Characterization of formaldehyde by gas chromatography using multiple pulsed-discharge photoionization detectors and a flame ionization detector

Formaldehyde, water, methanol, butanal, and butanone are characterized by gas chromatography using three pulsed-discharge photoionization detectors (PDPIDs) and a flame ionization detector (FID). One of the PDPIDs is operated in helium mode, and the other two are operated in argon and krypton modes. The FID is included for comparison. The PDPIDs are used to efficiently differentiate between and quantitatively identify formaldehyde and the other three compounds in a sample mixture. This is accomplished by using butanone as the internal standard and correlating the relative responses of the four organic compounds in the helium-, argon-, and krypton-mode PDPIDs with their relative retention times.     

A direct resistively heated gas chromatography column with heating and sensing on the same nickel element

Nickel clad or nickel wired fused silica column bundles were constructed and evaluated. The nickel sheathing or wire functions not only as the heating element for direct resistive heat, but also as the temperature sensor, since nickel has a large resistive temperature coefficient. With this method the temperature controller is able to apply power and measure the temperature simultaneously on the same nickel element, which can effectively avoid the temperature overshoot caused by any delayed response of the sensor to the heating element. This approach also eliminates the cool spot where a separate sensor touches the column. There are some other advantages to the column bundle structure: (1) the column can be heated quickly because of the direct heating and the column's low mass, shortening analysis time. We demonstrate a maximum heating rate of 13 °C/s (800 °C/min). (2) Cooling time is also short, increasing sample throughput. The column drops from 360 °C to 40 °C is less than 1 min. (3) Power consumption is very low – 1.7 W/m (8.5 W total) for a 5 m column and 0.69 W/m (10.4 W total) for a 15 m column when they are kept at 200 °C isothermally. With temperature programming, the power consumption for a 5 m column is less then 70 W for an 800 °C/min ramp to 350 °C. (4) The column bundle is small, with a diameter of only about 2.25 in. All these advantages make the column bundle ideal for fast GC analysis or portable instruments. Column efficiencies and retention time repeatability have been evaluated and compared with the conventional oven heating method in this study. For isothermal conditions, the column efficiencies are measured by effective theoretical plate number. It was found that the plate number with resistive heat is always less than with oven heat, due to uneven heat in the column bundle. However, the loss is not significant – an average of about 1.5% for the nickel clad column and 4.5% for the nickel wired column. Separation numbers are used for the comparison with temperature programming, with results similar to those observed for isothermal conditions. Retention time repeatability for direct heat were 0.010% RSD for isotheral and 0.037% RSD for temperature programming, which is similar to those obtained by oven heat. Applications have been demonstrated, including diesel and PAH analysis.     

Relationship between the ionic nature of some organoaluminum—transition metal catalysts and the rate of polymerization

The electrical conductivity of several trialkylaluminum and alkyl-aluminum halides was investigated in dry benzene at 25°C. within the concentration range of 10^?1–10^?3M. The equivalent conductance of the trialkylaluminum systems decreased in the following order: Al(n-C₆H₁₃)₃ > Al(n-C₁₀H₁₉)₃ > Al(n-C₄H₉)₃ > Al(i-C₄H₉)₃ > Al(n-C₃H₇)₃ > Al(C₂H₅)₃. The conductance (1/R) of a given series was also examined and found to decrease as each alkyl group was successively replaced by a chlorine atom, thus: Al(C₂H₅)₃ > Al(C₂H₅)₂Cl > Al(C₂H₅)_1.5Cl_1.5 > Al(C₂H₅)Cl₂ and Al(i-C₄H₉)₃ > Al(i-C₄H₉)₂Cl > Al(i-C₄H₉)Cl₂. The ion pair dissociation constants K were calculated and show in a qualitative manner the difference between various organoaluminum systems. The relative rate of olefin polymerization was related to the conductivity of various organoaluminum–transition metal catalyst systems used. The effect of Lewis bases such as monoglyme, diglyme, triglyme, and tetraglyme on triethylaluminum indicated that the first-mentioned base forms a 1:1 type of complex as ordinary ethers do, whereas the remaining three bases utilize only two of their available oxygen atoms to coordinate with triethylaluminum. The effect of TiCl₃ (in the presence of an ether) on the conductance was also determined.     

Characterization of a lipid-rich fraction synthesized by Streptomyces avermitilis

Isolation of the macrocyclic lactone parasiticide avermectin and other closely related natural products produced by Streptomyces avermitilis also yields a lipid-rich fraction. The latter has been characterized by techniques based on gas-liquid chromatography (GLC) and mass spectrometry (MS). Initial examination of the lipid-rich fraction by direct probe electron-impact (EI) MS and packed-column GLC showed that it consists primarily of a mixture of triglycerides possessing C14-C17 acyl groups. Further examination of this fraction by capillary column GLC-MS demonstrated that it contains low levels of C15-C17 free fatty acids, squalene and diglycerides and, as the major components, at least ten mixed acyl triglycerides (total number of acyl carbon atoms ranging from 43 to 50). Prominent among the triglycerides were a C15-C15-C16 species, a C15-C16-C16 species and a C15-C16-C17 species. Capillary-column GLC and GLC-MS of the fatty acid methyl esters resulting from transesterification demonstrated that the major triglyceride acyl groups are anteiso-C15 (12-methyltetradecanoyl), iso-C16 (14-methylpentadecanoyl), n-C16 (hexa-decanoyl) and anteiso-C17 (14-methylhexadecanoyl). Lower levels of the methyl esters of the following fatty acids were observed: iso-C14 (12-methyltridecanoic), n-C14 (tetradecanoic), iso-C15 (13-methyltetradecanoic), n-C15 (pentadecanoic), iso-C17 (15-methylhexadecanoic) and n-C17 (heptadecanoic). Little evidence was seen for either unsaturated acyl groups or acyl groups of less than 13 or more than 18 carbon atoms. Desorption chemical ionization MS (ammonia reagent gas) analysis confirmed the nature of the lipid-rich fraction, and is an attractive one-step approach for determining the molecular weights and distribution of triglycerides in a mixture.     

In situ DMSO hydration measurements of HTS compound libraries

Compounds used in high throughput screening (HTS) are typically dissolved in DMSO. These solutions are stored automation-friendly racks of wells or tubes. DMSO is hygroscopic and quickly absorbs water from the atmosphere. When present in DMSO compound solutions, water can accelerate degradation and precipitation. Understanding DMSO hydration in an HTS compound library can improve storage and screening methods by managing the impact of water on compound stability. A non-destructive, acoustic method compatible with HTS has been developed to measure water content in DMSO solutions. Performance of this acoustic method was compared with an optical technique and found to be in good agreement. The accuracy and precision of acoustic measurements was shown to be under 3% over the tested range of DMSO solutions (0% to 35% water by volume) and insensitive to the presence of HTS compounds at typical storage concentrations. Time course studies of hydration for wells in 384-well and 1536-well microplates were performed. Well geometry, fluid volume, well position and atmospheric conditions were all factors in hydration rate. High rates of hydration were seen in lower-volume fills, higher-density multi-well plates and when there was a large differential between the humidity of the lab and the water content of the DMSO. For example, a 1536-well microplate filled with 2microL of 100% DMSO exposed for one hour to a laboratory environment with approximately 40% relative humidity will absorb over 6% water by volume. Understanding DMSO hydration rates as well as the ability to reverse library hydration are important steps towards managing stability and availability of compound libraries.     

Correction of figure errors on optical surfaces by laser-induced contraction of Mo/Si multilayers

We demonstrate that laser annealing of Mo/Si multilayers can be used to make controlled modifications of the surface figure of an optical substrate on a nanometer scale. In this experiment a superpolished optical flat was exposed to single pulses from an excimer laser to produce surface depressions of widths that varied from 10 microm to 0.5 mm and of depths in the range 2-50 nm. Simulations of thermally induced contraction of the Mo/Si multilayers are in good agreement with the observed deformations and indicate that the technique can be extended to larger deformations and higher resolution.     

Strong interaction shifts and widths in light kaonic atoms

Energy shifts and line widths of X-ray transitions in kaonic atoms have been measured with an accuracy of about 10%. These data have been interpreted in terms of an optical potential. Whereas earlier approaches based on the free K⁻N scattering lengths fail to reproduce the data, a set of effective parameters consistant with all now available experiments could be derived.