Synthesis and fluorescence properties of DMCX+—a stable oxygen-bridged [4]helicenium dye

A one-step synthesis of the stable [4]helicenium dye, 1,13-dimethoxy-chromeno[2,3,4-kl]xanthenium hexafluorophosphate (DMCX⁺) from the readily available tris(2,6-dimethoxyphenyl)carbenium ion is reported. The crystal structure, the chemical stability, and dye properties of the DMCX⁺ helicenium system are described.     

Simulation of Counter-Current Spontaneous Imbibition Based on Momentum Equations with Viscous Coupling,Brinkman Terms and Compressible Fluids

Transport in Porous Media - A numerical model is investigated representing counter-current spontaneous imbibition of water to displace oil or gas from a core plug. The model is based on mass and...     

Synthesis of C-8 Deuterated Glycosides of 3-Deoxy-D-manno-oct-2-ulosonic Acid (Kdo) Related to Chlamydial Lipopolysaccharides

Summary.  Methyl glycosides of Kdo and a (2→8)-linked Kdo disaccharide were prepared which contain a deuterium label at C-8 of the reducing unit. The label was introduced in fair diastereoselectivity upon reduction of an aldehyde group using a chiral borane complex derived from N-benzyloxycarbonyl-(S)-proline which produced the 8-(S)-deuterated derivative as the major isomer. Further coupling with a Kdo bromide gave the α-(2→8)-linked disaccharide in good yield. The deprotected disaccharide serves as a model for NMR spectroscopic studies on the side chain conformation of a carbohydrate epitope from the bacterial pathogen Chlamydia. Received September 17, 2001. Accepted October 17, 2001     

Determination of 19 drugs of abuse and metabolites in whole blood by high-performance liquid chromatography–tandem mass spectrometry

A high-performance liquid chromatography (LC)–tandem mass spectrometry (MS/MS) method has been developed and validated for the determination of 19 drugs of abuse and metabolites and used in whole blood. The following compounds were included: amphetamine, methylenedioxyamphetamine, methylenedioxyethylamphetamine, methylenedioxymethamphetamine, methamphetamine, cocaine, benzoylecgonine, morphine, 6-acetylmorphine, codeine, methadone, buprenorphine, norbuprenorphine, ketobemidone, tramadol, O-desmethyltramadol, zaleplone, zolpidem, and zopiclone. The sample pretreatment consisted of solid-phase extraction using mixed-mode columns (Isolute Confirm HCX). Deuterated analogues were used as internal standards for all analytes, except for ketobemidone and O-desmethyltramadol. The analytes were separated by a methanol/ammonium formate gradient using high-performance LC (Agilent HPLC 1100) with a 3 mm × 100 mm Varian Pursuit 3 C₁₈ column, 3-μm particle size, and were quantified by MS/MS (Waters Quattro micro tandem quadrupole mass spectrometer) using multiple reaction monitoring in positive mode. Two transitions were used for all analytes, except for tramadol and O-desmethyltramadol. The run time of the method was 35 min including the equilibration time. For all analytes, responses were linear over the range investigated, with R ² > 0.99. One-point calibration was found to be adequate by validation, thereby saving analysis of multiple calibrators. The limits of quantification (LOQs) for the analytes ranged from 0.0005 to 0.01 mg/kg. Absolute recoveries of the analytes were from 34 to 97%, except for zaleplone (6%). Both the interday precision and the intraday precision were less than 15% (20% at the LOQ) for all analytes, except buprenorphine, norburprenorphine, and zaleplone (less than 18%). Accuracy (bias) was within ±15% (±20% at the LOQ) for all analytes, except MDMA and O-desmethyltramadol (within ±19%). No ion suppression or enhancement was seen nor was suppression from coeluted analytes seen. Matrix effects were found to be less than 23% for all analytes, except zopiclone (64%). High-concentration and low-concentration quality control samples gave acceptable values, and the method has been tried in international proficiency test schemes with good results. The present LC-MS/MS method provides a simple, specific, and sensitive solution for the quantification of some of the most frequent drugs of abuse and their metabolites in whole blood. The quantification by LC-MS/MS was successfully applied to 412 forensic cases from October 2008 to mid February 2009, where 267 cases were related to zero-tolerance traffic legislation.     

Der Einfluß von Carbonylgruppen auf die viskosimetrische Bestimmung des Molekulargewichtes von Zellstoffen in Lösungen

Zusammenfassung Durch Anwendung von Natriumborhydridreduktion wird gezeigt, daß Carbonylgruppen, die durch Oxydation in der Bleiche oder beim längeren Lagern von Zellstoff an der Luft eingeführt werden, eine wesentliche Rolle für die Nichtübereinstimmung der DP_Nitrat- und DP_{Cuoxam, Cuoxan}-Werte spielen.Die anomalen Gruppen verursachen einerseits einen Abbau der Zellstoffe in alkalischen Lösungsmitteln und andererseits Querbindungen zwischen den Ketten in der Nitrat-Aceton-Lösung.Die Gruppen können sowohl an den niedermolekularen Hemicellulosen wie auch an der höhermolekularen reinen Cellulose nachgewiesen werden.Durch einen Vergleich zwischen der Zahl der alkalilabilen Gruppen und dem gemessenen DP_Cuoxen-Wert, wird weiter gezeigt, daß die Verteilung der Gruppen an den Ketten nicht regelmäßig ist. Wahrscheinlich liegen sie an den Hemicellulosen und an den zugänglichen Bereichen des reinen Cellulosematerials angereichert vor.Vorgetragen auf der Jahrestagung der Deutschen Rheologen vom 11.–13. Mai 1964 in Berlin-Dahlem.     

Light charged particle emission and fission in238U+238U collisions at 1,740 MeV

Inclusive⁴He and⁴H energy spectra and heavy fragment coincidence correlations have been measured for reactions of 7.31 MeV/u²³⁸U with²³⁸U and^?197Au targets. The H/He production cross sections are in the range 15–26 mb, and their emission spectra are very similar for the two systems. The observed strong kinematic shifts with angle are reproduced in shape and magnitude by Monte Carlo simulations of particle evaporation from projectile-like and target-like fragments, indicating competition between charged particle emission and sequential fission. No evidence is found for high energy charged particle emission associated with ultra-highZ composite systems. Heavy fragment measurements indicate an abundance of quasielastic and deeply inelastic reaction fragments, as well as sequential fission of target and projectile nuclei. For²³⁸U nuclei, the fission occurs predominantly in an asymmetric mode, reminiscent of fission at low excitation energy. For²³⁸+²³⁸U reactions in the vicinity of the grazing angle, the frequency of single sequential fission (with survival of the partner fragment) is twice as large as double sequential fission in which both the target and projectile undergo fission. In²³⁸U+¹⁹⁷Au reactions, the survival probability of the heavy fragments is even greater. The surprisingly high survival probabilities of high-Z fragments imply a preponderance of very soft collisions in these very-heavy-ion reactions, at least at energies not very far over the Coulomb barrier.     

The consistency of the postulates of special relativity

In a recent article in this journal, Kingsley has tried to show that the postulates of special relativity contradict each other. Here we show that the arguments of Kingsley are invalid because of an erroneous appeal to symmetry in a non-symmetric situation. The consistency of the postulates of special relativity and the relativistic kinematics deduced from them is restated.     

A Model for Spontaneous Imbibition as a Mechanism for Oil Recovery in Fractured Reservoirs

The flow of oil and water in naturally fractured reservoirs (NFR) can be highly complex and a simplified model is presented to illustrate some main features of this flow system. NFRs typically consist of low-permeable matrix rock containing a high-permeable fracture network. The effect of this network is that the advective flow bypasses the main portions of the reservoir where the oil is contained. Instead capillary forces and gravity forces are important for recovering the oil from these sections. We consider a linear fracture which is symmetrically surrounded by porous matrix. Advective flow occurs only along the fracture, while capillary driven flow occurs only along the axis of the matrix normal to the fracture. For a given set of relative permeability and capillary pressure curves, the behavior of the system is completely determined by the choice of two dimensionless parameters: (i) the ratio of time scales for advective flow in fracture to capillary flow in matrix $\alpha =\tau ^f/\tau ^m$ ; (ii) the ratio of pore volumes in matrix and fracture $\beta =V^m/V^f$ . A characteristic property of the flow in the coupled fracture–matrix medium is the linear recovery curve (before water breakthrough) which has been referred to as the “filling fracture” regime Rangel-German and Kovscek (J Pet Sci Eng 36:45–60, 2002), followed by a nonlinear period, referred to as the “instantly filled” regime, where the rate is approximately linear with the square root of time. We derive an analytical solution for the limiting case where the time scale $\tau ^{m}$ of the matrix imbibition becomes small relative to the time scale $\tau ^{f}$ of the fracture flow (i.e., $\alpha \rightarrow \infty $ ), and verify by numerical experiments that the model will converge to this limit as $\alpha $ becomes large. The model provides insight into the role played by parameters like saturation functions, injection rate, volume of fractures versus volume of matrix, different viscosity relations, and strength of capillary forces versus injection rate. Especially, a scaling number $\omega $ is suggested that seems to incorporate variations in these parameters. An interesting observation is that at $\omega =1$ there is little to gain in efficiency by reducing the injection rate. The model can be used as a tool for interpretation of laboratory experiments involving fracture–matrix flow as well as a tool for testing different transfer functions that have been suggested to use in reservoir simulators.     

Poincaré stress and the Reissner-Nordström repulsion

The Reissner-Nordström repulsion is shown to be a consequence of Poincaré stresses in a static, charged object. The strong energy condition implies that the Reissner-Nordström repulsions do not stop a neutral test particle, falling freely from rest at infinity in the fields of a charged body, before it hits the surface of the body. However, if the particle falls from rest at a sufficiently small height above the surface of the body, it will not reach the surface due to the Reissner-Nordström repulsion.     

Fission reactions of 469-MeV56Fe+238U: Detection of4He/1H emission from pre- and post-fission sources

The emission of⁴He and¹H has been measured in coincidence with fission for reactions of 469-MeV⁵⁶Fe+²³⁸U. By using a gas-ionization telescope in kinematic coincidence with a position-sensitive avalanche detector, the folding angle between two fission fragments was determined in order to distinguish fusion reactions from fission following smaller-momentum-transfer collisions. In both fusion fission and sequential fission reactions, the⁴He/¹H energy spectra are relatively narrow with relatively flat angular distributions at backward angles and become broader in energy with enhanced cross-sections at forward angles. The extent of forward peaking is significantly greater for peripheral collisions than for central collisions. The light-charged-particle multiplicities are quite similar for⁴He and¹H, being much larger for fusion fission than for sequential fission. Detailed comparisons of the spectral shapes with Monte Carlo simulations of reaction kinematics impose strong constraints on the participation of different emission sources. We find important contributions to the observed⁴He/¹H emission both from accelerated fragments (FE) and from the composite system prior to fission (CE). For⁴He emission, the multiplicity of CE is much larger for fusion fission than for sequential fission, possibly as a consequence of the higher spins and shorter reaction times associated with deeply inelastic and quasi-elastic processes. For¹H emission, a corresponding but somewhat smaller difference is observed for the CE multiplicities. An excess of⁴He/¹H particles, found at forward angles in both fusion and sequential fission processes, cannot be attributed to evaporative emission from any fragments and therefore must originate in pre-thermalization emission.