选择离子流动管质谱对汽车尾气成分的分析

运用选择离子流动管质谱(SIFT／MS)装置,以H3O^ 、NO^ 、O2^ 为初始离子对安装有催化转换装置的汽油车引擎启动5min后的尾气进行了取样分析,结果表明,尾气中含有大量的C—H化合物(包括烷烃、烯烃、炔烃、二烯烃以及芳香烃),含氧有机物(包括醛、酮、醇)以及NH3和NOx等污染成分。其中,NO的含量最高,它的浓度比其它所有SIFT／MS装置所能测量到的各种物质的总和还多;在C—H化合物中以芳香烃的含量最高,约占整个C—H化合物含量的一半以上;在含氧有机物中以醛类物质的含量最高。初步讨论了这些成分的形成动力学过程,对引擎冷启动和热启动时的尾气成分进行了分析,结果表明：冷启动尾气中C—H化合物和NOx的含量是热启动的3—5倍,而含氧有机物的含量没有很大的变化,此结果也证明了尾气的催化转化装置是一种减少尾气中C—H化合物和NOx污染物的一种有效的控制方法。这也证明了SIFT／MS技术是一种有效的分析痕量有机污染物的方法。     

Polarized fluorescence and estimated lifetimes of the DNA bases at room temperature

Polarized fluorescence spectra are presented for thymine, cytosine, adenine and guanine in neutral aqueous solution and in rigid neutral ethylene glycol-water (6:4) at ca. ?125°C. For thymine and cytosine at 25°C the polarization is nearly as high as in rigid media. Analysis yields fluorescence lifetime (τf) estimates of ?2 ps. This limits the likelihood that emission is from a minor species or via a forbidden transition. The lower room temperature polarization for adenine and guanine indicates τf's of ≈ 10 ps which allows for emission from a fluorescent tautomer or via a slightly forbidden transition.     

Magnetic gap and magnetization curve for a mixed valent semiconductor: A variational approach

Zeitschrift für Physik B Condensed Matter - The ground state properties of the nondegenerate periodic Anderson model, which includes an external magnetic field, are studied variationally. We...     

Transfer of bisphenol A from thermal printer paper to the skin

Of 13 thermal printing papers analyzed, 11 contained 8–17 g/kg bisphenol A (BPA). When taking hold of a receipt consisting of thermal printing paper for 5 s, roughly 1 μg BPA (0.2–6 μg) was transferred to the forefinger and the middle finger if the skin was rather dry and about ten times more if these fingers were wet or very greasy. This amount transferred to dry skin was neither significantly increased when taking hold of the paper at up to 10 sites, nor reduced when BPA-free paper was contacted afterwards. After 60–90 min, BPA applied to the skin as a solution in ethanol was only partially or no longer at all extractable with ethanol, whereas BPA transferred to the skin by holding thermal printer paper remained largely extractable after 2 h. This suggests that penetration of the skin depends on the conditions. Extractability experiments did not enable us to conclude whether BPA passes through the skin, but indicated that it can enter the skin to such a depth that it can no longer be washed off. If this BPA ends up in the human metabolism, exposure of a person repeatedly touching thermal printer paper for 10 h/day, such as at a cash register, could reach 71 μg/day, which is 42 times less than the present tolerable daily intake (TDI). However, if more than just the finger pads contact the BPA-containing paper or a hand cream enhances permeability of the skin, this margin might be smaller.     

High sample throughput flow immunoassay utilising restricted access columns for the separation of bound and free label

A flow immunodetection system with high sample throughput capacity is described for the screening of various analytes. The immunochemical detection principle is based on the chromatographic separation of the formed immunocomplex (AbAg or AbAg*) and the free antigen (Ag) by a restricted access (RA) column, utilising size-exclusion and reversed-phase mechanism. A fluorescein labelled analyte (Ag*) was used in the competitive assay format with fluorescence detection. The speed and simplicity of the assay were the greatest advantages, allowing measurement of the analyte to be carried out in less than 1 min. The biocompatibility and capacity of the restricted access material allowed multiple injections of up to 5000, without any breakthrough of the fluorescent tracer molecule and thus need for regeneration. The flow immunoassay was developed using the well-known atrazine herbicide and some transformation products as model compounds, due to their human toxicity and widespread use. The sample throughput was 80 samples per hour and the detection limits were 1.4 nM (300 pg/ml) for atrazine (Ab I) and 2.3 nM (500 pg/ml) for the sum of triazines (Ab II–III). Different sample matrices, PBS buffer, creek water, and urine were successfully applied in the flow system without the need for any sample handling step. For plasma samples an additional clean-up step using solid-phase extraction had to be included. The resulting detection limits for atrazine in plasma and water samples using this clean-up and trace enrichment procedure were found to be 2 ng/ml and 20 pg/ml, respectively. The analysis could be performed at a sample throughput rate of 400 per 6-h working shift.     

Rapid internal conversion by nucleic acid components in solution

The fluorescence excitation spectra of 12 nucleic acid components in ethylene-glycol-H₂O solution at 160 K show quantum yields which are 2 to 10 times higher when excitation is near the 0-0 energy than at the first absorption maximum. Discussion leads to the conclusion that internal conversion which competes with vibrational relaxation is generally responsible.     

The polarization of excimer fluorescence from a dinucleotide

The polarization of the excimer fluorescence from the dinucleotide CpC has been observed to be strikingly different from that of the monomer. The mixed polarization in the absorption reflects significant ground state interaction. The mixed polarization in the fluorescence is most likely due to a component which is polarized between the chromophores, a manifestation of charge resonance character in the excimer state.     

A THEORETICAL STUDY OF THE CYTOSINE EXCIMER STATE: THE ROLE OF GEOMETRY OPTIMIZATION

Abstract A study of the lowest excited dimer (excimer) singlet state of the DNA base cytosine was performed with fully optimized geometry (near the cis-syn form) using a slightly modified version of MOPAC6 (AM1 hamiltonian) and 112 excited configurations involving an active space consisting of the four highest occupied and the two lowest empty MO of the dimer. A binding energy of 3 kcal/mol for the excimer state is demonstrated, and the excimer fluorescence is predicted to be shifted 150 nm to longer wavelengths relative to that of the monomer fluorescence. The excimer geometry has the planes nonparallel (40–45° interplanar angle) and distorted, with the C₅-C₆ bonds showing quite close contact (2.4 Å). Excitation is found to be more localized in the region of the C₅-C₆ bond than expected from the monomer wavefunction. No stable excimer was found if the planes were constrained to be planar, nor if the triplet state was selected. The results suggest that the excimer geometry found in this study may be a precursor to the cis-syn cyclobutane photodimer.     

Reactions of the natural lignan hydroxymatairesinol in basic and acidic nucleophilic media: formation and reactivity of a quinone methide intermediate

The chemical properties and synthetic modifications of the natural lignan hydroxymatairesinol in basic and acidic nucleophilic media were studied. Hydroxymatairesinol presumably reacts via a quinone methide and a carbonium ion mechanism under basic and acidic conditions, respectively. In these conditions the benzylic hydroxyl group was displaced by nucleophiles yielding new 7-substituted butyrolactone lignans. Reactions in alcoholic basic solutions yielded the 7-alkoxy ethers diastereoselectively. Several previously known lignans as well as new lignans and lignan derivatives were synthesised. The transformations were monitored and the products identified by HPLC-MS and NMR.