\u3cem\u3eDrosophila\u3c/em\u3e Vitelline Membrane Assembly: A Critical Role for an Evolutionarily Conserved Cysteine in the “VM domain” of sV23

The vitelline membrane (VM), the oocyte proximal layer of the Drosophila eggshell, contains four major proteins (VMPs) that possess a highly conserved “VM domain” which includes three precisely spaced, evolutionarily conserved, cysteines (CX7CX8C). Focusing on sV23, this study showed that the three cysteines are not functionally equivalent. While substitution mutations at the first (C123S) or third (C140S) cysteines were tolerated, females with a substitution at the second position (C131S) were sterile. Fractionation studies showed that sV23 incorporates into a large disulfide linked network well after its secretion ceases, suggesting that post-depositional mechanisms are in place to restrict disulfide bond formation until late oogenesis, when the oocyte no longer experiences large volume increases. Affinity chromatography utilizing histidine tagged sV23 alleles revealed small sV23 disulfide linked complexes during the early stages of eggshell formation that included other VMPs, namely sV17 and Vml. The early presence but late loss of these associations in an sV23 double cysteine mutant suggests that reorganization of disulfide bonds may underlie the regulated growth of disulfide linked networks in the vitelline membrane. Found within the context of a putative thioredoxin active site (CXXS) C131, the critical cysteine in sV23, may play an important enzymatic role in isomerizing intermolecular disulfide bonds during eggshell assembly

An Ion Ejection Technique for the Study of Ion-Molecule Reactions with Ion Cyclotron Resonance Spectroscopy

A novel technique involving a straightforward modification of an ion cyclotron resonance spectrometer has been developed which utilizes the excitation of the characteristic oscillatory motion of the ions, due to the trapping field, for ejecting ions from the cyclotron resonance cell. By pulsing the rf ejection field and referencing the detection system to the pulsing frequency, a spectrum of ions whose number density is modulated by the pulsed ejection field is obtained. This is directly applicable in studying ion-molecule reactions for the determination of product ion distributions, even when other processes, such as direct ionization or concurrent ion-molecule reactions, contribute to product ions of interest

Mass spectrometer calibration of Cosmic Dust Analyzer

The time of flight mass spectrometer of the Cosmic Dust Analyzer (CDA) instrument aboard the Cassini spacecraft, is expected to be placed in orbit about Saturn to sample the ring material and satellite impact ejecta. Upon impact of an incident dust particle against the target plate at velocities of 5-100 km/s, some 10–8 to 10–5 times the particle mass of positive valence, single-charged ions is induced. These are analyzed via a time-of-flight mass spectrometer. Initial experiments employing a pulsed N2 laser (>300 µJ/pulse, 4ns, 337nm) acting on a suite of samples are described. The laser beam is focussed to deliver the light pulses onto a laser power density (1011 W/cm2) to simulate the impact of particles. Laser ionization produced a charge of 4.6 pC per pulse for aluminum alloy. Estimating that each Al+1 ion require energy of 5.98 eV ionization energy/ion implies that 10–5% of the laser energy produced ions and the present system has a 5% efficiency of collecting the laser-irradiation induced ions. Employing a multi-channel plate detector in this mass spectrometer yields for Al-Mg-Cu alloy and kamacite (Fe-Ni mineral) targets well defined peaks at 24 (Mg+1), 27 (Al+1) and 64 (Cu+1), and 56 (Fe+1), 58 (Ni+1) and 60 (Ni+1) dalton, respectively

Easily fabricated ion source for characterizing mixtures of organic compounds by direct analysis in real time mass spectrometry

The increasing use of atmospheric pressure mass spectrometry has led to the development of many ambient ionization sources, for which sampling versatility and low cost are desired features. One such recent ambient ionization method is direct analysis in real time mass spectrometry (DART-MS), which has proven to be well suited to the analysis of native samples of both simple and complex natures. We describe a home-built DART source (EZ-DART) with versatile sampling capabilities, low power requirements, and low assembly cost which can be easily interfaced to mass spectrometers equipped with an atmospheric pressure inlet. The operating temperature range (22–250 °C) enables the acquisition of both temperature programmed desorption-based DART mass spectra and the collection of multistep collision-induced dissociation (CID) mass spectra. We present here the validation of the EZ-DART source and a demonstration of its performance in a number of relevant applications. Additionally, we introduce the new DART application of reagent assisted desorption ionization (RADI) for the targeting of specific chemical functionality in complex organic mixtures through a host–guest chemical system

New results on GP Com

We present high resolution optical and UV spectra of the 46 min orbital period, helium binary, GP Com. Our data contains simultaneous photometric correction which confirms the flaring behaviour observed in previous optical and UV data. In this system all lines show a triple peaked structure where the outer two peaks are associated with the accretion disc around the compact object. The main aim of this paper is to constrain the origin of the central peak, also called ``central spike''. We find that the central spike contributes to the flare spectra indicating that its origin is probably the compact object. We also detect that the central spike moves with orbital phase following an S-wave pattern. The radial velocity semiamplitude of the S-wave is ~10 km/s indicating that its origin is near the centre of mass of the system, which in this case lies very close to the white dwarf. Our resolution is higher than that of previous data which allows us to resolve structure in the central peak of the line. The central spike in three of the HeI lines shows another peak blueshifted with respect to the main peak. We propose that one of the peaks is a neutral helium forbidden transition excited in a high electron density region. This forbidden transition is associated with the permitted one (the stronger peak in two of the lines). The presence of a high electron density region again favours the white dwarf as their origin.Comment: 14 pages, 16 figures. Accepted for publication in A&

Time Resolved Study of Hydroxyl Radical Oxidation of Oleic Acid at the Air-Water Interface

The ubiquity of oleic acid (OA) renders it a poster child for laboratory investigations of environmental oxidation chemistry. In the current study, mechanistic details of the oxidation of OA by hydroxyl radicals at the air-water interface are investigated using field-induced droplet ionization mass spectrometry (FIDI-MS). Products from OH oxidation of both unsaturated and saturated carbon atoms are identified, and mechanisms for both types of oxidation processes are proposed. Uptake of oxygen in the interfacial layer increases linearly with time, consistent with Langmuir-Hinshelwood reaction kinetics. These results provide fundamental knowledge relating to OH initiated degradation of fatty acids in atmospheric aerosols

Stability of undissociated screw dislocations in zinc-blende covalent materials from first principle simulations

The properties of perfect screw dislocations have been investigated for several zinc-blende materials such as diamond, Si, $\beta$-SiC, Ge and GaAs, by performing first principles calculations. For almost all elements, a core configuration belonging to shuffle set planes is favored, in agreement with low temperature experiments. Only for diamond, a glide configuration has the lowest defect energy, thanks to an sp$^2$ hybridization in the core

Subtle Changes in Lipid Environment Have Profound Effects on Membrane Oxidation Chemistry

Nature carefully designs the components of amphiphile-composed monolayer and bilayer membranes to deliver specific functions. The compositions of these interfacial layered structures are so delicate that minute modifications can result in huge changes in function. Great effort has been expended to understand membrane physical properties, with only minimum attention given to associated chemical properties. Here we report the first examples of the delicate chemistry associated with membrane amphiphilic components by studying OH-mediated oxidation of six different unsaturated lipids/surfactants and their mixtures at the air–water interface using field-induced droplet ionization mass spectrometry (FIDI-MS). When the packing is loose or perturbed to be loose by other components or prior chemical modification, the double bond is oxidized without cleavage by adding oxygen functionality. In contrast, compact packing results in double bond cleavage through a Criegee intermediate mechanism. We postulate that constrained environments imposed by lipid packing limit the conformations of the reaction intermediates, controlling reaction pathways