relating wind intensity and fish recruitment, the extended homing strategy developing an ecology of individuals, the wasp-waist control of marine ecosystems, and the bird-forage fish interaction are the four patterns that are presented. Communicating results to a large audience is not simply an added value of a scientific career but a responsibility for scientists when considering global emerging challenges. I encourage young scientists to communicate in an open and organized manner, as it will contribute to changing stakeholder’s views and fisheries management. Love of science and ground-breaking ideas are key to scientific careers and creativity can be sustained in many ways throughout a scientist’s career. I provide several tricks inspired by my personal experience that can help young scientists to stay innovative in the long run. Finally, I combine ecology and music, my two favourite topics, illustrating that an obstinate nature and an unexpected combination of unrelated ideas are key when dealing with research.
Understanding consequences of adaptive monitoring protocols on data consistency: application to the monitoring of giant clam densities impacted by massive mortalities in Tuamotu atolls, French Polynesia
Authors: Georget Stéphane , Van Wynsberge Simon , Andréfouët Serge
Published: November 2018

During long-term monitoring, protocols suitable in the initial context may have to change afterward because of unforeseen events. The outcome for management can be important if the consequences of changing protocols are not understood. In Tuamotu Archipelago atolls, French Polynesia, the density of giant clams (Tridacna maxima) has been monitored for 12 years, but massive mortalities and collapsing densities forced to shift from a line-intercept transects and quadrats (LIT-Q) method to a belt-transect (BT) method. We investigated with a simulation approach the conditions (density, size structure, aggregation of giant clam populations) under which the two methods provided different results. A statistical model relating the BT density to the LIT-Q density was validated using new field data acquired on the same sites with both protocols, on two atolls. The BT method usually provided higher estimates of density than the LIT-Q method, but the opposite was found for very high densities. The shape of the relationship between measurements depended on population size structure and on aggregation. Revisiting with the model the historical LIT-Q densities suggested that densities have been underestimated in the past but previously detected trends in population trajectories remained valid. The implication of these findings for management are discussed.
Gravitational potential and non-relativistic Lagrangian in modified gravity with varying G
Authors: Christodoulou Dimitris M , Kazanas Demosthenes
Published: November 2018

We have recently shown that the baryonic Tully–Fisher (BTF) and Faber–Jackson (BFJ) relations imply that the gravitational ‘constant’ G in the force law vary with acceleration a as 1/a. Here we derive the converse from first principles. First we obtain the gravitational potential for all accelerations and we formulate the Lagrangian for the central-force problem. Then action minimization implies the BTF/BFJ relations in the deep MOND limit as well as weak-field Weyl gravity in the Newtonian limit. The results show how we can properly formulate a non-relativistic conformal theory of modified dynamics that reduces to MOND in its low acceleration limit and to Weyl gravity in the opposite limit. An unavoidable conclusion is that a0, the transitional acceleration in modified dynamics, does not have a cosmological origin and it may not even be constant among galaxies and galaxy clusters.
The Application of Forensic Linguistics in Cybercrime Investigations
Authors: Perkins Ria C
Published: November 2018

Forensic linguistics is the application of linguistic knowledge and theory to forensic, legal, or criminal contexts. This article sets out some of the ways the forensic linguists can and do contribute to cybercrime investigations, as well as indicating how a basic knowledge of linguistics can be of use to investigators. This article introduces both investigative and evidentiary applications, including comparative authorship analysis, sociolinguistic profiling, and the determination of meaning. Through a discussion of casework and research this article aims to increase awareness and provide an introduction into the field of forensic linguistics, and its potential applications within the field of cybercrime. This article will focus on native language influence detection as an example of an area of forensic linguistic research and methodology that can be applied in cybercrime casework, discussing both the research and its findings, and demonstrating potential application.
BASELINE EVALUATION STUDY OF NATURALLY OCCURRING RADIONUCLIDES IN SOIL SAMPLES FROM VICINITY OF INDIA’S FIRST FAST REACTOR FUEL CYCLE FACILITY (FRFCF), DAE COMPLEX, KALPAKKAM, INDIA
Authors: Bramha S N , Krishnan H , Subramanian V , Baskaran R , Venkatraman B
Published: November 2018

The activity concentration of 238U, 232Th and 40K were measured in the soil samples collected from Fast Reactor Fuel Cycle Facility (FRFCF) site, using high-resolution gamma-ray spectrometry. This study is aimed to establish the baseline data of naturally occurring radionuclides within the site. The average activity concentrations were found to be 416.5, 61.7 and 622.3 Bq kg−1 for 40K, 238U and 232Th, respectively. The activity concentrations and its radiological indices were evaluated and were compared with the international values reported by the United Nations Scientific Committee on the Effects of Atomic Radiation (UNSCEAR). The ratio of 40K/232Th and 40K /238U were calculated, which indicates the presence of 5.79 and 2.69 times more K-bearing minerals as compared with Th and U-bearing minerals in the soil samples, respectively. The study provides baseline information on concentration of radionuclides and background radiological assessment of the FRFCF site.
Perioperative Pressure Injuries: A Systematic Literature Review
Authors: Bulfone Giampiera , Bressan Valentina , Morandini Alessandro , Stevanin Simone
Published: November 2018

OBJECTIVE:

To conduct a systematic review to investigate risk factors, incidence, and preventive strategies for perioperative pressure injuries (PIs).

METHODS:

The authors reviewed four databases for literature published from January 2001 to December 2017. Selected articles included primary quantitative studies with prospective, descriptive, and longitudinal design or randomized controlled trials that evaluated risk factors, incidence, and preventive strategies for perioperative PIs. The studies included were evaluated for methodological quality using the Edwards Method Score. The authors used a standardized extraction form to extract inclusion and exclusion criteria, participant demographics, methodology, PI risk instrument and classification systems, type of surgery and anesthesia, PI risk factors, incidence, preventive strategies, and outcomes evaluation.

MAIN RESULTS:

Of the 115 publications identified, 11 met the inclusion criteria. The risk assessment and PI classification instruments used differed in every study. Incidence of PI varied throughout the studies and was reduced by warming therapy and by a skin care intervention program.

CONCLUSIONS:

Further studies are necessary to develop a standard risk assessment instrument and preventive strategies and to clarify some contradictions evident in the literature.
Changes in Healthcare Encounter Rates Possibly Related to Cannabis or Alcohol following Legalization of Recreational Marijuana in a Safety-Net Hospital: An Interrupted Time Series Analysis
Authors: Calcaterra Susan L. , Hopfer Christian J. , Keniston Angela , Hull Madelyne L.
Published: November 2018

Objectives:

Liberalization of marijuana laws in Colorado contributed to increases in cannabis-related adverse events over time. We examined characteristics of patients with healthcare encounters possibly related to cannabis and assessed the temporal association between legalization of recreational marijuana and healthcare encounters possibly attributed to cannabis.

Methods:

Annual encounter rates possibly related to cannabis and alcohol were compared using negative binomial regression. Two-time intervals, pre/post-recreational marijuana legalization (January 2009 to December 2013 and January 2014 to December 2015, respectively) were used to examine changes in monthly rates of emergency encounters and hospitalizations possibly related to cannabis. Level and trend changes on encounter rates by legalization period were assessed using interrupted time series analyses. Encounters possibly related to alcohol were used as a comparator group.

Results:

Most encounters identified during the study period had alcohol-related International Classification of Diseases Diagnosis and Procedural Codes (ICD-9/10-CM) codes (94.8% vs 5.2% for cannabis). Patients with encounters possibly related to cannabis were younger, more likely to be hospitalized and more likely to be admitted to the psychiatric unit than patients with encounters possibly related to alcohol. Initial and sustained effects of encounter rates possibly related to cannabis demonstrated an increased trend in slope before and after recreational marijuana legalization. The slope became more abrupt following legalization with a significant increase in trend during the post-legalization period (β = 2.7, standard error = 0.3, ρ < 0.0001). No significant change was noted for encounters possibly related to alcohol.

Conclusions:

Additional research should identify patients at highest risk of an adverse health event related to cannabis and quantify costs associated with cannabis-related healthcare delivery.
Predictive Factors for Hypotension Associated With Supine-to-Prone Positional Change in Patients Undergoing Spine Surgery
Authors: Yoon Hyun-Kyu , Lee Hyung-Chul , Chung Jaeyeon , Park Hee-Pyoung
Published: November 2018

Background:

Positional change during general anesthesia can cause hypotension. The objective of this retrospective study was to determine predictive factors for hypotension associated with supine-to-prone positional change in spinal surgery patients.

Materials and Methods:

Data on demographics, current medications, comorbidity, intraoperative mean arterial pressure (MAP), heart rate, pulse pressure variation, tidal volume, peak inspiratory pressure, and propofol and remifentanil effect-site concentrations were collected from 179 patients undergoing elective spine surgery. Hypotension associated with supine-to-prone positional change was defined as >20% reduction in MAP during positional change.

Results:

Hypotension associated with supine-to-prone positional change was observed in 16 (8.9%) patients. The median (interquartile range) effect-site concentration of remifentanil (5.3 [4.0 to 8.5] vs. 4.0 [3.1 to 4.0] ng/mL, P<0.001), MAP (95.0 [86.0 to 103.5] vs. 80.0 [70.0 to 94.0] mm Hg, P=0.014), peak inspiratory pressure (16.5 [15.0 to 18.5] vs. 15.0 [14.0 to 17.0] hPa, P=0.040) in the supine position, and pulse pressure variation in the prone position (12.0 [9.0 to 16.4] vs. 9.0 [7.0 to 12.0]%, P=0.019) were significantly higher in the hypotension group. In multivariate logistic regression analysis, the effect-site concentration of remifentanil (odd ratio [95% confidence interval], 2.12 [1.51-2.96], P<0.001), preoperative use of beta-blocker (7.64 [1.21-48.36], P=0.031), and MAP in the supine position (1.04 [1.00-1.07], P=0.033) were independent predictive factors for hypotension associated with supine-to-prone positional change.

Conclusions:

Increased effect-site concentration of remifentanil, preoperative use of beta-blocker, and high MAP in the supine position were predictive factors for hypotension associated with supine-to-prone positional change in spinal surgery patients.