From micro to nano: analysis of surface-enhanced resonance Raman spectroscopy active sites via multiscale correlations

Effective correlation of data from a number of analytical techniques over length scales spanning several orders of magnitude is required to more fully investigate the active sites on silver nanoparticles that are responsible for surface-enhanced resonance Raman scattering (SERRS). In this paper, a method is presented that uses fluorescent beads as optical markers to allow direct correlation between a SERRS/fluorescence map and a transmission electron microscope (TEM) collage of the same area. Factors influencing the accuracy of the technique include the flatness of the substrate, the size of the fluorescent beads, and the strength of the signal from the fluorescent beads. When the effect of each of these factors on the technique is addressed, a simple and accurate correlation between the optical spectroscopy and the electron microscopy is achieved. A statistically significant number of particles can then be easily and reliably located and characterized at both optical limits, by SERRS, and with subnanometer resolution in the high-resolution TEM. Examples of HRTEM images and the locations of these particles within the SERRS map/TEM collage are presented. Our findings reveal that the relative SERRS activity of single particles is very low compared to dimers and larger aggregates of particles. The relative activity of dimers is estimated to be 12.4 times greater than single particles, and as the number of particles in the aggregate increase, the relative SERRS activity also increases. The relative SERRS activities of single particles/dimers/trimers/aggregates of 4-9 particles/aggregates of 10-20 are estimated to be 1/12.4/15.6/23.2/43.     

Characterization of hemoglobin variants by MALDI-TOF MS using a polyurethane membrane as the sample support

A new method for the sampling and off-site analysis of hemoglobin variants by mass spectrometry is reported. This technique uses a nonporous polyurethane membrane as the collection device and transportation medium of a blood sample for analysis. The same membrane is then used as the MALDI-TOF MS sample support for mass spectrometric analysis. Minimal invasive sample collection is afforded by collecting less than 1 microL of blood using a common lancet device. MALDI-TOF MS is performed directly on the membrane, after washing off the interfering plasma components, followed by the addition of matrix. This reduces the time of analysis and prevents sample loss. Enzymatic digestion can be performed directly on the membrane, using in this case trypsin, allowing for further characterization of the sample. The method is much less invasive compared to drawing blood with a syringe. The sample may be transported to the laboratory by regular mail, and thus the method can serve remote locations. We demonstrate the procedure by characterizing the Hb Shepherds Bush hemoglobin variant, b74-(E18)Gly-->Asp.     

Experience with use of extended length peritoneal shunt catheters

The placement of a ventriculoperitoneal (VP) shunt is the current treatment of choice for diversion of cerebrospinal fluid associated with hydrocephalus. Although there are a host of reported potential abdominal complications related to the procedure, they are notably uncommon. The authors report their experience with the primary insertion of an extended length open-ended peritoneal tubing (120 cm) undertaken expressly to avoid the need for a lengthening procedure because of growth of the patient. In a review of new insertions of VP shunts using the extended length tubing over a 14-year period at Childrens Hospital of Los Angeles, a total 998 shunts were placed in 952 patients, with a mean follow-up period of 6.7 years. The patients experienced a total of 52 distal shunt revisions for a variety of malfunction etiologies. In patients ranging in age from premature neonate to 20 years, there was no increase in the distal complication rate, and specifically no complications were experienced that were directly related to the use of the extended length tubing. The authors conclude that the use of an extended length peritoneal shunt catheter is not associated with an increase in complications and eliminates the need to lengthen the peritoneal catheter for growth of the patient.     

ELNES investigations of the oxygen K-edge in spinels

The results of a systematic study of the oxygen K-edge electron energy-loss spectroscopy (ELNES) from a series of aluminium- and chromium-containing spinels are presented. Extra fine structure in the region up to 10 eV above the edge onset is observed for the chromium-containing compounds and is assigned to transitions to states created by mixing of oxygen 2p and metal 3d orbitals. The experimental data has been simulated using the multiple scattering code, FEFF8. Good agreement was obtained in the case of magnesium aluminate, but relatively poor agreement was obtained in the case of the chromites. The possible fingerprints in the oxygen K-edge ELNES corresponding to a high degree of inversion the spinel structure and to a tetragonal distortion of the cubic structure are discussed.     

Turbulent energy transfer in a nonlinear isotropic fluid

In this paper we consider a hypothetical non-Newtonian fluid, in which the usual Newtonian constitutive relationship is perturbed by the presence of a small quadratic term. It is argued that this model is worth studying because (a) such non-linearities are believed to lead to anomalous turbulent effects, (b) it is a necessary preliminary to a full treatment of a more realistic model, which takes account of fluid anisotropy. The equations of motion are derived in the Fourier wavenumber-time domain and specialised to the case of isotropic turbulence. Recent developments in the theory of turbulence are used to obtain a closed equation for the energy spectrum and this is solved for the dissipation-range energy spectrum. It is concluded that the inertial transfer of turbulent energy is reduced in such a way that the spectrum contains more energy, but falls off more rapidly, than in the Newtonian case.     

Preparation of polyacryloamidoxime chelating cloth for the extraction of heavy metals from water

Woven polyacryloamidoxime cloth was prepared from the polyacrylonitrile precursor via reaction in methanolic hydroxylamine. Preparation was controllable and reproducible and the reaction conditions were optimized with respect to the time of conversion, the concentration of NH₂OH⋅HCl, and the temperature of conversion. The cloth produced had a large capacity for Cu(II) and Pb(II) of 71.2 and 450 mg g^7minus;1 (1.12 and 2.17 mmol g⁻¹) respectively, and adequate physical properties suitable for rigorous use. Sorption profiles of Pb(II) and Cu(II) were similar to those of chelate ion exchange resins and fibers containing the amidoxime group. The rate of uptake of metals by the cloth was found to be dependent on the percent surface area converted to amidoxime groups, the concentration and type of metal being tested for, and the time of exposure. Anomalous kinetics of sorption for Pb(II) and Cu(II) by cloth of increasing amidoxime group content were explained by a two-part sorption mechanism. Distribution coefficients of 3.5 × 10⁶ and 1.5 × 10⁶ for Cu(II) and Pb(II) were observed, and the average rates of uptake for Cu(II) and Pb(II) were 600 and 200 μg g⁷⁻¹ day⁻¹ (9.4 and 0.96 μmol g⁷⁻¹ day⁻¹), respectively, from dilute solution ([Cu] = 5.9 μg L⁻¹, [Pb] = 2.8 μg L⁻¹). Treatment of the cloth with aqueous NaOH did not improve the capacities for Pb(II) and Cu(II). © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1175–1192, 1997     

Probing Local and Global Ferroelectric Phase Stability and Polarization Switching in Ordered Macroporous PZT

We describe the characterization, ferroelectric phase stability and polarization switching in strain‐free assemblies of PbZr_0.3Ti_0.7O₃ (PZT) nanostructures. The 3‐dimensionally ordered macroporous structures present uniquely large areas and volumes of PZT where the microstructure is spatially modulated and the composition is homogeneous. Variable temperature powder X‐ray diffraction (XRD) studies show that the global structure is crystalline and tetragonal at room temperature and undergoes a reversible tetragonal to cubic phase transition on heating/cooling. The measured phase‐transition temperature is 50–60 °C lower than bulk PZT of the same composition. The local ferroelectric properties were assessed using piezoresponse force spectroscopy that reveal an enhanced piezoresponse from the nanostructured films and demonstrate that the switching polarization can be spatially mapped across these structures. An enhanced piezoresponse is observed in the nanostructured films which we attribute to the formation of strain free films, thus for the first time we are able to assess the effects of crystallite‐size independently of internal stress. Corresponding polarization distributions have been calculated for the bulk and nanostructured materials using a direct variational method and Landau‐Ginzburg‐Devonshire (LGD) theory. By correlating local and global characterization techniques we have for the first time unambiguously demonstrated the formation of tetragonal and ferroelectric PZT in large volume nanostructured architectures. With the wide range of materials available that can be formed into such controlled architectures we conclude that this study opens a pathway for the effective studies of nanoscale ferroelectrics in uniquely large volumes.     

System Project Failure: The Heuristics of Risk

System project failures are a well-known part of systems development; however, all the potential risks of planning and executing a project effort are not This article offers heuristic guidelines to help IS managers assess these inherent risk factors before initiating and while executing a project. Case examples illustrate how a particular risk factor can result in a failed systems development effort.     

Unreinforced Concrete Masonry Walls Strengthened with CFRP Sheets and Strips under Pendulum Impact

Impact tests using drop-weight pendulum on nine 1.2-m-high full-scale concrete masonry block walls were conducted to investigate the out-of-plane impact behavior of unreinforced masonry (URM) walls externally strengthened with carbon-fiber-reinforced polymer (CFRP) composites. Three strengthening schemes on one side of the wall were studied: continuous unidirectional and continuous woven sheets, discrete strips in a vertical pattern, and discrete strips in orthogonal and diagonal patterns. All walls were vertically positioned resting on a knife-edge support with one face leaning against two steel rollers close to the upper and lower edges of the wall. The impact load was applied at the wall center through a drop-weight pendulum impact tester with various drop heights. Test results revealed that using composite laminates or strips could significantly improve the impact performance of URM walls. The wall strengthened with continuous woven sheets performed better than the one with unidirectional sheet. With the same amount of fiber-reinforced polymer strip material, the wall with narrower but more closely spaced strips performed slightly better than the one with wider strips.