A comparison of double-focusing sector field ICP-MS, ICP-OES and octopole collision cell ICP-MS for the high-accuracy determination of calcium in human serum

Human serum is routinely measured for total calcium content in clinical studies. A definitive high-accuracy and low-uncertainty method is required for reference measurements to underpin medical diagnoses. This study presents a novel octopole collision cell ICP-MS, high-accuracy, methodology and comparison of that technique with double-focusing sector field ICP-MS and an ICP-OES method. Double-matched isotope dilution mass spectrometry (IDMS) was employed for ICP-MS techniques and an exact matching bracketing technique using scandium as an internal standard was used for ICP-OES analysis. Medium resolution mode was utilised for double-focusing sector field ICP-MS analysis to resolve the dominant interferences on the ⁴⁴Ca/⁴²Ca isotope pair. Hydrogen reaction gas was employed to chemically resolve a number of polyatomic interferences predominantly through charge transfer reactions in the octopole collision cell. Comparison data presented for NIST CRM 909b human serum analysis from all three techniques demonstrates highest accuracy (99.6%) and lowest uncertainty (1.1%) for octopole collision cell ICP-MS. Data from ICP-OES using a non-IDMS technique produces comparably accurate data and low-uncertainties. The much higher total expanded uncertainties for double-focusing sector field ICP-MS compared with octopole collision cell data are explained by lower precision on the measurement of the ⁴⁴Ca/⁴²Ca isotope ratio. Data for octopole collision cell ICP-MS submitted for an international blind trial comparison (CCQM K-14) demonstrated excellent agreement with the mean of all participants with a low expanded uncertainty.     

Vitamin B12 as an allosteric cofactor; dual fluorescence, hysteresis, oscillations and the selection of corrin over porphyrin

Studies of the emission spectra of four Co(III) cobinamides (diaquo-, aquohydroxo-, dihydroxo- and dicyano-) show (1) that the excited states corresponding to the alphabeta and epsilon absorption bands behave like the S(1) and S(2) levels in the non-alternant hydrocarbon azulene (with emission from S(2)> S(1) in violation of Kasha's rule) and (2) that the excited states include a TICT (twisted intramolecular charge transfer) mechanism, as in the simpler cyanines, but where the TICT state gives rise to dual fluorescence instead of cis-trans isomerisation. Combined with the previously reported dual fluorescence from the S(1) level in synthetic metal corrinoids and in the naturally-occurring metal-free corrin, this provides evidence that the existence of an additional (metastable) ground state with a significantly different vibronic splitting and nuclear configuration is an intrinsic property of the basic corrin ligand (irrespective of the nature of the side-chains and the metal ion or even the absence of a metal) which distinguishes it from porphyrin. The occurrence of hysteresis (and its associated oscillations) in redox reactions of the cobinamides involving both the Co(III/II) and Co(II/I) couples indicates that the corrin ligand also has an intrinsic ability to exist in different conformations or "allosteric" forms with differing redox potential, which further distinguishes it from the porphyrin ligand. Possible links between the existence of an additional metastable ground state and of allosteric changes and the likely reasons for the selection of corrin over a porphyrin for the vitamin B(12)-dependent enzymes are discussed.     

The crystallographic structure of the natural air-hydrate in Greenland dye-3 deep ice core

We have carried out X-ray diffraction studies on single crystals of natural air-hydrate in deep ice cores recovered at Dye-3 Greenland. Integrated intensities for 470 diffracting planes were measured by an automated four-circle diffractometer. The space group determined is cubicFd3m and the lattice constant is 17.21(3) Å. These results indicate that the crystallographic structure is the Stackelberg's structure II, in contrast to the previously anticipated structure. This finding agrees with the recent results on the synthetic air-hydrate by Davidsonet al. It was also found by difference Fourier synthesis for guest molecules that electron density in a 16-hedral cage has multiple maxima displaced from the center of the cage while that in the 12-hedron was approximately spherical.Dedicated to Dr D. W. Davidson in honor of his great contributions to the sciences of inclusion phenomena.     

Determination of trace concentrations of citrate in aqueous systems

A fluorimetric method for the determination of citrate is described. Through a series of reactions, citrate is converted into citrazinic acid. The ammonium salt of this compound exhibits a fluorescence maximum at 430 nm when an excitation source of 340 nm is used. The method does not suffer from the normal interferences. The limit of detection is 0.01 μg ml^-, and the best working range is 0.1–10 μg ml^-1.     

Aminocyclodextrins to facilitate the deprotonation of 4-tert-butyl-alpha-nitrotoluene

6A-Amino-6A-deoxy-beta-cyclodextrin enhances the rate of the deprotonation of 4-tert-butyl-alpha-nitrotoluene. The rate constants for reaction of the cyclodextrin-bound species, kinc = 4 x 10(-3), 9 x 10(-3) and 19 x 10(-3) s(-1), at pH 6.0, 6.5 and 7.0, respectively, in 0.1 mol dm(-3) aqueous phosphate buffer containing 1% methanol at 298 K. These rate constants correspond to a rate acceleration (kinc/kun) of ca. 10 times at each pH. Under the same conditions, 6A-dimethylamino-6A-deoxy-beta-cyclodextrin and 6A-(2-aminoethylamino)-6A-deoxy-beta-cyclodextrin are more effective; at pH 6.0, 6.5 and 7.0, for the former, kinc = 3 x 10(-2), 7 x 10(-2) and 12 x 10(-2) s(-1), whilst for the latter, kinc = 4 x 10(-2), 5 x 10(-2) and 9 x 10(-2) s(-1), respectively. Each cyclodextrin also decreases the pKa of the nitrotoluene, from 6.8 in free solution, to 6.2 when bound. The accelerated deprotonation by 6A-amino-6A-deoxy-beta-cyclodextrin is reflected in the enhanced rates of hydrogen-deuterium exchange of the nitrotoluene in deuterium oxide, and in the conjugate addition of the nitrotoluene to methyl vinyl ketone in aqueous solution.     

Characterization of gem-difluoropropargyl synthons through HF loss from protonated molecules in methane chemical ionization mass spectra

Electron impact and methane chemical ionization mass spectra were obtained following gas chromatography/mass spectrometry for several gem-difluoropropargyl compounds, which had been synthesized as potential intermediates for synthesis of gem-difluoromethylene-containing C-3 acetylenes. EI spectra were variable with respect to the presentation of molecular ions, depending on substituent functional groups present. Methane-CI spectra were characterized by loss of 19 mass units from molecular weight with all compounds examined. These [M − 19]⁺ ions often presented as base peaks of the CI spectra, and were more reliably present and abundant than [M + 1]⁺ ions for these compounds. These ions could have been formed by elimination of HF from the protonated molecules under conditions of methane chemical ionization.     

Strong intramolecular secondary si.N bonds in trifluorosilylhydrazines

The simple silylhydrazines F(3)SiN(Me)NMe(2) (1), F(2)Si(N(Me)NMe(2))(2) (2), and F(3)SiN(SiMe(3))NMe(2) (3) have been prepared by reaction of SiF(4) with LiN(Me)NMe(2) and LiN(SiMe(3))NMe(2), while F(3)SiN(SnMe(3))NMe(2) (4) was prepared from SiF(4) and (Me(3)Sn)(2)NNMe(2) (5). The compounds were characterized by gas-phase IR and multinuclear NMR spectroscopy ((1)H, (13)C, (14/15)N, (19)F, (29)Si, (119)Sn), as well as by mass spectrometry. The crystal structures of compounds 1-5 were determined by X-ray crystallography. The structures of free molecules 1 and 3 were determined by gas-phase electron diffraction. The structures of 1, 2, and 4 were also determined by ab initio calculations at the MP2/6-311+G** level of theory. These structural studies constitute the first experimental proof for the presence of strong Si.N beta-donor-acceptor bonds between the SiF(3) and geminal NMe(2) groups in silylhydrazines. The strength of these non-classical Si.N interactions is strongly dependent on the nature of the substituent at the alpha-nitrogen atom of the SiNN unit, and has the order 3>4>1. The valence angles at these extremely deformed alpha-nitrogen atoms, and the Si.N distances are (crystal/gas): 1 104.2(1)/106.5(4) degrees, 2.438(1)/2.510(6) A; 3 83.6(1)/84.9(4) degrees, 2.102(1)/2.135(9) A; 4 89.6(1) degrees, 2.204(2) A.     

Molecular reactors and machines: applications, potential, and limitations

Molecular reactors are miniature vessels for the assembly of reactants at the molecular level, in order to change the nature of chemical transformations. It seems probable that those that will find most immediate applications are those that change product ratios or give products which would not readily form in the absence of the reactors, and thereby afford easy access to materials that are otherwise difficult to obtain. Molecular machines consist of interrelated parts with separate functions and perform some kind of work, at the molecular level. Practical examples are likely to be relatively uncomplicated and not based on individual functions of single-molecule devices. Instead they will probably rely on extensive redundancy of the molecular components and their interactions and reactions, as well as of the machines themselves.     

Two new standard reference materials for the determination of drugs of abuse in human hair

Two new standard reference materials (SRM) for drugs of abuse in human hair have been developed. SRM 2379 consists of hair spiked with cocaine, benzoylecgonine, cocaethylene, phencyclidine, amphetamine, and methamphetamine. SRM 2380 consists of hair spiked with codeine, morphine, monoacetylmorphine, and tetrahydrocannabinol (THC). The SRMs were prepared by soaking the hair in a solution of the target analytes in water-dimethylsulfoxide. The concentration of each analyte was determined using two methods, one based upon gas chromatography/mass spectrometry (GC/MS) and one based upon liquid chromatography/mass spectrometry (LC/MS). Both methods used 0.1 M HCl for extraction of all the analytes from the hair, except for THC, which was extracted with 1 M NaOH. For isolation of the analytes from the extracts, the GC/MS-based methods used different clean-up procedures from those used for the LC/MS-based methods. The results from the two methods were in good agreement with mean differences for the analytes ranging from 4% to 16%. These materials will enable laboratories performing analyses of hair for drugs of abuse to test the accuracy of their methods.     

Effects of reduction temperature and metal-support interactions on the catalytic activity of Pt/gamma-Al2O3 and Pt/TiO2 for the oxidation of CO in the presence and absence of H2

TiO2- and gamma-Al2O3-supported Pt catalysts were characterized by HRTEM, XPS, EXAFS, and in situ FTIR spectroscopy after activation at various conditions, and their catalytic properties were examined for the oxidation of CO in the absence and presence of H2 (PROX). When gamma-Al2O3 was used as the support, the catalytic, electronic, and structural properties of the Pt particles formed were not affected substantially by the pretreatment conditions. In contrast, the surface properties and catalytic activity of Pt/TiO2 were strongly influenced by the pretreatment conditions. In this case, an increase in the reduction temperature led to higher electron density on Pt, altering its chemisorptive properties, weakening the Pt-CO bonds, and increasing its activity for the oxidation of CO. The in situ FTIR data suggest that both the terminal and bridging CO species adsorbed on fully reduced Pt are active for this reaction. The high activity of Pt/TiO2 for the oxidation of CO can also be attributed to the ability of TiO2 to provide or stabilize highly reactive oxygen species at the metal-support interface. However, such species appear to be more reactive toward H2 than CO. Consequently, Pt/TiO2 shows substantially lower selectivities toward CO oxidation under PROX conditions than Pt/gamma-Al2O3.