Investigation of liquid MALDI and optimization for instrument tuning and quantitative measurements

The success of Matrix-assisted laser desorption / ionisation (MALDI) in fields such as proteomics has partially but not exclusively been due to the development of improved data acquisition and sample preparation techniques. This has been required to overcome some of the short comings of the commonly used solid-state MALDI matrices such as - cyano-4-hydroxycinnamic acid (CHCA) and 2,5-dihydroxybenzoic acid (DHB). Solid state matrices form crystalline samples with highly inhomogeneous topography and morphology which results in large fluctuations in analyte signal intensity from spot to spot and positions within the spot. This means that efficient tuning of the mass spectrometer can be impeded and the use of MALDI MS for quantitative measurements is severely impeded. Recently new MALDI liquid matrices have been introduced which promise to be an effective alternative to crystalline matrices. Generally the liquid matrices comprise either ionic liquid matrices (ILMs) or a usually viscous liquid matrix which is doped with a UV lightabsorbing chromophore [1-3]. The advantages are that the droplet surface is smooth and relatively uniform with the analyte homogeneously distributed within. They have the ability to replenish a sampling position between shots negating the need to search for sample hot-spots. Also the liquid nature of the matrix allows for the use of additional additives to change the environment to which the analyte is added.

Small-angle x-ray scattering study of flow alignment of a thermotropic liquid crystal in the nematic and smectic phases

WThe capillary flow alignment of the thermotropic liquid crystal 4-n-octyl-4′-cyanobiphenyl in the nematic and smectic phases is investigated using time-resolved synchrotron small-angle x-ray scattering. Samples were cooled from the isotropic phase to erase prior orientation. Upon cooling through the nematic phase under Poiseuille flow in a circular capillary, a transition from the alignment of mesogens along the flow direction to the alignment of layers along the flow direction (mesogens perpendicular to flow) appears to occur continuously at the cooling rate applied. The transition is centered on a temperature at which the Leslie viscosity coefficient α3 changes sign. The configuration with layers aligned along the flow direction is also observed in the smectic phase. The transition in the nematic phase on cooling has previously been ascribed to an aligning-nonaligning or tumbling transition. At high flow rates there is evidence for tumbling around an average alignment of layers along the flow direction. At lower flow rates this orientation is more clearly defined. The layer alignment is ascribed to surface-induced ordering propagating into the bulk of the capillary, an observation supported by the parallel alignment of layers observed for a static sample at low temperatures in the nematic phase.

The effect of feeding modified soyabean oil enriched with C18 : 4 n-3 to broilers on the deposition of n-3 fatty acids in chicken meat

Supplementing broiler diets with conventional vegetable oils has little effect on the long-chain n-3 PUFA (LC n-3 PUFA) content of the meat. The present study investigated the effect on fatty acid composition and sensory characteristics of chicken meat when broilers were fed oil extracted from soyabeans (SDASOY) that had been genetically engineered to produce C18 : 4n-3 (stearidonic acid (SDA), 240 mg/g oil). Three diets were fed to 120 birds (eight replicate pens of five birds) from 15 d to slaughter (41–50 d). Diets were identical apart from the oil added to them (45 and 50 g/kg as fed in the grower and finisher phases, respectively), which was either SDASOY, near-isogenic soya (CON) or fish oil (FISH). The LC n-3 PUFA content of the meat increased in the order CON, SDASOY and FISH. In breast meat with skin, the SDA concentration was 522, 13 and 37 (sem 14·4) mg/100 g meat for SDASOY, CON and FISH, respectively. Equivalent values for C20 : 5n-3 (EPA) were 53, 13 and 140 (sem 8·4); for C22 : 5n-3 (docosapentaenoic acid (DPA)) 65, 15 and 101 (sem 3·5); for C22 : 6n-3 (DHA) 19, 9 and 181 (sem 4·4). Leg meat (with skin) values for SDA were 861, 23 and 68 (sem 30·1); for EPA 87, 9 and 258 (sem 7·5); for DPA 95, 20 and 165 (sem 5·0); for DHA 29, 10 and 278 (sem 8·4). Aroma, taste and aftertaste of freshly cooked breast meat were not affected. Fishy aromas, tastes and aftertastes were associated with LC n-3 PUFA content of the meat, being most noticeable in the FISH leg meat (both freshly cooked and reheated) and in the reheated SDASOY leg meat.

Deposition of charged inhaled aerosols with transient airflow in sequential lung airway model

Transport and deposition of charged inhaled aerosols in double planar bifurcation representing generation three to five of human respiratory system has been studied under a light activity breathing condition. Both steady and oscillatory laminar inhalation airflow is considered. Particle trajectories are calculated using a Lagrangian reference frame, which is dominated by the fluid force driven by airflow, gravity force and electrostatic forces (both of space and image charge forces). The particle-mesh method is selected to calculate the space charge force. This numerical study investigates the deposition efficiency in the three-dimensional model under various particle sizes, charge values, and inlet particle distribution. Numerical results indicate that particles carrying an adequate level of charge can improve deposition efficiency in the airway model.

Numerical modeling of inhaled charged aerosol deposition in human airways

A new numerical modeling of inhaled charge aerosol has been developed based on a modified Weibel's model. Both the velocity profiles (slug and parabolic flows) and the particle distributions (uniform and parabolic distributions) have been considered. Inhaled particles are modeled as a dilute dispersed phase flow in which the particle motion is controlled by fluid force and external forces acting on particles. This numerical study extends the previous numerical studies by considering both space- and image-charge forces. Because of the complex computation of interacting forces due to space-charge effect, the particle-mesh (PM) method is selected to calculate these forces. In the PM technique, the charges of all particles are assigned to the space-charge field mesh, for calculating charge density. The Poisson's equation of the electrostatic potential is then solved, and the electrostatic force acting on individual particle is interpolated. It is assumed that there is no effect of humidity on charged particles. The results show that many significant factors also affect the deposition, such as the volume of particle cloud, the velocity profile and the particle distribution. This study allows a better understanding of electrostatic mechanism of aerosol transport and deposition in human airways.

Evidence that ice forms primarily in supercooled liquid clouds at temperatures > -27C

Using 4 years of radar and lidar observations of layer clouds from the Chilbolton Observatory in the UK, we show that almost all (95%) ice particles formed at temperatures >-20°C appear to originate from supercooled liquid clouds. At colder temperatures, there is a monotonic decline in the fraction of liquid-topped ice clouds: 50% at -27°C, falling to zero at -37°C (where homogeneous freezing of water droplets occurs). This strongly suggests that deposition nucleation plays a relatively minor role in the initiation of ice in mid-level clouds. It also means that the initial growth of the ice particles occurs predominantly within a liquid cloud, a situation which promotes rapid production of precipitation via the Bergeron-Findeison mechanism.

Hydrogen-bonding-driven self-assembly of PEGylated organosilica nanoparticles with poly(acrylic acid) in aqueous solutions and in layer-by-layer deposition at solid surfaces

PEGylated organosilica nanoparticles have been synthesized through self-condensation of (3-mercaptopropyl)trimethoxysilane in dimethyl sulfoxide into thiolated nanoparticles with their subsequent reaction with methoxypoly(ethylene glycol) maleimide. The PEGylated nanoparticles showed excellent colloidal stability over a wide range of pH in contrast to the parent thiolated nanoparticles, which have a tendency to aggregate irreversibly under acidic conditions (pH < 3.0). Due to the presence of a poly(ethylene glycol)-based corona, the PEGylated nanoparticles are capable of forming hydrogen-bonded interpolymer complexes with poly(acrylic acid) in aqueous solutions under acidic conditions, resulting in larger aggregates. The use of hydrogen-bonding interactions allows more efficient attachment of the nanoparticles to surfaces. The alternating deposition of PEGylated nanoparticles and poly(acrylic acid) on silicon wafer surfaces in a layer-by-layer fashion leads to multilayered coatings. The self-assembly of PEGylated nanoparticles with poly(acrylic acid) in aqueous solutions and at solid surfaces was compared to the behavior of linear poly(ethylene glycol). The nanoparticle system creates thicker layers than the poly(ethylene glycol), and a thicker layer is obtained on a poly(acrylic acid) surface than on a silica surface, because of the effects of hydrogen bonding. Some implications of these hydrogen-bonding-driven interactions between PEGylated nanoparticles and poly(acrylic acid) for pharmaceutical formulations are discussed.

Electro-optical properties of liquid crystal copolymers and their relationship to structural order

A range of side chain liquid crystal copolymers have been prepared using mesogenic and non-mesogenic units. It is found that high levels of the non-mesogenic moieties may be introduced without completely disrupting the organization of the liquid crystal phase. Incorporation of this comonomer causes a marked reduction in the glass transition temperature (Tg), presumably as a result of enhanced backbone mobility and a corresponding lowering of the nematic transition temperature, thereby restricting the temperature range for stability of the liquid crystal phase. The effect of the interactions between the various components of these side-chain polymers on their electro-optic responses is described. Infrared (i.r.) dichroism measurements have been made to determine the order parameters of the liquid crystalline side-chain polymers. By identifying a certain band (CN stretching) in the i.r. absorption spectrum, the order parameter of the mesogenic groups can be obtained. The temperature and composition dependence of the observed order parameter are related to the liquid crystal phase transitions and to the electro-optic response. It is found that the introduction of the non-mesogenic units into the polymer chain lowers the threshold voltage of the electro-optic response over and above that due to the reduction in the order parameter. The dynamic electro-optic responses are dominated by the temperature-dependent viscosity and evidence is presented for relaxation processes involving the polymer backbone which are on a time scale greater than that for the mesogenic side-chain units.

The effect of the molecular weight on the electro-optic properties of methacrylate-based side-chain liquid crystal polymers

A series of methacrylate-based side-chain liquid crystal polymers has been prepared with a range of molecular weights. For the high molecular weight polymers a smectic phase is observed with a very narrow nematic range; however, for low molecular weight polymers only the nematic phase is observed. A marked reduction in the glass transition temperature, TSN and TNI is observed with a reduction in the molecular weight. The orientational order parameters for these polymers in the liquid crystal phase have been determined using infra-red dichroism. It is found that the higher the molecular weight of the polymer, the greater is the threshold voltage of the electro-optic response and the lower the order parameter. The increase in the threshold voltage with increasing molecular weight may be related to the intrinsic curvature elasticity and hence to the coupling between the mesogenic units and the polymer backbone.

Dielectric relaxation around the nematic-isotropic transition of liquid crystalline polymers

This study is concerned with a series of acrylate based side-chain liquid crystalline (LC) polymers. Previous studies have shown that these LC polymers have a preference for parallel or perpendicular alignment with respect to the polymer chain which depends on the length of the coupling chain joining the mesogenic unit to the polymer backbone. On the other hand, the dielectric relaxation of these side-chain LC polymers shows a strong relaxation associated to the mesogenic unit dynamics. For samples with parallel alignment, it was found that the dielectric relaxation of the nematic is weaker and broader than the relaxation of the isotropic. By contrast, for samples with perpendicular alignment, the isotropic to nematic transition reduces the broadening the relaxation and increases the relaxation strength. These two features are more evident for samples with short coupling units for which the dielectric relaxation observed appears to be strongly coupled with the backbone dynamics.

Orientational behaviour of thermotropic and lyotropic liquid crystal polymer systems under shear flow

A comparison is made of the development of global orientation during shearing of lyotropic solutions of hydroxypropylcellulose with that observed for the thermotropic phase of hydroxypropylcellulose. At shear rates the behaviour of the two systems is similar, both during steady-state shear, and in terms of relaxation following cessation of shear flow. At low shear rates, the levels of orientation observed for the thermotropic system are substantially greater than observed for the lyotropic solutions. The relationship of these differences to variations in molecular parameters, viscous stress and to director tumbling is discussed.