Formation and dissociation of the chloroethylene anions

Electron attachment spectroscopy is employed to study the formation of negative ions from the chloroethylenes. It is found that the resonances recently observed in the total electron scattering cross section are predominantly associated with the formation of Cl^?. Only in tetrachloroethylene is a long-lived parent negative ion observed.     

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.     

Possible acceleration of cosmic rays in a rotating system: Uehling-Uhlenbeck model

We illustrate the possible acceleration of cosmic rays passing through a kind of amplification channel (via diffusion modes of propagating plane-wave fronts) induced by a rotating system. Our analysis is mainly based on the quantum discrete kinetic model (considering a discrete Uehling-Uhlenbeck collision term), which has been used to study the propagation of plane (e.g., acoustic) waves in a system of rotating gases.     

Synthesis and Biological Activity of Oxidation Products of the Antiprogestine Mifepristone

Summary.  Selenium dioxide oxidation allows the selective introduction of a hydroxyl group at position 6 of the steroid skeleton of the antihormone (11β, 17β)-11-(4-dimethylamino-phenyl)-17-hydroxyl-17-(1-propynyl)-estra-4,9-dien-3-one (mifepristone, RU 486) and leads in a one-step procedure to two diastereomeric oxidation products. Their structure (6α- and 6β-hydroxy-mifepristone) was determined by NMR spectroscopy. The antiprogestinic activity of the oxidation products is comparable to that of mifepristone. Received August 25, 2000. Accepted (revised) October 24, 2000     

Species-specific isotope-ratio measurements of volatile tin and antimony compounds using capillary GC–ICP–time-of-flight MS

The analytical performance of an axial inductively-coupled-plasma time-of-flight mass spectrometer (ICP–TOFMS) as a detector for fast transient chromatographic signals resulting from the coupling to capillary gas chromatography (CGC) was investigated. A cryotrapping GC–ICP–TOFMS method for the determination of volatile metal(loid) compounds (VOMs) in gases was used and the suitability of the TOF mass analyzer for multi-elemental speciation analysis and multi-isotope ratio determinations was studied in terms of accuracy and precision. Isotope ratios ¹¹⁸Sn/¹²⁰Sn and ¹²¹Sb/¹²³Sb have been determined in in-house gas standard atmospheres in Tedlar bags at two different levels (100 pg and 1 ng) for different elemental species (SnH₄, MeSnH₃, Me₂SnH₂, Me₃SnH, BuSnH₃, SbH₃, and MeSbH₂). A limitation arising from counting statistics in both detection modes could be shown. A solution containing rhodium (10 ng mL^–1) and cadmium (40 ng mL^–1) was introduced simultaneously to the GC outlet. Rhodium acts as a continuous internal standard and Cd is used for mass-bias correction (by measuring the ¹¹¹Cd/¹¹³Cd ratio). The detection system in both pulse counting and analog mode was examined. The best attainable precision was established for Me₂SnH₂ (analog mode, 12 replicates, 1 ng, RSD 0.34%, accuracy 0.31%) whereas most other species ranged between 0.4 and 0.5% RSD if higher concentrations were used. The limitations of the pulse counting system are clearly seen, with peak heights of more than 2000 counts reaching saturation (for an integration time of 100 ms), which reduces the accuracy of isotope ratio determinations. A dozen VOM could be detected in an aged landfill gas sample; several unidentified Sn compounds were present. Although their isotope ratios are within the confidence value of the standards, it is not yet clear if the acquired precision is good enough to identify isotopic fractionation of metal(loid)s through biovolatilization processes. With the precision achieved, the combination of cryotrapping GC and ICP–TOFMS is a powerful tool for monitoring volatile multi-element species in multi-tracer experiments and isotope dilution methodology. Received: 23 November 2000 / Revised: 19 February 2001 / Accepted: 24 February 2001     

ROS‐Responsive N‐Alkylaminoferrocenes for Cancer‐Cell‐Specific Targeting of Mitochondria

Mitochondrial membrane potential is more negative in cancer cells than in normal cells, allowing cancer targeting by delocalized lipophilic cations (DLCs). However, as the difference is rather small, these drugs affect also normal cells. Now a concept of pro‐DLCs is proposed based on an N‐alkylaminoferrocene structure. These prodrugs are activated by the reaction with reactive oxygen species (ROS) forming ferrocenium‐based DLCs. Since ROS are overproduced in cancer, the high‐efficiency cancer‐cell‐specific targeting of mitochondria could be achieved as demonstrated by fluorescence microscopy in combination with two fluorogenic pro‐DLCs in vitro and in vivo. We prepared a conjugate of another pro‐DLC with a clinically approved drug carboplatin and confirmed that its accumulation in mitochondria was higher than that of the free drug. This was reflected in the substantially higher anticancer effect of the conjugate.     

Ca3Ni8In4—An Ordered Noncentrosymmetric Variant of the BaLi4 Type

The title compound was synthesized by reacting the elements in an arc-melting apparatus under purified argon and subsequent annealing at 870 K. Ca₃Ni₈In₄ was investigated using X-ray diffraction on both powders and single crystals: P6₃mc, a=898.9(1) pm, c=752.2(2) pm, wR2=0.0591, 327 F² values, and 35 parameters. This structure is an ordered, noncentrosymmetric variant of the BaLi₄ type. The nickel and indium atoms build a complex three-dimensional [Ni₈In₄] polyanion in which the calcium atoms fill distorted hexagonal channels. To a first approximation the formula may be written as (3 Ca²⁺)⁶⁺ [Ni₈In₄]⁶⁻. Within the polyanion the Ni1, Ni3, and Ni4 atoms form one-dimensional cluster units which extend in the c direction while the Ni2 atoms have only indium neighbors in a distorted tetrahedral coordination. The Ni–Ni distances in the cluster range from 241 to 266 pm. The cluster units are surrounded and interconnected by indium atoms. The group– subgroup relation from centrosymmetric BaLi₄ to noncentrosymmetric Ca₃Ni₈In₄ is presented. Chemical bonding in Ca₃Ni₈In₄ and the structural relation with Lu₃Co_7.77Sn₄, Ca₃Au_6.61Ga_4.39, and Co₂Al₅ is briefly discussed.     

Tying up loose ends: some mechanistic aspects of catalytic chain transfer

Polymerisation of methyl methacrylate in the presence of two catalytic chain transfer agents has been investigated. Several factors were examined to see how they would affect the chain transfer process. Oxygen and initiator impurities added to the system were found to be detrimental. The transfer process was highly intolerant of initiator impurities, but was able to endure a large excess of oxygen. The temperature dependencies of the chain transfer process were determined for cobaloxime boron fluoride (COBF) and cobalt(meso‐Ph₄‐porphyrin) (CoP). The results showed that a study of MW, or k_tr would be a better gauge of the catalyst activity. Activation energies were determined at two concentrations of initiator and it was discovered that the transfer process has a dependence on the initiator concentration. A mechanism for this dependency is proposed that involves a reduction in the active catalyst concentration. As a result, the measured values for C_tr, and k_tr, must be apparent values. An additional consequence of the initiator dependence is that the MW of the polymer products will be directly dependent on the concentration of the initiator.