Regularized inversion of the Laplace transform for series of experiments

Not only in low-field nuclear magnetic resonance, Laplace inversion is a relevant and challenging topic. Considerable conceptual and technical progress has been made, especially for the inversion of data encoding two decay dimensions. Distortion of spectra by overfitting of even moderate noise is counteracted requiring a priori smooth spectra. In this contribution, we treat the case of simple and fast one-dimensional decay experiments that are repeated many times in a series in order to study the evolution of a sample or process. Incorporating the a priori knowledge that also in the series dimension evolution should be smooth, peak position can be stabilized and resolution improved in the decay dimension. It is explained how the standard one-dimensional regularized Laplace inversion can be extended quite simply in order to include regularization in the series dimension. Obvious improvements compared with series of one-dimensional inversions are presented for simulated as well as experimental data. For the latter, comparison with multiexponential fitting is performed.     

Green-Light Electroluminescence of Conjugated Copolymer Containing p-Phenylene-ethynylene and Oxadiazole

IntroductionSince the first report,in 1 990 ,of the electro-luminescence of the conjugated polymers in the filmof poly(p- phenylenevinylene) (PPV) sandwichedbetween an anode and a cathode of appropriatework functions[1] ,enormous efforts have been de-voted to the synthesis of light emitting poly-mers[2— 4 ] .Having been found potential applicationof conjugated polymers in photoluminescence(PL)and electro- luminescence (EL ) ,their importantproperties,polymer processability,band gap tun-abil…     

Die Kristallstruktur von wasserfreiem Melaminiumchlorid

Crystal Structure of non‐aqueous Melaminium Chloride Melaminium chloride was obtained as colorless, needle‐shaped, single crystalline material from solid state reactions between melamin and ammonium chloride. The structure of [C₃N₆H₇]Cl was refined by single crystal X‐ray diffraction: I2/m, Z = 8, a = 852.87(4), b = 1704.4(1) c = 918.44(4) pm and β = 92.165(6)°. The crystal structure contains melaminium ions stacked to columns along [100] and linked via N‐H···N bridges to form bands along [001]. Both of the two distinct chloride ions are stabilized by six hydrogen bonds through distorted trigonal prismatic arrangements of hydrogen atoms to yield a supramolecular structure.     

Energetic and stereochemical effects of the protein environment on substrate: a theoretical study of methylmalonyl-CoA mutase

QM/MM methods were used to study the isomerization step from (2R)-methylmalonyl-CoA to succinyl-CoA. A pathway via a "fragmentation-recombination" mechanism is ruled out on energetic grounds. For the other radicalic pathway, involving an addition recombination step, geometries and vibrational contributions have been determined, and a barrier height of 11.70 kcal/mol was found. The effect of adjacent hydrogen-donating groups was found to reduce the energy barrier by 1-2 kcal/mol each and thus to provide a significant catalytic effect for this reaction. By means of molecular dynamics studies, the stereochemistry of the methylmalonyl-CoA mutase catalyzed reaction was examined. It is shown that TYR89 is essential for maintaining stereoselectivity of the abstraction of a hydrogen in the backreaction. The subsequent selective formation of one isomer of methylmalonyl-CoA is probably due to the presence of a bulky side chain.     

Determination of carnitine and acylcarnitines in urine by high-performance liquid chromatography-electrospray ionization ion trap tandem mass spectrometry

A high-performance liquid chromatography-mass spectrometry method has been developed for the simultaneous determination of native carnitine and eight acylcarnitines in urine. The procedure uses a solid-phase extraction on a cation-exchange column and the separation is performed without derivatization within 17 min on a reversed-phase C8 column in the presence of a volatile ion-pairing reagent. The detector was an ion trap mass spectrometer and quantification was carried out in the MS-MS mode. Validation was done for aqueous standards at ranges between 0.75 and 200 micromol/l, depending on the compound. Carnitine was quantified in urine and comparison with a radioenzymatic assay gave a satisfactory correlation (R2 = 0.981). The assay could be successfully applied to the diagnostic of pathological acylcarnitines profile of metabolic disorders in urines of patients suffering from different organic acidurias.     

Regioselective coupling of pentafluorophenyl substituted alkynes: mechanistic insight into the zirconocene coupling of alkynes and a facile route to conjugated polymers bearing electron-withdrawing pentafluorophenyl substituents

The reaction of Cp(2)ZrCl(2) with 2 equiv of BuLi at -78 degrees C, followed by the addition of an unsymmetrical tetra- or pentafluorophenyl substituted alkyne R(1)C[triple bond]CAr(f) (R(1), Ar(f) = (CH(2))(4)Me, p-C(6)F(4)H; Me, p-C(6)F(4)H; Ph, C(6)F(5)), resulted in regioselective couplings of these alkynes to zirconacyclopentadienes in which the Ar(f) substituents preferentially adopt the 3,4-positions (beta beta) of the zirconacyclopentadiene ring. With Cp(2)Zr(py)(Me(3)SiC[triple bond]CSiMe(3)) as the zirconocene reagent, the couplings could be carried out at room temperature; however, at higher temperatures significant quantities of the 2,4-fluoroaryl substituted (alpha beta) isomers were also formed. None of the conditions employed produced the 2,5-fluoroaryl substituted (alpha alpha) isomers. These fluoroaryl-substituted zirconacyclopentadienes were readily converted to butadienes via reactions with acids. The zirconacyclopentadiene Cp(2)ZrC(4)-2,5-Ph(2)-3,4-(C(6)F(5))(2), which resulted from the coupling of PhC[triple bond]C(C(6)F(5)), was converted to the corresponding thiophene by reaction with S(2)Cl(2), and to an arene by reaction with MeO(2)CC[triple bond]CCO(2)Me/CuCl. Mechanistic studies on zirconocene couplings of (p-CF(3)C(6)H(4))C[triple bond]C(p-MeC(6)H(4)) indicate that the observed regioselectivities are determined by an electronic factor that controls the orientation of at least one of the two alkynes as they are coupled. Additionally, these studies suggest an unsymmetrical transition state for the zirconocene coupling of alkynes, and this is supported by DFT calculations. The reaction of [(C(6)F(5))C[triple bond]CCH(2)](2)CH(2) with Cp(2)Zr(py)(Me(3)SiC[triple bond]CSiMe(3)) resulted in a zirconacyclopentadiene in which the pentafluorophenyl substituents have been forced into the 2,5-positions (alpha alpha). Zirconocene coupling of the diyne (C(6)F(5))C[triple bond]C-1,4-C(6)H(4)-C[triple bond]C(C(6)F(5)) provided a route to conjugated polymers bearing electron-withdrawing pentafluorophenyl groups.     

15‐Hydroperoxy‐PGE2: Intermediate in Mammalian and Algal Prostaglandin Biosynthesis

Arachidonic‐acid‐derived prostaglandins (PGs), specifically PGE₂, play a central role in inflammation and numerous immunological reactions. The enzymes of PGE₂ biosynthesis are important pharmacological targets for anti‐inflammatory drugs. Besides mammals, certain edible marine algae possess a comprehensive repertoire of bioactive arachidonic‐acid‐derived oxylipins including PGs that may account for food poisoning. Described here is the analysis of PGE₂ biosynthesis in the red macroalga Gracilaria vermiculophylla that led to the identification of 15‐hydroperoxy‐PGE₂, a novel precursor of PGE₂ and 15‐keto‐PGE₂. Interestingly, this novel precursor is also produced in human macrophages where it represents a key metabolite in an alternative biosynthetic PGE₂ pathway in addition to the well‐established arachidonic acid‐PGG₂‐PGH₂‐PGE₂ route. This alternative pathway of mammalian PGE₂ biosynthesis may open novel opportunities to intervene with inflammation‐related diseases.     

Synthetic Humic Acids Solubilize Otherwise Insoluble Phosphates to Improve Soil Fertility

Artificial humic acids (A‐HA) made from biomass in a hydrothermal process turn otherwise highly insoluble phosphates (e.g. iron phosphate as a model) into highly available phosphorus, which contributes to the fertility of soils and the coupled plant growth. A detailed electron microscopy study revealed etching of the primary iron phosphate crystals by the ‐COOH and phenolic groups of humic acids, but also illustrated the importance of the redox properties of humic matter on the nanoscale. The combined effects result in the formation of then bioavailable phosphate nanoparticles stabilized by humic matter. Typical agricultural chemical tests indicate that the content of total P and directly plant‐available P improved largely. Comparative pot planting experiments before and after treatment of phosphates with A‐HA demonstrate significantly enhanced plant growth, as quantified in higher aboveground and belowground plant biomass.     

Low-Valent Group 14 NHC-Stabilized Phosphinidenide ate Complexes and NHC-Stabilized K/P-Clusters

The N-heterocyclic carbene (NHC)-stabilized phosphinidenide, SIMesPK [SIMes=1,3-bis(2,4,6-trimethylphenyl)imidazolidine-2-ylidene], was used as an (NHC)P-transfer reagent for the synthesis of the low-valent Group 14 ate complexes K[(SIMesP)₃E] (E=Ge: 2 , Sn: 3 , Pb: 4 ), which were characterized by ¹H NMR, ³¹P NMR, IR spectroscopy as well as elemental and X-ray analysis. Furthermore, SIMesPK was used in reactions with potassium amides and alkoxides to form the molecular phosphorus–potassium clusters [K₄(SIMesP)₂(hmds)₂] [ 5 , hmds=N(SiMe₃)₂] and [K₆(SIMesP)₂(OtBu)₄] ( 6 ). Finally, the reaction of SIMesPK with Li[Al(OC₄F₉)₄] led to the potassium-rich ionic compound [(SIMesP)₄K₅][Al(OC₄F₉)₄] ( 7 ).