bluuebunny/crossref_metadata_2025 huggingface dataset:
The Role of Isotope Fractionation Effects in Atmospheric Chemistry
Authors: Stevens C. M. , Wagner A. F.
Published: February 2015

Kinetic isotopic fractionation plays an important role in the quantitative analysis by isotopic studies of the cycles of the two atmospheric trace gases, CO and CH4, which are important because of their impact on the environment. These gases are scavenged from the atmosphere mainly by homogeneous gas phase oxidation reactions with OH radicals. The isotopic composition of these gases provides constraints on the relative distribution of the fluxes from sources, natural or anthropogenic, of different isotopic compositions. The relationship between the composition of the gas in the atmosphere and the average value of the sources is determined by the fractionation effect of the scavenging processes, in particular the reaction with OH. Thus, knowledge of the fractionation effect is essential to determining the relative distribution of the fluxes from isotopically different sources. The reactions CO + OH and CH4 + OH exhibit several types of KIE’s including normal, inverse, and compound effects resulting from the bimodal character of the former. A brief discussion of the measured values of the KIE for these reactions and their application to interpretation of the atmospheric cycles of CO and CH4 is presented.
Evaluationof Isotope Effectson Henry's Law Constants by a Molecular DynamicsTechnique
Authors: Dang Liem X. , Bopp Philippe , Wolfsberg Max
Published: February 2015

Solute isotope effects on Henry’s law constants of aqueous solutions of argon atoms, of helium atoms, and of nitrogen molecules are considered. A cell model is employed; the translational and rotational motions are treated in the first quantum approximation while the vibrational motion of nitrogen is fully treated (but assumed to be separable and harmonic). The required mean square forces (or equivalent frequency parameters) are evaluated by classical molecular dynamics calculations.
A General Theorem for Complex Chemical Systems Amenable to the Horiuti Approach
Authors: Popa V. Tudor , Vlad Marcel O. , Segal E.
Published: February 2015

This paper deals with complex chemical systems for which Horiuti’s theory of stoichiometric numbers may bc applied. A general theorem is proved, linking the mechanistic and overall representations: the number of linearly dependent overall reactions equals the number oflinearly dependent steps.
The Effect of Deuteration on the Molecular Dipole Moments of Haloacetylenes
Authors: Heineking N. , Andresen U. , Dreizler H.
Published: February 2015

The dipole moments of chloro-, bromo-, and iodoacetylene, and those of the respective deuterated species, have been accurately determined using microwave Fourier transform spectrometers equipped with Stark cells. In each case, deuteration resulted in a change of the value of the dipole moment of about 0.012 D. The results provide strong evidence that the orientation of the dipole moment vector of iodoacetylene is opposite to that of the other haloacetylenes.
On the Validity of Macroscopic Models
Authors: Kerner W. , Pfirsch D. , Weitzner H.
Published: February 2015

The validity of macroscopic models in the limit of large mean-free path is examined by solving a one-dimensional model equation, where the term v Vf1 is retained in the kinetic equation. A standard thirteen-moments approximation yields accurate results in all collisionality regimes if the fluid velocity is sufficiently small. In contrast, the Chapman-Enskog scheme is only accurate in the collision-dominated regime
LiBa4[Mo2N7] und LiBa4[W2N7]: Neue Nitridomolybdate/wolframate(VI) mit dimeren Tetraeder-Anionen / LiBa4[Mo2N7] and LiBa4[W2N7]: New Nitridomolybdates/tungstates(VI) with Dimeric Tetrahedral Anions
Authors: Höhn Peter , Kniep Rüdiger , Maier Joachim
Published: February 2015

Abstract Black crystals of the isotypic phases LiBa4[Mo2N7] and LiBa4[W2N7] (monoclinic, P2/n; a = 1552.2(3)/1555.2(4), b = 642.2(1)/644.4(1), c = 1039.9(2)/1042.4(2) pm; β = 99.23(2)/99.30(3)°; Z = 4) were grown from the melt (Li, Ba3N2, Mo/W; molar ratio 20 : 5 : 1;Tmax = 1323 K; reaction with N2, 1 atm, 18 h) by cooling (20 K/h). The crystal structures contain two independent dimeric units [ MO2N7]9- / [W2N7]9- (staggered conformation; Mo/W -N -Mo/W : 173.6/173.7° and 180°/180°; Mo/W -N(term): 180(2)-185(1)/181(3)-185(1) pm; Mo/W -N(bridg) : 195(1)/194(1) pm and 193(1)/194(1) pm).
Über Metallalkyl- und -arylverbindungen, 51. Mittlg.* Unsymmetrische Diorganomagnesiumverbindungen. MgRR'(L) und solvensgetrennte Ionenpaare mit R = Me, Et, R' = Cyclopentadienyl, Indenyl, Fluorenyl, Phenylethinyl, L = Tetramethylethylendiamin, Pentamethyldiethylentriamin / On Metal Alkyl and Aryl Compounds, Part 51 Unsymmetrical Diorganomagnesium Compounds. MgRR'(L) and Solvens Separated Ion Pairs with R = Me, Et, R' = Cyclopentadienyl, Indenyl, Fluorenyl, Phenylethynyl, L = Tetramethylethylenediamine, Pentamethyldiethylenetriamine
Authors: Viebrock Heiko , Abein Dirk , Weiss Erwin
Published: February 2015

Amine adducts of diorganomagnesium compounds MgR2(L) are soluble in hydrocarbons and therefore valuable synthons for reactions in non-polar solvents. In this way unsymmetrically substituted derivatives MgRR'(L) become available by substituting one organic group by a different carbanion via acid-base reactions, according to eq. (1):

R2Mg(L) + HR' -> RR'Mg(L) + HR (1)

with HR' being stronger CH-acids than HR.

Using the amin adducts R2Mg(L) (R = Me, Et) with chelating amines (L = tetramethyl­ ethylenediamine, TMEDA, pentamethylethylenetriamine, PMDTA) and the strong CH-acids cyclopentadiene, indene, fluorene and alkynes the following compounds have been synthesized and their structures derived by X-ray analyses: MgMe(η3-cyclopentadienyl)(tmeda) (1), MgMe(η3-indenyl)(tmeda) (2), MgMe(η1-fluorenyl)(tmeda) (3), [Mg2Me2(pmdta)2]2+[fluorenyl]−
2
benzene (4) and [Mg2Et(phenylethynyl)3(tmeda)]2 ∙ benzene (5). It is remarkable, that cyclopentadienyl, indenyl, and fluorenyl ligands have a lower hapticity than η5 to the metal, due to steric repulsion by the other ligands. In 4 the bulky tridentate base PMDTA prevents any direct interaction between the fluorenide anion and magnesium, giving solvens separated ion pairs with the unusual and hitherto rare example of an organomagnesium cation [Mg2Me2(pmdt)2]2+. The 1:3 compound 5 has a more complicated structure, related to that of alkali metal alkynyl magnesates.
Excitonic Bands in the Optical Absorption Spectra of A3MX6 and A3M2X9 (A = MeNH3, Me2NH2, Me3NH, Me4N; M = Bi, Sb; X = Cl, Br, I)
Authors: Papavassiliou G. C. , Koutselas I. B.
Published: February 2015

The title compounds (natural low-dimensional semiconductors) show strong excitonic optical absorption bands in the UV-visible spectral region, because of the dielectric confinement of excitons. as in the cases of other similar systems based on PbX2-
4, SnX2-
4. PtI - X - PtIV-X , Cdx,Sy-clusters etc
Ein Dimer von Ferroceno[1,2]cyclohexen-1-on-3 / A Dimer of Ferroceno[1,2]cyclohexen-1-one-3
Authors: Brunner Henri , Muschiol Manfred , Nuber Bernhard
Published: February 2015

A new by-product in the synthesis of ferroceno[1,2]cyclohexen-1-one-3 (1) is the dimer 2, which has been characterized by an X-ray analy­sis. Molecular structure of 2: Space group C 2h/6, C2/c, (15). Unit cell (Å): a = 42.54(3); b = 10.062(6); c = 22,04(1); monoclin; Z = 8.
Silaethene XVI [1]. Bildung und Reaktivität der Silaethene Me(Vi)Si=CHCH2
tBu und Vi2Si=CHCH2
tBu / Silaethenes XVI [1]. Formation and Reactivity of the Silaethenes Me(Vi)Si=CHCH2
tBu and Vi2Si=CHCH2
tBu
Authors: Grobe Joseph , Ziemer Harald
Published: February 2015

The reactions of Vi2(Me)SiCl or Vi3SiCl with tBuLi in pentane solution at low temperatures (-78 to 20 °C) are governed by the addition of tBuLi to one of the vinyl groups, followed by LiCl elimination to yield the silaethenes Vi(Me)Si=CHNp (1) and Vi2Si=CHNp (2), re­spectively. The following reactions of 1 and 2 without or with trapping reagents have been studied in some detail. Both silaethenes undergo dimerization with formation of 1,3-disilacyclobutane derivatives, in case of 2 accompanied by trimers. A surprise is the generation of the disilanes Vi(Me)Si(CH=CHtBu)Si(Me)Vi(CH2CH2
tBu) (3) and Vi2Si(CH=CHtBu)SiVi2(CH2CH2
tBu) (17) very probably by intermolecular ene-type reac­tions. With DMB or isoprene as trapping agents [4 + 2]-cycloadducts 11, 14, 15, 21, ene-pro- ducts 10, 13 and substitution products 12, 22 are obtained. A very efficient indirect detection of 1 and 2 has been achieved with Me3SiOMe as quenching reagent, which gives excellent yields of the adducts Vi(Me)Si(OMe)CH(SiMe3)Np (16, 91%) and Vi2Si(OMe)CH(SiMe3)Np (23, 76%). respectively. Problems in the characterization of iso­mer mixtures arise from difficulties in the GC separation procedure and from the limited thermal stabilities of some of the products. 1 and 2 are very similar with respect to the reactivity of the Si=C double bond, but differ considerably in their tendency to undergo polymerization which is connected to the number of vinyl groups. Therefore, the yields of the typical Si=C products is drastically reduced in the case of 2. In spite of separation pro­blems most of the products have been characterized by a combination of GC/MS. GC/FT-IR and NMR measurements.
Alkalimetallformiate, VI. Die Kristallstruktur von Rubidiumhydrogendiformiat, RbH(HCO2)2 [1] / Alkali Metal Formates, VI. The Crystal Structure of Rubidium Hydrogen Diformate, RbH(HCO2)2 [1]
Authors: Müllera Kerstin , Range Klaus-Jürgen , Heyns Anton M.
Published: February 2015

Single crystals of the title compound have been obtained by neutralization of formic acid with solid rubidium carbonate and subsequent solvent evaporation at room temperature. The very hygroscopic crystals are orthorhombic, space group Pbca (Nr. 61), with a = 7.614(1), b = 17.926(2), c = 7.862(1) Å and Z = 8. The structure, which has been refined to R = 0.072 and Rw = 0.067 for 1008 unique reflections, is isotypic with that of the analogous potassium compound. It comprises layers of edge-sharing distorted RbO8 square antiprisms, sandwiched between two adjacent formate layers. The sandwiches are hold together by O···H···O inter­actions, which are, however, rather weak.
Neue mono-und spirobicyclische Aminosilane: Synthese, Struktur und Eigenschaften / New Mono-and Spirobicyclic Aminosilanes: Synthesis, Structure and Properties
Authors: Schlosser Th. , Sladek A. , Hiller W. , Schmidbaur H.
Published: February 2015

The reactions of the N.N'-dialkyl/aryl-ethylenediamines l a - e with equimolar amounts of tetrachlorosilane give the monocyclic aminosilanes 2 a - e in good yields. With two equivalents of the diamines 1 only one spirobicyclic compound, l,4,6,9-tetrabenzyl-l,4,6,9-tetraaza-5-silaspiro[ 4.4]nonane, 4e, can be prepared. It is only via an independent double deprotonation of the diamines that the spirobicyclic ethyl- and isopropyl derivatives 4a and 4b are also becoming available. A ll compounds have been characterized by multi-NMR and mass spectrometry. In three cases (2d, 2e and 4e), the crystal and molecular structures have been determined by X-ray diffraction analysis. A planar silaimidazolidine ring system has been confirmed for the phenyl substituted species 2d, while in the corresponding benzyl substituted homologue 2 e both nitrogen atoms are pyramidal and lead to ring puckering. The silicon atom in 4 e shows a strongly distorted tetrahedral coordination. The endocyclic angle N 1 - Si - N2 = 92.8(1)° is nearly orthogonal, and the angle between the planes defined by the silicon and the two nitrogen atoms of the five-membered rings is 81.4(1)°.
Er2Au2Sn and other Ternary Rare Earth Metal Gold Stannides with Ordered Zr3Al2-Type Structure
Authors: Pöttgen Rainer
Published: February 2015

The ternary stannides RE2Au2Sn (RE = Y, Dy, Ho, Er, Tm, Lu) were prepared by arcmelting of the elemental components and subsequent annealing at 800 °C. The structure of Er2Au2Sn (single crystal, X-ray, P42/mnm, Z = 4, a = 778.2(2) pm, c = 739.6(3) pm, V = 0.4479 nm3 and R = 0.026) is described as the ternary ordered version of the Zr3Al2-type structure, a superstructure of the U3Si2-type. It consists of two-dimensionally infinite layers (Au2Sn)n which are separated by the erbium atoms. The structure is built up from slightly distorted [SnEr8) square prisms and [AuEr6] trigonal prisms which are condensed in all three directions. These fragments are derived from the well known AlB2 and CsCl-type structures.
Synthese und Kristallstruktur von NaMgl,64Cu0,36V3O10/ Synthesis and Crystal Structure of NaMgl,64Cu0,36V3O10
Authors: Martin F.-D. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of NaMg1.64Cu0.36V3O10 have been prepared by heating mixtures of Na2CO3, MgCO3, CuO and V2O5 above the melting point. The yellow crystals show triclinic symmetry, space group Ci
1-P1̅, a = 6.726(8), b = 6.743(7), c = 9.625(2) Å, α = 100.705(9), β = 104.57(1), γ = 101.700(9)°, Z = 2. NaMg1.64Cu0.36V3O10 represents a new structure type showing V3O10 groups, a statistical distribution of Mg2+ and Cu2+ on two point positions, and Na+ in an irregular coordination.
Die Kristallstrukturen von Magnesiumdibromid-Diglym-Addukten / Crystal Structures of Magnesium Dibromide Diglyme Adducts
Authors: Metzler Nils , Nöth Heinrich , Schmidt Martin , Treitl Andreas
Published: February 2015

(MgBr2·diglyme)2 (1) crystallized in low yield from an ether solution of the Grignard compound mesMgBr (mes = mesityl) on adding diglyme. It is more conveniently prepared from an ether solution of MgBr2 by addition of diglyme. The mixed solvate MgBr2·diglyme thf (2) crystallized from a diglyme/tetrahydrofuran solution of 1 after addition of ether. An X-ray structure determination of 1 reveals dimeric units containing hexacoordinated Mg atoms surrounded by three oxygen atoms and three bromide atoms, with each kind of atoms arranged in a meridional fashion. The two octahedral MgO3Br3 units share a common edge with two Br atoms. Compound 2 is a mononuclear complex with the Br atoms in cis-position. The diglyme ligand occupies meridional positions of a distorted MgBr2O4 octahedron.
Produkte der Carbodiimid-Hydroborierung mit (9H -9-BBN)2 [1] / Hydroboration Products of Carbodiimides with (9H-9-BBN)2 [1]
Authors: Boese Roland , Köster Roland , Yalpani Mohamed
Published: February 2015

The hydroboration of H11C6N=C=NC6H11(A) with (9H-9-BBN)2 (C2) gives H11C6N= C(H)N(C6H11)BC8H14 (1), which reacts with 9H-9-BBN to form the six-membered hetero­cycle mixed dimer

(2). Compound 2 crystallizes in the monoclinic space group C 2/c, a = 27.776(3). b = 17.140(2), c = 12.302(2) Å, β = 113.31° (at 120 K). - On heating. 2 is transformed by intramolecular hydroboration into H2C[N(C6H11)B(C8H14)]2 (3a). - 1 reacts with Et2O-BF3 to give 9F-9-BBN (4) and

(5). - The total hydroboration of H5C6N=C=NC6H5 (B) with C2 affords H2C[N(C6H5)B(C8H14)]2 (3b).
Insertion of Isocyanides into the Palladium-Carbon Bond of Cyclopalladated Complexes
Authors: Zografidis Anastassios , Polborn Kurt , Beck Wolfgang , Markies Bertus A. , Koten Gerard van
Published: February 2015

Insertion of isocyanides into the Pd-C bond has been observed in the reactions of PdBr[C6H3(CH2NMe2)2-2,6] with isocyanides CNR which give the complexes PdBr[C(=NR)C6H3(CH2NMe2)2-2,6-C̲,N̲](CNR) (2a-d). An imino bridged complex 5 is formed on heating the imino complex PdCl[C(=NCH2CO2Et){C6H4(CH2NMe2)-2}](CNCH2CO2Et). The structures of 2c (R = nBu) and 5 have been determined by X-ray crystallography.
π-Olefin-Iridium-Komplexe, XXII [1]. C-H-Aktivierung von aromatischen und aliphatischen Solvensmolekülen RH bei der Reaktion von [Cp*IrCI2]2 mit Butadienmagnesium unter Bildung von [Cp*Ir(η3-C4H7)R] sowie Kristallstruktur von [Cp*Ir(η3-C4H7)C6H5] / π-Olefin Iridium Complexes, XXII [1]. C-H Activation of Aromatic and Aliphatic Solvent Molecules RH in the Reaction of [Cp*IrCl2]2 with Butadienemagnesium with Formation of [Cp*Ir(η3-C4H7)R], and Crystal Structure of [Cp*Ir(η3-C4H7)C6H5]
Authors: Müller Jörn , Gaede Petra Escarpa , Qiao Ke
Published: February 2015

Reactions of [Cp*IrCl2]2 (Cp*=η3-C5Me5) with [MgC4H6·2 THF]n at low temperature give [Cp*Ir(η4-C4H6)] together with [Cp*Ir(η3-C4H7)R] compounds, the latter being formed via C-H activation of solvent molecules RH (RH = benzene, toluene, anisole, thiophene, furane, N-methylpyrrole, pentane, cyclohexane. THF). In the case of pyrrole, C-N -activation occurs. The ratio of syn and anti isomers of the 1-methylallyl complexes as well as the sites of C-H activation of RH were investigated by NMR spectrometry. An enantiomorphous crystal of [Cp*Ir(η3-C4H7)C6Hs] was characterized by X-ray diffraction analysis which reveals trigonal planar coordination at the Ir atom and an exo, syn conformation of the 1-methylallyl ligand. A mechanism of the reaction which involves 16-electron intermediates is discussed. The corresponding system [Cp*RhCl2]2/butadienemagnesium/RH gives only [Cp*Rh(η4-C4H6)], and no C-H activation is observed.
Lanthanoiden-Komplexe, IX [1]. Reaktivitätsbestimmender Einfluß der Ligandenkonstitution bei Seltenerdamiden: Herstellung und Struktur sterisch überladener Alkoxid-Komplexe / Lanthanoid Complexes, IX [1]. Reactivity Control of Lanthanoid Amides through Ligand Effects: Synthesis and Structures of Sterically Congested Alkoxy Complexes
Authors: Herrmann Wolfgang A. , Anwander Reiner , Munck Florian C. , Scherer Wolfgang , Dufaud Veronique , Huber Norbert W. , Artus Georg R. J.
Published: February 2015

It is shown that the introduction of sterically demanding ligands in lanthanoid metal complexes can depend more on the precise composition of the lanthanoid precursor than on the size of the new ligand. Thus, tris(r-butyl)methanol (“rmojt-H”) does not react with the amides Ln[N(SiMe3)2]3 of the “late” (small) lanthanoid metals. However, fast and clean reactions occur with the sterically less demanding derivatives Ln[N(SiHMe2)2]3, with new homoleptic complexes Ln(tritox)3 (Ln = Y, Nd) being formed with practically all metals of this group of elements. The molecular and crystal structures of some lanthanoid amides and alkoxides are described.
Einkernige und oxoverbrückte zweikernige Fe(III)-Komplexe von N-Alkyl-N,N-bis(2-pyridylmethyl)aminen / Mononuclear and Oxo-Bridged Binuclear Fe(III) Complexes of N-Alkyl-N,N-bis(2-pyridylmethyl)amines
Authors: Dick Stefan , Weiss Armin , Wagner Ursel , Wagner Friedrich , Große Gerhard
Published: February 2015

Tridentate amines of the type N-alkyl-N,N -bis(2-pyridylmethyl)amine with alkyl = methyl L1, benzyl L2 and adamantyl L3 form mononuclear Fe(III) complexes LFeCl3. In the presence of various carboxylates binuclear μ-oxo-bis(μ-carboxylato) Fe(III) complexes [L2Fe2O(RCO2)2]2+ are formed. These compounds can be synthesized from mono-, bi-, tri- and tetranuclear iron complexes as starting materials.

The crystal structures of three mononuclear and four binuclear complexes show that the tridentate ligand is always facially coordinated to Fe. While in binuclear complexes of L1 and L2 the Namin-atom is trans to the oxo-bridge, in a complex of L3 a coordination with one Npyridin atom trans to that bridge is found. In all complexes the Fe-Namine distances increase with increasing space requirement of the alkyl substituent. The effects of different ligands trans to Namine and Npyridin are discussed.

57Fe Mößbauer spectra show that the electric field gradient at Fe vanishes in L1FeCl3 and L2FeCl3 despite non-cubic ligand spheres. For both mono- and binuclear complexes a correlation between isomer shift δ and Fe-N distances exists. The strong increase of Lamb-Mößbauer factors on cooling to 4,2 K and the Goldanski-Karyagin effect observed for some complexes can be explained by the displacement parameters of the Fe-atoms obtained by X -ray structure analysis.
Ternary Rare Earth Transition Metal Zinc Compounds RT2Zn20 with T = Fe, Ru, Co, Rh, and Ni
Authors: Nasch Tono , Jeitschko Wolfgang , Rodewald Ute Ch.
Published: February 2015

Forty eight new compounds RT2Zn20 were prepared by annealing cold-pressed pellets of the elemental components in an argon atmosphere. They crystallize with the cubic CeCr2Al20 type structure (Fd3̅̅m , Z = 8), which was refined from single-crystal diffractometer data of TbFeiZn20 (a = 1411.1(1) pm ), YRu2Zn20 (a = 1422.6(1) pm ), DyRu2Zn20 (a = 1422.1(1) pm), GdCo2Zn20 (a = 1406.0(1) pm ), DyRh2Zn20 (a = 1418.2(1) pm ), and TmNi2Zn20 (a= 1401.6(1) pm) to conventional residuals varying betw een R = 0.011 and R - 0.024. The com pounds have a tendency for tw inning, thus m im icking hexagonal sym metry, with the cubic [111] axis as the axis w ith the pseudohexagonal symmetry. M inor inconsistencies in the cell volum es of these com pounds indicate slight deviations from the ideal com position. N evertheless, the five atom ic sites of this structure w ere found to be fully occupied w ithin the error lim its w ith the exception of one zinc site of TmNi2Zn20. The coordination for the site of the rare earth atom s is a Frank-K asper polyhedron with coordination num ber (CN) 16. The transition metal atom s occupy a site w ith icosahedral zinc coordination (CN 12). Two of the three zinc sites are in pentagonal prism atic coordination of zinc atom s, capped by rare earth and/or transition metal atom s (CN 12), w hile the third zinc site has 12 zinc neighbors form ing a hexagonal prism , w hich is capped by tw o rare earth atom s (CN 14).
Syntheses, Structures, and Spectroscopic Properties of Alkoxide, Hydroxide, and Siloxide Complexes with (η3-Allyl)Mo Moieties
Authors: Borgmann Cornelia , Limberg Christian , Zsolnai László , Heinze Katja
Published: February 2015

Salts with binuclear anions of the general formula [(η3-C3H4R)(CO)2Mo(μ-OR′)2(μ-OR″)-Mo(CO)2(η3-C3H4R)]- (R = h , R′, R″ = Me, 2 ; R = CH3, R′ = CH(CH3)2, R″ = OH, 3; R = CH3, R′ = OH, R″ = OSiMe3, 4) have been synthesised via reaction of [(η3-C3H4R)- Mo(CO)2(CH3CN)2(thf)]+BF4
- , 1, with NaOMe, NaOiPr, and KOSiMe3. All products were characterised spectroscopically and investigated by single crystal X-ray analysis. In the case of 3 low temperature 2D-NMR spectra revealed that the solid state structure is maintained in solution and that the compound shows a trigonal twist-rearrangement at room temperature.
Umsetzung von Cyclopentadienylmetallcarbonylen mit Thionylhalogeniden - Neue Synthese halogenoverbrückter Cp*Co-Komplexe / Reaction of Cyclopentadienyl Metal Carbonyles with Thionylhalides - New Synthesis of Halogeno-Bridged Cp*Co Complexes
Authors: Stoll Carola , Lorenz Ingo-Peter , Polbom Kurt , Paulus Erich Friedrich
Published: February 2015

The reaction of Cp*Co(CO)2 with thionylchloride in hexane affords the doubly bridged dimer (Cp*CoCl2)2. Whereas the same reaction in more polar solvents such as CH2Cl2 or thf gives the triply bridged dinuclear cations in the salt [(Cp*Co)2(μ-Cl)3]2 [Co2Cl6], no influence of the solvent is observed in the reaction of Cp*Co(CO)2 with thionylbromide, which results in the formation of the neutral dimer (Cp*CoBr2)2. The X-ray structure analysis of (Cp*CoBr2)2 shows two edge-sharing octahedra, while that of [(Cp*Co)2(μ-Cl)3]2[Co2Cl6] shows two facesharing octahedra in the cation and two edge-sharing tetrahedra in the anion.
Mixed-Sandwich η5/η7 Vanadium Complexes. The Molecular Structure of (η5-2-Methyl-indenyl)-(η7-cycloheptatrienyl)-vanadium
Authors: Herberhold Max , Köppl Silke , Milius Wolfgang
Published: February 2015

The diamagnetic halfsandwich complexes [V(η7-C7H7)(CO)3] and [V(η5-L5)(CO)4] have been used as intermediates in the conversion of hexcarbonylvanadium, V(CO)6, to the paramagnetic trovacene derivatives, [V(η5-L5)(η7-C7H7)] [L5 = cyclopentadienyl ligand, C5H4-R (R = H (1), Me (1a), tBu (1b)) and C5Me5 (1c); indenyl (2) and 2-methylindenyl (2a)]. The molecular structure of 2a has been determined: the distances between vanadium and the center Z of the (nearly parallel) ring ligands are 193.0 pm (V-Z5) and 146.2 pm (V-Z7).
Alkyl Heteroaromatics as Building Blocks in Organic Synthesis: The Reactivity of Alkyl Azoles toward Electrophilic Reagents
Authors: Hafiz I. S. Abdel , Hassanien A. A. , Hussein A. M.
Published: February 2015

Oxazolone (1) couples with aromatic diazonium salts to yield the arylhydrazones (3a-c). Compound 3 reacts with aniline to give aryl hydrazone (5). Compound 5 was also obtained via converting 1 into the imidazolone (4) and subsequent treatment of 4 with aromatic diazonium salts. Compounds 1 and 12 reacted with arylidenemalononitrile (6) to yield compounds 8 and 14 respectively. Also compounds 1, 12 condensed with an aromatic aldehydes to yield 11 and 17. Compounds 11, 17 reacted further with one molecule of malononitrile to give compounds 8 and 14, respectively. Compound 20 which was generated in situ by heating phenacylthiocyanate (19) in acetic anhydride on treatment with hydrazine hydrate or phenyl hydrazine gives 21 and 22 respectively. A lso 20 reacted with malononitrile or with ethyl cyanoacetate to give 23 and 24, respectively.
Thioanalogs of Sparteine Lactams [6]. Part II. (+)-2-Thionosparteinium Perchlorate
Authors: Borowiak Teresa , Dutkiewicz Grzegorz , Wysocka Waleria , Kolanoś Renata
Published: February 2015

(+)-2-Thionosparteinium perchlorate has been obtained and characterized by IR and NMR spectroscopy. On the basis of the coupling constant J7 - J17β and chemical shifts for C(12) and C( 14) a boat conformation of ring C is proposed. The infrared spectrum in the solid state indicates an intermolecular hydrogen bond N+-H···S. This has been ascertained by X-ray crystal structure determination: H···S - 2.44(8)Å, N+···S - 3.279(6)Å, N+- H···S - 160(6)°. The solution NMR spectra clearly show that the solid state stucture is retained in solution.
Attempted Synthesis of Divalent Neodymium Derivatives. Crystal Structure of the Nd(III) Complex [{NdCl2 (2 ,4 ,6-t-Bu3C6H2O )(μ-Cl)(THF)}Li(THF)2]2
Authors: Kirillov E. N. , Trifonov A. A. , Nefedov S. E. , Eremenko I. L. , Edelmann F. T. , Bochkarev M. N.
Published: February 2015

The interaction of NdCl3 with lithium metal in THF in the presence of naphthalene produces a mixture of naphthalene complexes of di- and trivalent neodymium chloride of an aggregate composition [NdCl2(THF)2LiCl]nC10H8 (n = 4- 7). By the reaction of these compounds with 2,4,6-t-Bu3C6H2OH in THF the complex [{NdCl2(2,4,6-t-Bu3C6H2O)(μ-Cl)(THF)}Li(THF)2]2 has been obtained in 70% yield and its X-ray crystal structure determined.
Die Kristallstruktur von [YbCl2(THF)5]+[WOCl4(THF)]- / Crystal Structure of [YbCl2(THF)5]+[WOCl4(THF)]-
Authors: Karl M. , Seybert G. , Massa W. , Dehnicke K.
Published: February 2015

Blue moisture sensitive single crystals of [YbCl2(THF)5]+[WOCl4(THF)]- were obtained as a by-product from the reaction of the ytterbium trisamide Yb[N(SiMe3)2]3 with tungsten hexachloride in THF solution. The crystals were suitable for an X-ray crystal structure determination. Space group P2/c, Z = 2, lattice dimensions at -80 °C: a = 1192.5(1), b = 1117.1(1), c = 1349.9(1) pm, ß = 104.115(7)°, R = 0.0424. The structure consists of cations [YbCl2(THF)5]+ in which the ytterbium atom is coordinated in a pentagonalbipyramidal way by the chlorine atoms in the axial positions and by the oxygen atoms of the THF molecules in equatorial positions. Counterions are the well-known [WOCl4(THF)]- ions.
Reaction between Yttrium Nitrate and 2,2':6',2"-Terpyridine (terpy) in MeCN: Preparation, Crystal Structures and Spectroscopic Characterization of [Y (NO3)3(terpy)(H2O )] and [Y(NO3)3(terpy)(H2O )] · terpy · 3 MeCN
Authors: Boudalis Athanassios K. , Nastopoulos Vassilios , Terzis Aris , Raptopoulou Catherine P. , Perlepes Spyros P.
Published: February 2015

The reaction of Y(NO3)3 · 5H2O and 2,2':6',2"-terpyridine (terpy) in MeCN leads to [Y(N03 )3(terpy)(H2O )] (1) and [Y(N03 )3(terpy)(H2O )] terpy-3MeCN (2) in good yields depending on the isolation conditions. The structures of both complexes were determined by single-crystal X-ray crystallography. The YIII atom in 1 is 9-coordinate and ligation is provided by one terdentate terpy molecule, two chelating nitrates, one monodentate nitrate and one terminal H2O molecule; the coordination polyhedron about the metal may be viewed as a tricapped trigonal prism. The YIII atom in 2 is 10-coordinate and its coordination sphere consists of three nitrogen atoms from the terdentate terpy, six oxygen atoms from the three chelating nitrates (one of them being “anisobidentate”) and one oxygen atom from a terminal H2O molecule; the polyhedron about the metal may be viewed as a distorted sphenocorona. The interstitial terpy is strongly hydrogen-bonded to the O atom of the coordinated H2O molecule to form [Y(NO3 )3(terpy)(H20)] ··· terpy pairs. The new complexes were characterized by IR and 1H NMR spectroscopies. The YIII/NO3
-/terpy chemistry is compared to the already well-developed LnIII/NO3
-/terpy chemistry (Ln = lanthanide).
Darstellung und Charakterisierung von Bis(trichlorsilyl)phenylamin und 2,2,4,4-TetrachIor-1,3-diphenyl-[ 1,3,2,4]diazadisiletidin / Preparation and Characterization of Bis(trichlorosilyl)phenylamine and 2,2,4,4-Tetrachloro-1,3-diphenyl-[ 1,3,2,4]diazadisiletidine
Authors: Bzik S. , Jansen M.
Published: February 2015

Bis(trichlorsilyl)phenylamine (1) and 2,2,4,4-tetrachlor-l,3-diphenyl-[l,3,2,4]diazadisiletid-ine (2) have been synthesized as potential precursors for the preparation of porous oxygen-free solids by the reaction of tetrachlorosilane with dilithiated aniline. Both compounds were characterized by crystal structure analysis. 1 crystallizes monoclinically, P2/n, a = 10.124(2), b = 12.701(2), c = 11.425(3) Å, β = 109.34(2)° and Z = 4 (R1 = 4.6%, wR2 = 11.6%, 1297 independent reflections). 2 crystallizes orthorhombically, Pbca, a = 11.42(1), b = 8.17(1), c = 17.05(1)Å, and Z = 4 (R1 = 3.7%, wR2 = 8.2%, 1923 independent reflections). Ammonolyses and polycondensation of 1 and 2 yield amorphous solids with low porosities.
Fluoreliminierung aus Graphitfluorid mit Magnesium / Defluorination of Graphite Fluoride Applying Magnesium Emst-Christian Koch
Authors: Koch Emst-Christian
Published: February 2015

Consolidated stoichiometric mixtures of graphite fluoride (1) and magnesium (2) upon igni­ tion under argon atmosphere (0,1 MPa) yield very high flame temperature of ~ 5600 K as determined by infrared emission spectroscopy. The combustion product was analysed by X-ray powder diffraction and revealed the presence of magnesium fluoride and graphite as well as structurally low ordered carbon. A possible reaction mechanism is discussed.
Silyltrielane R' nHal3-n (E = Al, Ga, In; R' = SitBu2Ph): Synthesen, Charakterisierung, Strukturen [1] / Silyltrielanes R'nEHal3-n (E = Al, Ga, In; R' = SitBu2Ph): Syntheses, Characterization, Structures [1]
Authors: Wiberg Nils , Blank Thomas , Lemer Hans-Wolfram , Nöth Heinrich , Habereder Tassilo , Fenske Dieter
Published: February 2015

Water- and oxygen-sensitive compounds of the type R ’nEHal3-n (R' = SitBu2Ph; E = Triel) with or without donors, viz. RAlBr2, R'3Al, R'GaCl2'THF, R'GaCl2, R'3Ga, R'InCl2·THF and R'3In have been synthesized by reaction of EX3 with NaSitBu2Ph (prepared for this purpose) in the absence or presence of donors. The dihalides R'EHal2 have also been obtained by reaction of R'3E with EHal3, whereas monohalides R'2EHal are not accessible via these and other routes up to date. All trielanes have been characterized by NMR and the structures of the R'3E compounds have been determined by X-ray analyses.
2.3-Dihydro-2-Methoxyethylimino-L,3-Dimethylimidazol - Ein Neuer Hemilabil Koordinierender Chelatligand [1]
Authors: Kuhn Norbert , Grathwohl Martin , Nachtigal Christiane , Steimann Manfred
Published: February 2015

The bifunctional 2,3-dihydro-2-methoxyethylimino-l,3-dimethylimidazole (C8H 15N3O , 10) is obtained from the reaction of methoxyethyl tosylate (7) and 2,3-dihydro-2-imino-1,3- dimethylimidazole (8) followed by deprotonation in good yield. 10 reacts with {(COD)RhCl}2 (COD = 1,5-cyclooctadiene) to give the imine complex (C8H 15N3O)Rh(COD)Cl (11), which is converted into the chelate complex [(C8H15N3O)Rh(COD)]BF4 (12) on treatment with AgBF4. The imine complex (C8H15N3O) 2PdCl2 (13) is formed through the reaction of 10 with (PhCN)2PdCl2. The X-ray structures of 11, 13 and 2 C8H15N3O · H2PdCl4 (15) are reported
Antiferromagnetic Coupling In A (μ-Hydroxo)(μ-Pyrazolato)Dicopper(II) Complex. Synthesis, Crystal Structure, Magnetic Properties, And Theoretical Studies
Authors: Kara H. , Elerman Y. , Prout K.
Published: February 2015

Preparation, crystal structure and magnetic properties of a 3,5-dimethylpyrazolate bridged binuclear copper(II) complex [Cu2(L1)(3,5 prz)] (L1 = 1,3-Bis(2-hydroxy-1-napthylideneamino) propan-2-ol) (1) are reported. Variable-temperature magnetic susceptibility measurements for a powdered sample of the complex were carried out in the temperature range 5 - 350 K and analysed to obtain values of the parameter J in the exchange Hamiltonian H = -2JS1·S2 . In the dicopper(II) complex [Cu2(L2)(3,5 prz)], (L2 = l,3-Bis(2-hydroxy-5-chlorosalicylideneamino) propan-2-ol) (2) reported recently the antiferromagnetic interaction is much less than that of 1 (-27 = 440 cm-1 ), as result which is difficult to explain in terms of structural factors on the basis of widely accepted criteria. The differences in the magnetic behaviour now have been rationalized using the “ligand orbital complementary” concept
Preparation And Crystal Structures Of (Hg3 )(PO4 )Cl, (Hg3)(AsO4)Cl And (Hg3)(AsO4)Br - Mercury Compounds With The Triangular Hg3
4+ Cluster
Authors: Weil Matthias
Published: February 2015

The compounds (Hg3)(PO4)Cl, (Hg3)(AsO4)Cl and (Hg3)(AsO4 )Br have been prepared under hydrothermal conditions at 200 °C, starting from stoichiometric mixtures of the corresponding mercury halides and mercury phosphates or arsenates, respectively. The formula (Hg3)(AsO4)Cl is identical with that of the mineral kuznetsovite. All compounds are isotypic and crystallize with four formula units in the space group P21 3 [(Hg3)(PO4)Cl: a = 8.2912(5) Å; (Hg3)(AsO4)Cl: a = 8.3983(6) Å; (Hg3)(AsO4)Br: a = 8.4611(5) Å]. All crystal structures have been refined from single crystal diffractometer data sets under consideration of merohedral twinning according to a diagonal mirror plane as twin element. The structures comprise of equilateral mercury triangles with mean distances d̄(Hg-Hg) = 2.659 Å, which are bonded to halogen and oxygen atoms of nearly perfect PO4 or ASO4 tetrahedra, respectively
Synthesis and Coordination Chemistry of Novel Binucleating Macrocyclic Ligands with Amine-thioether and Amine-thiophenolate Donor Functions
Authors: Klingele Marco H. , Steinfeld Gunther , Kersting Berthold
Published: February 2015

The ability of the aromatic tetraaldehyde l,2-bis(4-tert-butyl-2,6-diformylphenylsulfanyl)-ethane (1) to function as a precursor in the preparation of binucleating hexaamine-dithiolate ligands has been investigated. Reductive amination of compound 1 with bis(aminoethyl)amine under medium-dilution conditions affords the macrobicyclic hexaamine-dithioether compound L1. Deprotection of the [1+2] condensation product gives the corresponding 24-membered hexa-amine-dithiophenol ligand H2L2. The formulation of L1 as a macrobicyclic amine-thioether was confirmed by an X-ray crystal structure determination of the tetranuclear nickel(II) complex of L1, [{(L1)Ni2Cl2}2(μ-Cl)3](BPh4) (2b). The formulation of the doubly deprotonated form (L2)2- of H2L2 as a 24-membered amine-thiophenolate ligand was confirmed by an X-ray crystal structure determination of the dinuclear cobalt(III) complex, [(L2)CoIII(μ-OH)](ClO4)2 · Cl (3). The preparation and the crystal structures of the new compounds are described.
Tetraberyllium-η4-oxo-hexa(arylcarboxylates)
Authors: Berger Raphael J. F. , Schmidt Michael A. , Jusélius Jonas , Sundholm Dage , Sirsch Peter , Schmidbaur Hubert
Published: February 2015

Tetraberyllium-oxo-hexabenzoate and -hexa(mesitylcarboxylate) were prepared from benzoic / mesitylcarboxylic acid and freshly precipitated beryllium hydroxide in a tetrahydrofuran / water two-phase system. The crystal structure of the benzoate was deter­ mined from Be4O(OCOPh)6(C6H6)3 , and that of the mesitylcarboxylate from the phase Be4O(OCOMes)6(CCl4). The two clusters have the μ4-oxo cage structure also detected for the acetate and nitrate complexes, and for the related hexacarbonato hexaanion. The high symmetry of the cluster allows the observation of 9Be and l7O signals in the solution NMR spectra.

The terminal atoms of the rigid carboxylate groups may be expected to lie at the vertices of large octahedra enclosing the cluster molecules. The axes of the six aryl groups would thus coincide with the axes of the cartesian coordinates with the μ4 oxygen atom at the origin. This disposition suggests a connectivity suitable for cubic lattices if p-difunctional arene-dicarb-oxylate anions are employed instead of aryl-monocarboxylate anions. However, the new results show that significant deviations of the OBe2O2C-Ar six-membered rings from planarity cause major deviations from octahedral symmetry and therefore no connectivity in cubic symmetry is to be expected.

Fragmentation of the Be4O(OCOR)6 clusters upon ionization in a mass spectrometer leads predominantly to cations [Be3O(OCOR)3]+ which can be assigned a planar, highly symmet­rical tricyclic core structure of D3h symmetry. Quantum chemical calculations confirm dis­ crete energy minima for these cations and show that their stability is largely due to the favourable arrangement of alternating charges of neighbouring core atoms. The high polar­ ity of Be-O bonds rules out any significant contributions from aromaticity. The reactions of Be(OH)2 with 4 -HS-C6H4 -COOH and HS(CH2)2COOH give the corresponding cluster com­ pounds Be4O(OCORSH)6, [R = C6H4 , (CH2)2] with six terminal mercapto functions.
N-Silylaminotin Trichlorides. Synthesis and Characterisation by Multinuclear Magnetic Resonance Spectroscopy
Authors: Wrackmeyer Bernd , Pedall Andreas , Weidinger Jürgen
Published: February 2015

N-Silyl-aminotin trichlorides, R1R2N-SnCl3[R1 = R2 = SiMe3 (1a), R1 = SiMe3, R2 = tBu (1b), R = SiMe3, R2 = 9-borabicyclo[3.3.1]nonyl (1c), R1R2 = Me2 SiCH2CH2SiMe2 (1d)] were prepared by the reaction of tin tetrachloride with the respective bis(amino)plumbylenes, (R1R2N)2Pb 4. The analogous reactions with bis(amino)stannylenes, (R1R2N)2Sn 3, afforded only mixtures of the aminotin trichlorides 1 and bis(amino)tin dichlorides, (R1R2N)2 SnCl2 2 . The products were characterised by 1H, 11B, 13C, 15N, 29Si and 119Sn NMR spectroscopy, and the NMR data of 1 were compared with those of the corresponding N-silylamino(trimethyl)tin compounds 8.
Importance of Orbital Complementarity in Spin Coupling through Two Different Bridging Groups. Synthesis, Crystal Structure, Magnetic Properties and Magneto-Structural Correlations in a Dicopper(II) Complex of Endogenous Alkoxo Bridging Ligand with Exogenous Pyrazolate
Authors: Elerman Y. , Karab H. , Elmali A.
Published: February 2015

[Cu2(L3)(3,5-prz)] (L3 = 1,3-bis(2-hydroxy-4-methoxybenzylideneamino)-propan-2-ol) (3) was synthesized and its crystal structure determined. The compound consists of discrete binuclear units, in which copper atoms are linked by the alkoxide oxygen atom of the ligand and the pyrazolate nitrogen atoms. Variable-temperature magnetic susceptibility measurements for a powdered sample of the complex were carried out in the temperature range 4.4 - 308 K and analysed to obtain values of the parameter J in the exchange Hamiltonian H = -2JS1-S2. Recently, the dicopper(II) complexes [Cu2(L1)(3,5-prz)] (L1 = 1,3-bis(2-hydroxy-1-napthylideneamino)- propan-2-ol) (1) and [Cu2(L2)(3,5-prz)], (L2 = 1,3-bis(2-hydroxy-5-chlorosalicylideneamino)- propan-2-ol) (2) were reported. These compounds show antiferromagnetic behaviour (-2J: 444 cm-1 for 1 164 cm-1 for 2, and 472 cm-1 for 3). The strength of the super-exchange interaction (-2J) of 2 is much less than that of 1 and 3, a result which is difficult to explain in terms of structural factors on the basis of widely accepted criteria. The differences in the magnetic behaviour have been rationalized in terms of the bridging ligand orbital complementary / countercomplementary concept.
Prmt5: a guardian of the germline protects future generations
Authors: Berrens Rebecca V , Reik Wolf
Published: February 2015

Primordial germ cells (PGCs) are the embryonic precursors of the germ cell lineage that form sperm and egg cells. It is of great importance to preserve the germline from DNA damage and potentially from epimutations in order to ensure the survival of future generations. Recent research highlights the role of the protein arginine methyltransferase 5 (PRMT5) as an important player in DNA protection during germline development in the mouse (Kim et al, & Li et al, ).
Excess perigestational folic acid exposure induces metabolic dysfunction in post-natal life
Authors: Keating Elisa , Correia-Branco Ana , Araújo João R , Meireles Manuela , Fernandes Rita , Guardão Luísa , Guimarães João T , Martel Fátima , Calhau Conceição
Published: February 2015

The aim of this study was to understand whether high folic acid (HFA) exposure during the perigestational period induces metabolic dysfunction in the offspring, later in life. To do this, female Sprague–Dawley rats (G0) were administered a dose of folic acid (FA) recommended for pregnancy (control, C, 2 mg FA/kg of diet,n=5) or a high dose of FA (HFA, 40 mg FA/kg of diet,n=5). Supplementation began at mating and lasted throughout pregnancy and lactation. Body weight and food and fluid intake were monitored in G0 and their offspring (G1) till G1 were 13 months of age. Metabolic blood profiles were assessed in G1 at 3 and 13 months of age (3M and 13M respectively). Both G0 and G1 HFA females had increased body weight gain when compared with controls, particularly 22 (G0) and 10 (G1) weeks after FA supplementation had been stopped. G1 female offspring of HFA mothers had increased glycemia at 3M, and both female and male G1 offspring of HFA mothers had decreased glucose tolerance at 13M, when compared with matched controls. At 13M, G1 female offspring of HFA mothers had increased insulin and decreased adiponectin levels, and G1 male offspring of HFA mothers had increased levels of leptin, when compared with matched controls. In addition, feeding of fructose to adult offspring revealed that perigestational exposure to HFA renders female progeny more susceptible to developing metabolic unbalance upon such a challenge. The results of this work indicate that perigestational HFA exposure the affects long-term metabolic phenotype of the offspring, predisposing them to an insulin-resistant state.
Conserved RNA-Binding Proteins Required for Dendrite Morphogenesis inCaenorhabditis elegansSensory Neurons
Authors: Antonacci Simona , Forand Daniel , Wolf Margaret , Tyus Courtney , Barney Julia , Kellogg Leah , Simon Margo A , Kerr Genevieve , Wells Kristen L , Younes Serena , Mortimer Nathan T , Olesnicky Eugenia C , Killian Darrell J
Published: February 2015

The regulation of dendritic branching is critical for sensory reception, cell−cell communication within the nervous system, learning, memory, and behavior. Defects in dendrite morphology are associated with several neurologic disorders; thus, an understanding of the molecular mechanisms that govern dendrite morphogenesis is important. Recent investigations of dendrite morphogenesis have highlighted the importance of gene regulation at the posttranscriptional level. Because RNA-binding proteins mediate many posttranscriptional mechanisms, we decided to investigate the extent to which conserved RNA-binding proteins contribute to dendrite morphogenesis across phyla. Here we identify a core set of RNA-binding proteins that are important for dendrite morphogenesis in the PVD multidendritic sensory neuron in Caenorhabditis elegans. Homologs of each of these genes were previously identified as important in the Drosophila melanogaster dendritic arborization sensory neurons. Our results suggest that RNA processing, mRNA localization, mRNA stability, and translational control are all important mechanisms that contribute to dendrite morphogenesis, and we present a conserved set of RNA-binding proteins that regulate these processes in diverse animal species. Furthermore, homologs of these genes are expressed in the human brain, suggesting that these RNA-binding proteins are candidate regulators of dendrite development in humans.
Sucrose and Warmth for Analgesia in Healthy Newborns: An RCT
Authors: Gray Larry , Garza Elizabeth , Zageris Danielle , Heilman Keri J. , Porges Stephen W.
Published: February 2015

BACKGROUND AND OBJECTIVE:

Increasing data suggest that neonatal pain has long-term consequences. Nonpharmacologic techniques (sucrose taste, pacifier suckling, breastfeeding) are effective and now widely used to combat minor neonatal pain. This study examined the analgesic effect of sucrose combined with radiant warmth compared with the taste of sucrose alone during a painful procedure in healthy full-term newborns.

METHODS:

A randomized, controlled trial included 29 healthy, full-term newborns born at the University of Chicago Hospital. Both groups of infants were given 1.0 mL of 25% sucrose solution 2 minutes before the vaccination, and 1 group additionally was given radiant warmth from an infant warmer before the vaccination. We assessed pain by comparing differences in cry, grimace, heart rate variability (ie, respiratory sinus arrhythmia), and heart rate between the groups.

RESULTS:

The sucrose plus warmer group cried and grimaced for 50% less time after the vaccination than the sucrose alone group (P < .05, respectively). The sucrose plus warmer group had lower heart rate and heart rate variability (ie, respiratory sinus arrhythmia) responses compared with the sucrose alone group (P < .01), reflecting a greater ability to physiologically regulate in response to the painful vaccination.

CONCLUSIONS:

The combination of sucrose and radiant warmth is an effective analgesic in newborns and reduces pain better than sucrose alone. The ready availability of this practical nonpharmacologic technique has the potential to reduce the burden of newborn pain.
Moisture Damage and Asthma: A Birth Cohort Study
Authors: Karvonen Anne M. , Hyvärinen Anne , Korppi Matti , Haverinen-Shaughnessy Ulla , Renz Harald , Pfefferle Petra I. , Remes Sami , Genuneit Jon , Pekkanen Juha
Published: February 2015

BACKGROUND:

Excess moisture and visible mold are associated with increased risk of asthma. Only a few studies have performed detailed home visits to characterize the extent and location of moisture damage and mold growth.

METHODS:

Structured home inspections were performed in a birth cohort study when the children were 5 months old (on average). Children (N = 398) were followed up to the age of 6 years. Specific immunoglobulin E concentrations were determined at 6 years.

RESULTS:

Moisture damage and mold at an early age in the child’s main living areas (but not in bathrooms or other interior spaces) were associated with the risk of developing physician-diagnosed asthma ever, persistent asthma, and respiratory symptoms during the first 6 years. Associations with asthma ever were strongest for moisture damage with visible mold in the child’s bedroom (adjusted odds ratio: 4.82 [95% confidence interval: 1.29–18.02]) and in the living room (adjusted odds ratio: 7.51 [95% confidence interval: 1.49–37.83]). Associations with asthma ever were stronger in the earlier part of the follow-up and among atopic children. No consistent associations were found between moisture damage with or without visible mold and atopic sensitization.

CONCLUSIONS:

Moisture damage and mold in early infancy in the child’s main living areas were associated with asthma development. Atopic children may be more susceptible to the effects of moisture damage and mold.