Theoretical and experimental study of the achievable separation power in resistive‐glass atmospheric pressure ion mobility spectrometry

We present a detailed investigation of the performance of our previously reported nanoelectrospray high‐resolution resistive‐glass atmospheric pressure drift tube ion mobility spectrometer constructed with monolithic resistive‐glass desolvation and drift regions. Using experimental spectral data and theoretical pulse width and diffusion variables, we compare theoretical and experimental resolving powers achievable under a variety of field strengths and ion gate pulse widths. The effects of instrumental and operational parameters on the resolution achievable in chromatographic terms are also discussed. Following characterization of the separation power of the instrument, experimental spectral peak width data is fitted by a least‐squares procedure to a pre‐existing semi‐empirical model developed to study contributions to peak width other than initial pulse width and diffusional broadening. The model suggests possible contributions to the final measured peak width from electric field inhomogeneity and minor contributions from instrumental parameters such as anode size, anode‐to‐anode grid distance and drift gas flow rate. The model also reveals an unexpected ion gate width dependence on the final measured peak width that we attribute to non‐ideal performance of the Bradbury‐Nielsen ion gate and limitations in the design of our pulsing‐electronics. Copyright © 2010 John Wiley & Sons, Ltd.     

A study of diffractometer line shapes in melt crystallized polyethylene

Wide angle X-ray diffraction scans of isothermally crystallized samples of polyethylene containing known levels of chain defects have been investigated. An analysis of scattering curves using a powder diffractometer is reported. The analytical deconvolution of Lorentz and Lorentz squared profiles for the PE experimental scattering curve and the standard is performed to give the pure profile for the polymer. The separate contribution of paracrystalline lattice distortions and coherently diffracting domains, in different crystallographic directions, to the broadening of the diffraction profiles is discussed in the light of the level of defects present.     

Unit-cell dilation in model ethylene copolymers

Single crystals of model ethylene copolymers have been grown in dilute solution. The effects of narrow molecular weith distribution (MWD) and a perfectly random distribution of ethyl branches (ca. 17 per 1000 main-chain carbon atoms) on the unit cell of this ethylene copolymer analog were examined. X-ray diffraction on dried powder samples revealed expansions of up to 1.5% in a and 0.5% in b. a increased as a mild function of molecular weight; the dependence of b on MW was not as clearly defined. Electron diffraction studies on isolated suspensiongrown single crystals yielded lattice parameters much more strongly expanded. The large expansion in the basal plane of the unit cell is hypothesized to be accompanied by a fore-shortening of the projected c -axis distance. This is accomplished by and orthorhombic-to-hexagonal polymorphic transformation in which the chains are hypothesized to adopt a disordered helical conformation. The driving force for this transformation is electron irradiation damage of the single-crystal specimens. The rapidity of the transformation is believed to be due to the model polyethylene crystals being in a higher-energy, defect-containing condition prior to irradiation.     

Determination of the molecular weight spread of narrow peaks in the gel-permeation chromatograms of nitric acid-degraded polyethylene

A method for the determination of the molecular weight spread in the narrow peaks in the GPC chromatograms of nitric acid-degraded polyethylene is presented. It is found that polar endgroups added to the polymer chains during scission cause the peaks to be broader than those of paraffins with the same molecular weight spread. After allowing for this extra instrumental broadening, estimates are made of the molecular weight spread for unannealed and annealed single crystals of polyethylene and bulk polyethylene as a function of degradation time. It is proposed that after long degradation times the molecular weight spread is a measure of fluctuations in the original crystalline lamellar thickness.     

Separation and characterization of sub-microm- and microm-sized particles by capillary zone electrophoresis

The analytical separation and characterization of particles in the size range of sub-microm and microm diameters by capillary zone electrophoresis (CZE) has been reviewed. The theoretical basis, on which the mobility can be interpreted to provide information regarding characteristics of particle surface, has shortly been presented. Particular emphasis was put on the model dependence of that interpretation and the need in most applications to forego the classical idealized model of spherical particles with "smooth" surfaces and to apply more realistic models, which take the "hairy" surface of real particles into account. Some highlights of the literature on the CZE of polystyrene latex microspheres, organic and inorganic colloids, lipoprotein particles, viruses, liposomes, biological membrane vesicles, and biological cells have been discussed. Also summarized are the reports on the particle size dependence of mobility and peak broadening in CZE and on electrophoretic behavior of rodlike particles and particle aggregates. Finally, the effects of neutral polymers in the background electrolyte on particle mobility and peak width are reviewed.     

Structural and dynamic properties of a new type of discotic nematic compounds

Thermodynamic, structural and dynamical properties of a new type of discotic compounds, a hydrocarbon without any heteroatoms, displaying a nematic discotic phase have been investigated by means of X-ray diffraction, electro-optical relaxation, and calorimetric studies. Of particular interest are the strength of the first order nematic—isotropic phase transition and the nature of the orientational fluctuations in the isotropic phase. The short range positional order was found to be biaxial in both the isotropic and the nematic phase. The isotropic phase displays strong pretransitional effects originating from orientational fluctuations in the neighbourhood of the transition to the nematic phase. The character of these pretransitional effects differs from that found for calamitic systems in that the number of correlated molecules g₂ is extremely large, of the order of 600 at the clearing temperature and the electro-optical relaxation time is very large, caused by the large value of g₂.     

SAXS determination of the amorphous surface layer thickness of polymer single crystals

Polyethylene single crystals were grown from 0.1% solutions in xylene at 80 and 87°C. Oriented mats were made from each preparation and the small-angle x-ray scattering (SAXS) profiles obtained. Following treatment of the raw data for main-beam position and width, background scatter, and the Lorentz factor, five Bragg reflections were resolved. A one-dimensional lattice was used as a model for the oriented mats of single crystals. This model contains three parameters. An additional parameter G_x was also introduced to demonstrate the general effect of a broadening factor on the model. The effect of each parameter on the calculated diffraction pattern was examined. From this examination it was found that by assuming that the broadening functions are zero we can determine directly from the number of observable peaks the maximum possible thickness of the amorphous surface. Further, we find that the thickness of the amorphous layer must be less than the maximum value calculated if G_x is assigned values greater than zero. A “best-fit” diffraction pattern was generated in order to estimate how much smaller the surface thickness can be such that one can still resolve five diffraction maxima. The range of amorphous surface thicknesses found from the calculated diffraction profile is 12–20 Å. This is in good agreement with complementary studies performed on the same crystal preparations.     

Calibration of Separation and Instrumental Peak Broadening in Sec Coupled with Light Scattering of Simple Polymers

Abstract

A recently developed procedure for calibration of separation and instrumental peak broadening in SEC was used for a comparative study of separation and axial dispersion of polystyrene, poly(methyl methacrylate) and poly(vinylchloride). The influence of the uncertainty in the volume lag between the concentration and LALLS detectors upon peak broadening was investigated and a new procedure for the determination of the lag was proposed. The applicability of the universal calibration concept was tested; all the polymers have been found to match a single universal calibration function. Polystyrene and poly(methyl methacrylate) also coincided very well with respect to the instrumental spreading, but for poly(vinylchloride) spreading was found to be a function of polymer concentration.     

Hydrogen cycling induced diffraction peak broadening in C14 and C15 Laves phases

The diffraction peak broadening induced by hydrogen absorption-desorption cycling has been analyzed in four different Laves phase compounds with the C14 and C15 structures. The broadening is due to strain most probably originating from dislocations generated at the interface between the α and β hydride phases in connection with the cell volume difference between the two phases. It has been shown that it is strongly compound dependent. In the case of the C14 structure, the broadening is large and isotropic, and the latter can be related to the isotropy of the elastic constants of the metallic phase. The broadening is less for the compounds with the C15 structure, which can be related to a possibly softer lattice. Better ageing properties after long-term cycling are predicted for this crystal structure.     

Thermal expansivity of tetrahydrofuran clathrate hydrate with diatomic guest molecules

The guest dynamics and thermal behavior occurring in the cages of clathrate hydrates appear to be too complex to be clearly understood through various structural and spectroscopic approaches, even for the well-known structures of sI, sII, and sH. Neutron diffraction studies have recently been carried out to clarify the special role of guests in expanding the host water lattices and have contributed to revealing the influence factors on thermal expansivity. Through this letter we attempt to address three noteworthy features occurring in guest inclusion: (1) the effect of guest dimension on host water lattice expansion; (2) the effect of thermal history on host water lattice expansion; and (3) the effect of coherent/incoherent scattering cross sections on guest thermal patterns. The diatomic guests of H 2, D 2, N 2, and O 2 have been selected for study, and their size and mass dependence on the degree of lattice expansion have been examined, and four sII clathrate hydrates with tetrahydrofuran (THF) have been synthesized in order to determine their neutron powder diffraction patterns. After thermal cycling, the THF + H 2 clathrate hydrate is observed to exhibit an irreversible plastic deformation-like pattern, implying that the expanded lattices fail to recover the original state by contraction. The host-water cage dimension after degassing the guest molecules remains as it was expanded, and thus host-guest as well as guest-guest interactions will be altered if guest uptake reoccurs.     

Extra-column effects in multi-dimensional switching systems (MDSS) — GC

In order to permit valveless MDSS operation and easy column change, the hardware designed contains several connections. These can give rise to extra-column band broadening effects. In order to quantitate such effects, the packed-capillary column configuration (without trap) was used. The band broadening caused by the connections was found to be small: 120 ms². A more practical approach was used to check the performance of the trap (re-injection) in the capillary-trap-capillary column configuration. Here the results obtained with re-injection from the trap were compared with results obtained in transfer and heart-cutting modes while the trap was heated. Re-injection was tested with n-alkanes ranging from n-C₆ to n-C₂₈. A starting peak width of 1.6 s was found.     

Effects of stretching on microstructures of polymer-immobilized non-close-packed colloidal crystalline array

Non-close-packed silica colloidal crystalline array was immobilized by polymer, and effects of stretching on the change of the optical properties and microstructure of the colloidal crystalline arrays have been demonstrated. The immobilization was a two-step polymerization process: the first step was with hydrophilic polyethylene glycol acrylate (PEGA) polymer gel, and the second step was with 2-hydroxyethyl acrylate polymer matrix. The structure of the three-dimensional array was maintained during the immobilizing process with lock in periodic order. The peak wavelength of Bragg diffraction of the polymer-immobilized colloidal crystalline array shifted to shorter wavelength with stretching. The peak shift was caused by the compression of the polymer proportional to the stretching ratio, and the compression was homogeneous throughout the polymer-immobilized colloidal crystalline arrays. These results show that by using polymer-immobilized non-close-packed colloidal crystalline array, mechanically tunable photonic crystals can be realized, and they open the possibility of tuning the microstructure of colloidal crystalline array for photonic crystal.     

High-resolution absorption cross sections of formaldehyde in the 30,285-32,890 cm(-1) (304-330 nm) spectral region

Absolute room temperature (294 ± 2 K) absorption cross sections for the ?(1)A(2)-X?(1)A(1) electronic transition of formaldehyde have been measured over the spectral range 30,285-32,890 cm(-1) (304-330 nm) using ultraviolet (UV) laser absorption spectroscopy. Accurate high-resolution absorption cross sections are essential for atmospheric monitoring and understanding the photochemistry of this important atmospheric compound. Absorption cross sections were obtained at an instrumental resolution better than 0.09 cm(-1), which is slightly broader than the Doppler width of a rotational line of formaldehyde at 300 K (～0.07 cm(-1)) and so we were able to resolve all but the most closely spaced lines. Comparisons with previous data as well as with computer simulations have been made. Pressure broadening was studied for the collision partners He, O(2), N(2), and H(2)O and the resulting broadening parameters have been measured and increase with the strength of intermolecular interaction between formaldehyde and the collision partner. The pressure broadening coefficient for H(2)O is an order of magnitude larger than the coefficients for O(2) and N(2) and will contribute significantly to spectral line broadening in the lower atmosphere. Spectral data are made available as Supporting Information.     

Overloading control of gas chromatographic systems

Increasing the interlaboratory reproducibility of gas chromatographic retention indices requires avoiding measurements distorted by overloading effects. Several criteria of evaluating the limits of the mass overloading of gas chromatographic systems are compared and reconsidered. The criteria mostly appropriate for practical purposes are based on (i) the dependences of factors of peak broadening (ratio of peak height and its width) vs. amount of analyte injected into the chromatographic column and (ii) the dependence of parameters characterizing the peak distortion (asymmetry factor) vs. the amount of analyte. Both these criteria provide mutually comparable evaluations of the overloading limits for analytes of different polarity. At the same time, the dependence of retention indices vs. amounts of analyte injected in the chromatographic column cannot be recommended for overloading control, because the parameters of the corresponding linear regressions indicate temperature dependence. The interpretation of certain gas chromatographic anomalies requires the correct evaluation of overloading limits. For example, the unusual temperature dependence of retention indices of polar analytes on non‐polar stationary phases and the dependence of retention indices on ratio of amounts of target analytes and reference compounds.     

Motional narrowing in the time-averaging approximation for simulating two-dimensional nonlinear infrared spectra

The diagonal linewidth in two-dimensional infrared spectra is often narrower than the distribution of transition frequencies. The width along the antidiagonal is broader than predicted by the lifetime broadening. These effects arise from time-dependent fluctuations of the transition frequencies. They can be accounted for with a semiclassical approach. For systems with many coupled vibrational modes, this approach, however, becomes computationally too demanding to be practically applicable. A time-averaging approximation was suggested for linear infrared absorption spectra. In this paper, we demonstrate that the averaging can be optimized to fit a broader scale of frequency fluctuations by using a Gaussian weight function instead of the originally proposed box function. We further generalize the time-averaging method to allow the simulation of two-dimensional infrared spectra and demonstrate the method on a simple system. The approximation delivers a large speed-up of the calculation without losing significant accuracy.     

Mössbauer investigation of 57Fe-doped TlSr2CoO5

The thallium cobaltite TlSr₂CoO₅ undergoes a metal—insulator transition near room temperature. Mössbauer investigation of a ⁵⁷Fe-doped sample shows that iron actually enters into the lattice and that a long range antiferromagnetic order sets in below 150 K explaining the origin of a peak previously observed in the temperature dependence of the magnetic susceptibility. An unexpected complex behaviour is found for the high temperature phase for which previous electron diffraction and X-ray diffraction studies revealed a single site for Co atoms. The results are interpreted in terms of a dynamical formation of two types of structural domains characterized by a fluctuation of Co-O bond lengths inducing a fluctuation of Co spin state.     

VOPO4·H2O: a stacking faults structure studied by X-ray powder diffraction and DFT-D calculations

The dehydration process of VOPO(4)·2H(2)O occurs in two steps corresponding to successive elimination of the two crystallographically distinct water molecules. The intermediate phase VOPO(4)·H(2)O has been stabilized for X-ray powder diffraction studies. The resulting data suggest a tetragonal cell (a = 6.2203(2) ? and c = 6.18867(7) ?), but an important anisotropy in the line broadening points out the necessity of considering a not perfectly organized structure. Because of the layered structure of this compound, density functional theory calculations including dispersion corrections have been carried out to evaluate the possible presence of stacking faults. The results of these calculations give information about the nature of the translations and their probabilities using a Boltzmann distribution. DIFFaX+ simulations of the X-ray powder diffraction pattern have been carried out using the results of the theoretical calculations and confirm the presence and nature of stacking faults.     

Divergent dispersion behavior of ssDNA fragments during microchip electrophoresis in pDMA and LPA entangled polymer networks

Resolution of DNA fragments separated by electrophoresis in polymer solutions ("matrices") is determined by both the spacing between peaks and the width of the peaks. Prior research on the development of high-performance separation matrices has been focused primarily on optimizing DNA mobility and matrix selectivity, and gave less attention to peak broadening. Quantitative data are rare for peak broadening in systems in which high electric field strengths are used (>150 V/cm), which is surprising since capillary and microchip-based systems commonly run at these field strengths. Here, we report results for a study of band broadening behavior for ssDNA fragments on a glass microfluidic chip, for electric field strengths up to 320 V/cm. We compare dispersion coefficients obtained in a poly(N,N-dimethylacrylamide) (pDMA) separation matrix that was developed for chip-based DNA sequencing with a commercially available linear polyacrylamide (LPA) matrix commonly used in capillaries. Much larger DNA dispersion coefficients were measured in the LPA matrix as compared to the pDMA matrix, and the dependence of dispersion coefficient on DNA size and electric field strength were found to differ quite starkly in the two matrices. These observations lead us to propose that DNA migration mechanisms differ substantially in our custom pDMA matrix compared to the commercially available LPA matrix. We discuss the implications of these results in terms of developing optimal matrices for specific separation (microchip or capillary) platforms.     

The motional model in the electron spin relaxation of large Mn(II) complexes: Rotational or fluctuational process?

The solution ESR spectra of Mn(II) bound to ATP have been analyzed at three microwave frequencies. The liquid-type relaxation process induced by rapid fluctuations of the crystal-field symmetry does not account for the frequency dependence of the linewidth. The ESR lineshapes are better explained in terms of a static distribution of crystalfield sites which induces field dependent inhomogeneous broadening.     

Modeling ssDNA electrophoretic migration with band broadening in an entangled or cross-linked network

We use a coarse-grained model proposed by Graham and Larson based on the temporary network model by Schieber et al.. [1] to simulate the electrophoretic motion of ssDNA and corresponding band broadening due to dispersion. With dimensionless numbers reflecting the experimental physical properties, we are able to simulate ssDNA behavior under weak to moderate electric field strengths for chains with 8-50 entanglements per chain ( approximately 1000-8500 base pairs), and model smoothly the transition from reptation to oriented reptation. These results are fitted with an interpolation equation, which allows the user to calculate dimensionless mobilities easily from input parameters characterizing the gel matrix, DNA molecules, and field strengths. Dimensionless peak widths are predicted from mobility fluctuations using the central limit theorem and the assumption that the mobility fluctuations are Gaussian. Using results from previous studies of ssDNA physical properties (effective charge xiq and Kuhn step length b(K)) and sieving matrix properties (pore size or tube diameter a), we give scaling factors to convert the dimensionless values to "real" experimental values, including the mobility, migration distance, and time. We find that the interpolation equation fits well the experimental data of ssDNA mobilities and peak widths, supporting the validity of the coarse-grained model. The model does not account for constraint release and hernia formation, and assumes that the sieving network is a homogeneous microstructure with no temperature gradients and no peak width due to injection. These assumptions can be relaxed in future work for more accurate prediction.