Floquet spin states in OLEDs.

Electron and hole spins in organic light-emitting diodes constitute prototypical two-level systems for the exploration of the ultrastrong-drive regime of light-matter interactions. Floquet solutions to the time-dependent Hamiltonian of pairs of electron and hole spins reveal that, under non-perturbative resonant drive, when spin-Rabi frequencies become comparable to the Larmor frequencies, hybrid light-matter states emerge that enable dipole-forbidden multi-quantum transitions at integer and fractional g-factors. To probe these phenomena experimentally, we develop an electrically detected magnetic-resonance experiment supporting oscillating driving fields comparable in amplitude to the static field defining the Zeeman splitting; and an organic semiconductor characterized by minimal local hyperfine fields allowing the non-perturbative light-matter interactions to be resolved. The experimental confirmation of the predicted Floquet states under strong-drive conditions demonstrates the presence of hybrid light-matter spin excitations at room temperature. These dressed states are insensitive to power broadening, display Bloch-Siegert-like shifts, and are suggestive of long spin coherence times, implying potential applicability for quantum sensing.

Organic electronics. Room-temperature coupling between electrical current and nuclear spins in OLEDs.

The effects of external magnetic fields on the electrical conductivity of organic semiconductors have been attributed to hyperfine coupling of the spins of the charge carriers and hydrogen nuclei. We studied this coupling directly by implementation of pulsed electrically detected nuclear magnetic resonance spectroscopy in organic light-emitting diodes (OLEDs). The data revealed a fingerprint of the isotope (protium or deuterium) involved in the coherent spin precession observed in spin-echo envelope modulation. Furthermore, resonant control of the electric current by nuclear spin orientation was achieved with radiofrequency pulses in a double-resonance scheme, implying current control on energy scales one-millionth the magnitude of the thermal energy.

Superconducting coplanar waveguide resonators for low temperature pulsed electron spin resonance spectroscopy.

We discuss the design and implementation of thin film superconducting coplanar waveguide micro-resonators for pulsed electron spin resonance experiments. The performance of the resonators with P doped Si epilayer samples is compared to waveguide resonators under equivalent conditions. The high achievable filling factor even for small sized samples and the relatively high Q-factor result in a sensitivity of 4.5 × 10(8) spins per shot, which is superior to that of conventional waveguide resonators, in particular to spins close to the sample surface. The peak microwave power is on the order of a few milliwatts, which is compatible with measurements at ultra-low temperatures. We also discuss the effect of the nonuniform microwave magnetic field on the Hahn echo power dependence.

Profiling preparations of recombinant birch pollen allergen Bet v 1a with capillary zone electrophoresis in pentamine modified fused-silica capillaries.

Three preparation batches of the recombinant birch pollen allergen Bet v 1a have been analyzed by capillary zone electrophoresis (CZE) using a separation electrolyte consisting of 100 mmol L(-1) phosphate at pH 6.50 with 2.0 mmol L(-1) tetraethylenepentamine (TEPA) added. TEPA improved the resolution by wall shielding and selective attachment to allergens, but reduced migration repeatability at concentrations >2.0 mmol L(-1). Heterogeneity of preparations determined by CZE and electrospray ionization-quadrupole-time-of flight-MS were in accordance and revealed chemically modified (carbamylated) allergens in one of the preparations. The method was validated according to the ICH-guidelines. Repeatability of effective electrophoretic mobility (mu(eff)) was <0.55% R.S.D. (n = 5). Migration time corrected peak areas were used for quantification. Limit of quantification (LOQ) was 25 microg mL(-1) for the major isoform Bet v 1a, based on a signal-to-noise ratio of 10, and detector response was linear between LOQ and 0.90 mg mL(-1). Purity of the different rBet v 1a preparations was determined to be between 40 and 92% depending on the manufacturing protocol.

Malignant autosomal recessive osteopetrosis caused by spontaneous mutation of murine Rank.

UNLABELLED: We report the first case of lethal autosomal recessive osteopetrosis in mice caused by a spontaneous 8-bp deletion in exon 2 of the Rank gene. The phenotype, including a block in RANKL-dependent osteoclast differentiation and lymph node agenesis, copies that of Rank(-/-) mice, which have been produced by targeted recombination. INTRODUCTION: Commitment of osteoclast progenitors to the osteoclast lineage requires RANKL/RANK-mediated intercellular signals. Gene-targeted defects in this signaling pathway resulted in osteoclast deficiency and severe osteopetrosis in mice, but to date, there have been no reports of spontaneous mutations in Rankl or Rank resulting in osteopetrosis. MATERIALS AND METHODS: Mice with malignant osteopetrosis and absent lymph nodes appeared spontaneously in a highly inbred colony. Appropriate crosses were analyzed to establish the pattern of inheritance. Tissues from affected pups and littermates were evaluated grossly, histopathologically, and radiographically. Osteoclast development from splenocytes was tested in vitro under a variety of conditions, including after infection with RANK-encoding retrovirus. Rank mutational analysis was performed by direct sequencing of RT-PCR products and genomic DNA. RESULTS: The inheritance pattern was consistent with autosomal recessive inheritance, and the phenotype resembled that of either Rankl or Rank knockout mice with the exception of as yet unexplained death of most mice 2-3 weeks after weaning. Osteoclast precursors from the spleens of affected pups failed to form osteoclasts in vitro when stimulated with macrophage-colony stimulating factor (M-CSF) and RANKL, unless they were forced to express wildtype Rank cDNA. Molecular genetic studies identified an 8-bp deletion in exon 2 of the Rank gene. The resulting allele, termed Rank(del8), encodes only a small portion of the RANK extracellular domain, which is probably nonfunctional. CONCLUSIONS: The phenotypic similarities between Rank(del8) and mice previously described with a combined insertion and deletion in Rank confirm the role of this receptor in osteoclastogenesis and lymph node development and suggest that some forms of malignant osteopetrosis in humans could result from a similar defect.

Genetic background modifies intestinal pseudo-obstruction and the expression of a reporter gene in Hox11L1-/- mice.

BACKGROUND & AIMS: The transcription factor Hox11L1 is expressed by enteric neurons. Two groups mutated murine Hox11L1, and reported lethal intestinal pseudo-obstruction and colonic hyperganglionosis in many, but not all, homozygous null mutants. We investigated the regulation of Hox11L1 and factors that influence the penetrance of pseudo-obstruction in Hox11L1-null mice. METHODS: Expression of beta-galactosidase (lacZ), under control of putative Hox11L1 regulatory sequences, was assessed in transgenic mice wild-type, heterozygous, and null for native Hox11L1. Transgene expression and signs of pseudo-obstruction were compared in null mice with different genetic backgrounds. RESULTS: In enteric neurons and other parts of the nervous system, the transgene was expressed in a pattern consistent with native Hox11L1. Enteric beta-galactosidase activity initiated in the proximal small intestine and spread cranially and caudally in a subset of postmitotic enteric neurons. Hox11L1-lacZ transgene expression persisted in Hox11L1-null animals, suggesting that Hox11L1 is not required cell autonomously for neuronal survival. Genetic background dramatically affected the phenotypes of Hox11L1-null animals, with complete penetrance of severe proximal colonic distention on a predominantly C57BL/6J (B6) background and very low penetrance of dysmotility on a 129SvJ (129) background. Coincidently, Hox11L1-lacZ expression by most enteric neurons, but not CNS neurons, was lost on a 129 background. CONCLUSIONS: Cis-acting, 5' regulatory elements are sufficient to regulate site-specific expression of Hox11L1 in vivo. Expression of the transgene by enteric neurons and penetrance of pseudo-obstruction in Hox11L1-null animals are influenced by one or more modifier genes, counterparts of which may play a similar role in human disease.

Multiclass/multiresidue method for monitoring widely applied plant protecting agents in air during field dispersion work.

A multiclass/multiresidue method for surveying the uptake of plant protecting chemicals by inhalation during field spraying work is described. Eleven nowadays mainly dispersed compounds, which cover a wide range of chemical properties, are analysed in air with personal active sampling and in one single analytical run. This has the advantage, that one basic method only needs to be implemented, calibrated and validated in a laboratory to perform varying monitoring tasks without changing the method itself. Samples were taken with Tenax sorbent tubes operated to collect the active compounds simultaneously in the vapour state, in aerosol state or bound to particles. The procedure consists of four unit operations only: sampling, elution, dilution and HPLC measurement, and is described in SOP-format. The limits of quantification, calculated as method detection limits, were between 1 and 9 microg m(-3) based on 1 m3 air volume sampled (8 h). Method performance was characterised by way of generated test atmospheres and field spraying trials.

Determination of quaternary alkylammonium compounds by capillary zone electrophoresis and indirect UV detection as a real alternative to ion chromatography with suppressed conductivity detection.

A capillary electrophoretic (CE) method for the determination of residual mid-chain alkyltrimethylammonium compounds in the pharmaceutical product Welchol (an alkylated, crosslinked polyallylamine) was developed, validated and compared with the existing ion chromatographic (IC) method with suppressed conductivity detection. Excellent reproducibilities of migration times (RSD<0.5% within a series of 55 sample injections) and relative peak areas (RSD<2%) make the method suitable for quality control as a real alternative to IC. Limits of quantification of 0.01% w/w of each impurity in the active substance were achieved. Buffer systems for indirect UV detection based on creatinine as visualization reagent with different inorganic and organic acids (phosphoric, sulfuric, formic, acetic, oxalic and citric acid) and their effect on selectivity to ten quaternary ammonium compounds were studied. Selectivity changes were observed for the di- and trivalent analytes depending on the buffer applied. Also, the influence of acetonitrile, methanol, 1,4-dioxane and tetrahydrofuran on selectivity was investigated. In addition, CE-MS experiments were carried out in order to identify several impurities in the product.

Potential of microbore HPLC within a multiresidue method for the trace analysis of plant-protective substances in water.

The performance of microbore HPLC as a "measurement channel" within a true multiclass/multiresidue method for monitoring plant protectants in raw and potable water is demonstrated. The method has a modular design and consists of a non-selective sampling and preparation line generating 250 microL of an "extract" from a 100-mL water sample; this extract can be introduced to up to four measurement channels, as required by the analytical task. The microbore HPLC channel can be used to quantify 34 plant protectants in the 0.1 microg L(-1) concentration range by use of diode-array detection at seven different wavelengths. A solvent change is necessary to link sample preparation to microbore HPLC; this uses 50 microL of the "extract" and is accomplished directly in an autosampler vial. Performance characteristics were evaluated for tap water spiked at 0.2 microg L(-1). Average recoveries were between 65 and 100% and method detection limits were 0.07 microg L(-1) or better. The ability to provide comparable and accurate results was proven by participation in an interlaboratory comparison trial. The procedure for preparing microbore columns from 750 microm i.d. PEEK tubing is described in detail to enable the reader to prepare his own columns. The reproducibility of this preparation procedure was proven by an analysis-of-variance test.

Determination of regularly distributed plant protectants in raw and drinking waters, using a multiresidue method with cyclodextrin-modified micellar electrokinetic chromatography.

Eighteen plant protectant compounds were separated and determined by cyclodextrin-modified micellar electrokinetic chromatography (MEKC) in a multiclass/multiresidue method. The pesticides included are those dispersed in the greatest amounts today over agricultural acreage, and they represent 8 different classes of compounds (azoles, benzoic acids, chloroacetanilides, phenoxy acids, phenylureas, sulfonylureas, thiocarbamates, and triazines) covering a wide range of chemical reactivities and physicochemical properties. A 500 mL sample of tap water is preconcentrated by solid-phase extraction (SPE) with 300 mg combined polystyrene-divinylbenzene and methacrylate macroporous resins. Trapped analytes are eluted collectively with diethyl ether. Concentration and solvent change yield 250 microL of an acetone "concentrate," which is further worked up and concentrated 1:10 to produce the MEKC injection solution containing 10 mmol/L sodium dodecyl sulfate (SDS) surfactant. For MEKC, 2 phosphate/SDS buffer systems were designed, each allowing complete separation of all pesticides in a single run. Sensitivity was enhanced by a self-etched bubble cell and an injection procedure which employs stacking at reversed polarity. The ability of MEKC to determine plant protectants in raw and drinking waters at the 0.1 microgram/L level, as demanded by the guidelines of the European Union, was demonstrated with spiked tap waters. Recoveries were between 75 and 110%, and limits of quantification, evaluated as method detection limits according to guidelines of the U.S. Environmental Protection Agency, ranged between 0.03 and 0.10 microgram/L. The precisions of the relative migration times were all below 0.5%.

Direct serum injection in ion chromatography on packing materials with a semi-permeable surface.

Reversed-phase packing materials with restricted access of proteins to the hydrophobic sites were tested for their applicability in the ion-interaction chromatography of anions. Especially C8-modified silica, which had been coated with a hydrophilic polymer acting as a semi-permeable barrier, could be used successfully for the separation of several anions in a proteinaceous matrix without removing the proteins prior to injection. In combination with UV or conductivity detection, this technique allows the determination of some physiologically important anions in serum samples.

Information theory in analytical chemistry: basic terms, definitions and interpretations. Arbeitskreis "Automation in der Analyse".

The most important terms in information theory (information, character, code, message and signal) are defined and interpreted with reference to automation in analytical chemistry. The aim of this communication and the earlier one dealing with systems theory, is to facilitate communication and understanding between all specialists working on or with automated systems for analysis.