Towards molecular-scale electronics and biomolecular self-assembly

This paper provides an overview of recent research developments in the field of nanoelectronics with organic materials such as carbon nanotubes and DNA-templated nanowires. Carbon nanotubes and gold electrodes are chemically functionalized in order to contact carbon nanotubes by self-assembly. The transport properties of these nanotubes are dominated by charging effects and display clear Coulomb blockade behaviour. A different approach towards nanoscale electronics is based on the molecular recognition properties of biomolecules such as DNA. As an example, DNA is stretched between electrodes using a molecular combing technique. A two-step metallization procedure leads to the formation of highly conductive gold nanowires.     

Unified nomenclature for chromatography

The background of the new Unified Nomenclature for Chromatography just accepted by the International Union of Pure and Applied Chemistry (IUPAC) is explained and selected highlights of the new rules are elaborated.     

Investigation of the reaction order for nucleophilic substitution of dialkyl methylphosphonates by alkoxides

The rate of nucleophilic substitution at the phosphorus centre of dialkyl methylphosphonates by methoxide and ethoxide has been studied to investigate the possible involvement of hexacoordinated phosphorus species in this reaction. For alkoxide concentrations less than ca. 1.5 M the rate increases with the square of alkoxide concentration. However, consideration of the activity of the alkoxides, represented by an appropriate acidity function, reveals that only one equivalent of alkoxide is involved in the rate-determining step. Thus, there is no requirement to invoke the intermediacy of a hexacoordinated species in the reaction pathway. © John Wiley & Sons, Inc.     

A New Flow Instrument for Conductance Measurements at Elevated Temperatures and Pressures: Measurements on NaCl(aq) to 458 K and 1.4 MPa

A new flow electrical conductance instrument was constructed and tested on dilute NaCl solutions up to 458 K, and on more concentrated solutions (maximum 0.436 mol⋅kg⁻¹) at 373 K. The results of the new instrument agreed with those of previous authors within the estimated experimental errors. The model of Bernard et al. (J. Phys. Chem. 96, 3833–3840 (1992), MSA) was found to represent the high-temperature results without introducing an ion-pairing equilibrium constant. The Fuoss–Hsia conductance equation as given by Fernandez-Prini was found to represent the dilute concentrations with Λ° (NaCl) as the only adjustable parameter. It was found that Λ° (NaCl) could be expressed as a function of solvent viscosity and density by using three parameters found by regression of literature results between 278.15 and 523 K. This equation along with the FHFP theory permits the equivalent conductivity of dilute sodium chloride solutions to be calculated within the accuracy of the existing experimental measurements.     

The potential role of ultrasound in differentiating solid and cystic swellings of the true vocal fold

This study was designed to investigate the potential role of ultrasound in the diagnosis of cysts of the true vocal fold. Materials and Methods: Grayscale ultrasound of the larynx was carried out in 29 patients with a swelling of the true vocal fold and dysphonia. The findings were then compared with those at subsequent microlaryngoscopy, in the majority of cases. Results and Conclusions: Whereas preoperative laryngeal ultrasound correctly predicted the surgical findings of a cystic lesion in only 5 of 11 cases, it correctly identified that no cyst was present in 15 of 16 instances when this had been queried. This study suggests that ultrasound may have some role in investigation of unilateral vocal fold pathology, but that further fine-tuning of the technique may be necessary.     

The variation of carrier gas viscosities with temperature

After describing simplified equations exspressing the temparature dependency of the viscosity of carrier gases (helium, nitrogen and hydrogen ) relative to a base value, absolute relationships based on the kinetic theory of gases are discussed. Comparative data obtained using various calculation methods are given and are compared to measured values. Based on the kinetic relationshipsm, of viscosity. Finally, the influence of pressure on the viscosity is also briefly discussed. As a supplement, Viscosity data are tabulated for the three gases in the range of 0°C to 400°C in increments of 2 K, calculated using the kinetic relationships.     

SO42-/Zr-ZSM-5 超强酸催化剂的制备和表征

以硅溶胶和氧氯化锆为硅源和锆源，采用水热合成的方法制得具有ZSM-5结构的Zr-Si分子筛；用0.5mol/L的硫酸处理该分子筛，并在550℃焙烧，制得具有ZSM-5结构的SO4^2-/ZrO2-SiO2分子筛型的固体超强酸。采用XRD、SEM、TG、IR、NH3-PHD和指示剂法对其结构和酸性进行表征。结果表明，该SO4^2-/ZrO2-SiO2具有ZSM-5结构和超强酸性，其酸强度大于-13.75，且具有良好的热稳定性。     

Determination and confirmation of malachite green and leucomalachite green residues in salmon using liquid chromatography/mass spectrometry with no-discharge atmospheric pressure chemical ionization

A liquid chromatography/mass spectrometry (LC/MS) method was developed to quantitate and confirm residues of leucomalachite green (LMG) in salmon tissue after their conversion to chromic malachite green (MG) in the extraction process. The method uses no-discharge atmospheric pressure chemical ionization (APCI) in conjunction with an ion-trap instrument to generate product-ion spectra. In the sample preparation procedure, salmon tissue is extracted with acetonitrile/buffer, the LMG residue is partitioned into methylene chloride, the LMG is converted to MG using an organic oxidizing agent, and the MG is isolated on alumina/propylsulfonic acid solid-phase extraction cartridges. The method was validated by fortifying salmon with different levels of LMG, and then detecting the residue as MG The LC/MS conditions, including a comparison of electrospray and no-discharge APCI, were evaluated and optimized. MG was not confirmed in any of the control tissue extracts, and all fortified samples analyzed during validation met the confirmation criteria as described. In addition to providing confirmatory data, this method can provide an alternative method for quantitation of MG in salmon. The recoveries of LMG measured as MG by this LC/MS method, at fortification levels of 1-10 ng/g were very high (86-109%), with low relative standard deviation(RSD) values (6.4-13%). The results agreed very closely with those obtained for the same extracts using an LCNIS procedure, indicating that matrix suppression was not an issue. The presence of LMG in salmon tissue samples fortified at 0.25 ng/g was confirmed by this method, with an average recovery of 70.1% and an RSD of 12.0%. Sample extracts from fish exposed to MG were also analyzed.     

Efficient low-temperature oxidation of carbon-cluster anions by SO2

Carbon-cluster anions, CN-, are very reactive toward SO2 (sticking probability of 0.012 +/- 0.005 for C27- at 25 degrees C), in contrast to their inertness toward other common atmospheric gases and pollutants. In flow reactor experiments at ambient temperature and near atmospheric pressure, primary adsorption of SO2 by the carbon cluster anions, N = 4-60, yields CNSO2- or CN-1S-. The inferred elimination of neutral CO2 is also detected as meta-stable decay in collision-induced dissociation. At higher temperatures, the reaction of SO2 with nascent carbon clusters yields CN-1SO- as well as undetected CO. The size-dependent initial reactivity reflects the previously established structural transitions (i.e., from chain to cyclic to cage structures). Such carbon clusters are formed in sooting flames and may act as nuclei for the formation of primary soot particles and serve as models for the local structural features of active soot particle sites for black-carbon soot. The facile generation of reactive carbon-sulfide and -sulfinate units may therefore have implications for understanding the health and environmental effects attributed to the coincidence of soot and SO2.