Measurement and modeling of the glass transition temperatures of multi-component solutions

Protein crystals are usually grown in multi-component aqueous solutions containing salts, buffers and other additives. To measure the X-ray diffraction data of the crystal, crystals are rapidly lowered to cryogenic temperatures. On flash cooling, ice frequently forms affecting the integrity of the sample. In order to eliminate this effect, substances called cryoprotectants are added to produce a glassy (vitrified) state rather than ice. Heretofore, the quantity of cryoprotectant needed to vitrify the sample has largely been established by trial and error. In this study, differential scanning calorimetry (DSC) was used to measure the melting (T_m), devitrification (T_d) and glass transition (T_g) temperatures of solutions with a range of compositions typical of those used for growing protein crystals, with the addition of glycerol as cryoprotectant. The addition of cryoprotectant raises the T_g and lowers the T_m of bulk solution thereby decreasing the cooling rates required for vitrification of protein crystals. The theoretical T_g value was calculated using the apparent volume fraction using the Miller/Fox equation extended for multi-component systems. The experimental values of T_g were within approximately ±4% of that predicted by the model. Thus, the use of the model holds the promise of a rational method for the theoretical determination of the composition of cryoprotectant requirement of protein crystallization solutions.     

Capillary gas chromatography of lower aliphatic C2?C5 aldehydes in the free form as a group of pungent odorants in air

The capillary gas chromatography of the C₂-C₅ lower aliphatic aldehydes (e.g.,acetaldehyde, propionaldehyde, n- and i-butyraldehydes, n- and i-valeraldehydes) which, in the free form in air, have unpleasant odors and low threshold odor values, has been studied using cold-trap preconcentration with liquid oxygen. The capillary column outlet was connected to enable simultaneous detection by FID, ECD, FPD AND FTD (SID).     

Cis- and trans-3-hexene: infrared spectrum in liquid argon solution, ab initio calculations of equilibrium geometry, normal coordinate analysis, and vibrational assignments

The infrared spectra of cis-3-hexene and trans-3-hexene dissolved in liquid argon have been obtained at temperatures from 93 to 120 K. The absorptions were observed with a low-temperature cell and a Fourier transform infrared spectrophotometer. Ab initio molecular orbital calculations were performed to obtain the equilibrium geometry, vibrational frequencies, force fields, and infrared intensities. The calculations were done at the Hartree-Fock level using 6-31G basis set. The Cartesian force fields from ab initio calculations have been converted to the force field in symmetry coordinates. The scale factors of ab initio calculated force fields were determined. Normal coordinate calculations were performed using a scaled quantum mechanical (SQM) force field. Vibrational normal modes calculated for the lowest energy rotamers of cis- and trans-3-hexene have been assigned to infrared absorption bands observed in liquid argon solution. The assignments were based on calculated frequencies and potential energy distributions. The equilibrium geometries of the two lowest energy rotamers (symmetry C₂ and C_s) of cis-3-hexene and of the three lowest energy rotamers (symmetry C_i, C₂, and C₁) of trans-3-hexene were calculated. Variable temperature studies of the infrared spectrum of cis- and trans-3-hexenes dissolved in liquid argon were done to obtain the ΔH of conversion between the rotamers C₂ and C_s of cis-3-hexene and between the rotamers C_i, C₂, and C₁ of trans-3-hexene.     

Dynamic light scattering and cryogenic transmission electron microscopy investigations on metallo-supramolecular aqueous micelles: evidence of secondary aggregation

Metallo-supramolecular diblock copolymers consisting of a polystyrene (PS) block connected to a poly(ethylene oxide) (PEO) block by a bis(terpyridine)ruthenium complex (PS₂₀-[Ru]-PEO _y ) were used to prepare aqueous micelles. The length of the PS block was kept constant, while two PEOs of different molecular weight were used. The resulting hydrated micelles and aggregates were characterized by a combination of cryogenic transmission electron microscopy (cryo-TEM) and dynamic light scattering measurements. The results were compared to those obtained for a covalent counterpart (PS₂₂-b-PEO₇₀). Cryogenic transmission electron microscopy allowed visualization of the PS core of the micelles. Moreover, the aggregates result from clustering of individual micelles.     

The MPE/UCB far-infrared imaging Fabry-Perot interferometer (FIFI)

FIFI is an imaging spectrometer with two or three Fabry-Perot interferometers (FPI) in series for airborne astronomical observations in the far-infrared range (=40...200m). It employs 5×5 arrays of photoconducting detectors and offers spectral resolutions as small as 2km/s. Resolution and bandwidth can be set over a wide range to match a variety of astronomical sources. Cryogenic optics minimizes thermal background radiation and provides for in-flight step tunable spatial resolution. At 158 m wavelength the background-limited NEP is 3 × 10^-15W/Hz at 40 km/s resolution and with two FPI's; with three FPI's the expected NEP is 10^-15WHz at 5 km/s resolution.The frequency-chopping mode of the high-resolution Fabry-Perot allows for line detection in extended objects. Absolute internal flux calibration ensures adequate flat fielding of the array elements.     

The reinforcing effect of polydopamine functionalized graphene nanoplatelets on the mechanical properties of epoxy resins at cryogenic temperature

In order to obtain epoxy nanocomposites with excellent mechanical properties at cryogenic temperature, an efficient method to functionalize graphene nanoplatelets (GNPs) is proposed. Through a simple dip-coating procedure, the GNPs were first functionalized with deposition of polydopamine coating (PDA@GNPs). Then, using polydopamine as a bridge, the PDA@GNPs were modified with amine groups after polyetheramine T403 grafting (T403-PDA@GNPs). Fourier transform infrared spectroscopy, thermogravimetric analysis and X-ray photoelectron spectroscopy analyses proved the successful functionalization of PDA and polyetheramine T403 on the surface of GNPs. Adding 0.1 wt% T403-PDA@GNPs significantly improved the cryogenic tensile strength and impact strength of the epoxy nanocomposites by 34.5% and 64.5%, which showed greater reinforcing effect than the pristine GNPs (12.6% and 19.1%) and PDA@GNPs (26.3% and 50.1%). The results of dynamic mechanical analysis and scanning electron microscopy observations indicated that the PDA and further polyetheramine T403 functionalization improved the interfacial interactions between GNPs and matrix, which ensured the much improved mechanical properties.     

The Determination Of Sub Part-Per-Billion Levels Of Volatile Organic Compounds In Air By Pre-Concentration From Small Sample Volumes

Abstract

Trace level Volatile Organic Compounds (VOCs) in ambient air are normally determined according to EPA Method TO-14. This method describes the analysis in ambient air of 41 VOCs, ranging in boiling point from -29 to 215°C. It covers a concentration range from 0.2 to 20 parts per billion, volume/volume (ppb), and specifies sample enrichment of a 400 mL air sample on glass beads at -160°C. While this sample volume provides sub-ppb levels of VOC detection for target analytes when using a quadrupole mass spectrometer detector in SIM mode or when using GC detectors, the identification of non-target analytes may only be done in full scan mode for higher concentrations. Also with this sample volume a Nafion dryer is needed for water removal thereby lowering the recovery of polar VOCs.

Because of the very high sensitivity of the ion trap MS, relatively small air volumes (60 mL) are adequate to obtain the required or lower detection levels. An integrated air analysis system based on a GC-ion-trap MS has been investigated and is described. This system has a built-in cryogenic trap and necessary valving, internal standard gas sampling loop, and is controlled from the GC-MS workstation. The linearity, precision, and method detection levels obtainable with this system when using small volumes are reported. In addition, examples of the quantitative and qualitative analysis of ambient air samples are shown.     

Flame stabilization in high pressure LOx/GH2 and GCH4 combustion

Planar laser induced fluorescence (PLIF) of OH is used to examine flame stabilization in high pressure cryogenic flames formed by injecting a central jet of low speed liquid oxygen surrounded by a high speed gaseous stream of hydrogen or methane. In the LO_x/GH₂ experiments injection conditions are transcritical as the chamber pressure is above critical but the temperature is below critical . In the LO_x/GCH₄ experiments the chamber pressure and LO_x injection temperature are below critical , . Hydrogen or methane are injected at room temperature LIF images delineate the flame edge in the injector nearfield. The two flames are stabilized in the vicinity of the liquid oxygen injector lip but the anchor point is found to lie closer to the lip in the LO_x/GH₂ case and its displacement from shot to shot is of a smaller amplitude than that corresponding to the LO_x/GCH₄ flame. Interpretation of these data is based on a previous analysis which indicates that stabilization is essentially controlled by a dimensionless group formed by comparing the lip thickness to the flame edge thickness Ψ = h_s/δ_f. It is found that Ψ slightly exceeds unity in the LO_x/GH₂ case essentially fulfilling the stability condition while Ψ < 1 in the LO_x/GCH₄ case. In this last situation the flame is thicker than the characteristic thickness h_s and it is therefore sensitive to the high speed methane stream. Anchoring is imperfect and the flame edge moves with the turbulent eddies shed from the lip. Global stabilization is achieved dynamically but the reactive layer is not well established and the large amplitude motion of the edge is a symptom of a possible lift-off. Theoretical estimates indicate that LO_x/GCH₄ flame stabilization requires a thicker lip size than the LO_x/GH₂ propellant couple.     

Temperature Dependence for Fluorescence of β-NADH in Glycerol/Water Solution and in Trehalose/Sucrose Glass

Fluorescence imaging of cells and tissue can be used to evaluate β-NADH redox and location. At low temperature, β-NADH fluorescence intensity increases and therefore sensitivity of imaging increases. In this paper, the temperature dependence of fluorescence was evaluated for β-NADH in glycerol/water solution and in trehalose/sucrose glass. The average fluorescence lifetime for NADH in glycerol/water is 0.66 ns, compared with 5.3 ns in trehalose/ sucrose at 20°C. Emission spectra were recorded from 290 to 12 K. The fluorescence of β-NADH in glycerol/water increases ∼16 fold and the emission shifts about 35 nm to the blue as temperature decreases. Much smaller change is seen for fluorescence of β-NADH in sugar glass. Below 77 K, the β-NADH spectral features did not change significantly with temperature change, and so no increase in sensitivity is obtained by going to very low temperatures. It is suggested that the sensitivity of β-NADH fluorescence is related to water relaxation around the excited state molecule. Differences in water in various tissues may contribute to β-NADH fluorescence changes when cells are altered.     

防污染的自消应力高纯度气体低温换热器的设计

该设计解决了低温工程与低温技术等领域所使用的高纯度气体介质换热的要求,具有显著的经济效益和社会效益。其换热器是由四个管壳式热交换器串联组合而成,壳体呈窄矩形,换热管采用U形换热管,四个管壳式热交换器呈方阵置放在低温换热器筒体内。低温换热器采用的材料是0Cr18N i9/304,该种材料的透气性小、耐磨损、抗腐蚀能力强和性能稳定,防止了气体被污染。另外在低温下,考虑了材料的热胀冷缩所产生的应力,使应力能够自行消除,提高了它的密封性能,最终使低温换热器密封性能好,防止了气体被污染,保证了气体的高纯度。