Subsurface Raman imaging with nanoscale resolution

We report on chemically specific, subsurface imaging with high spatial resolution. Using tip-enhanced Raman spectroscopy, we probe carbon nanotubes buried beneath a host dielectric media. We demonstrate our ability to map and resolve specific vibrational modes with 30 nm spatial resolution for dielectric layers with different thicknesses.     

Effect of hydrocarbon chain length of amphiphilic ruthenium dyes on solid-state dye-sensitized photovoltaics

We studied the influence of the hydrophobic hydrocarbon chain length of amphiphilic ruthenium dyes on the device performance in solid-state dye-sensitized solar cells. We found that the dyes with longer hydrocarbon chains gave higher efficiency values when used as a sensitizer in solid-state dye-sensitized solar cells. With increasing chain length, we observed higher currents and open-circuit voltages up to a limiting chain length. We attribute this improvement to the expected larger distance between TiO2 and the hole conductor, which seems to suppress recombination effectively.     

Mass + retention time = structure: a strategy for the analysis of N-glycans by carbon LC-ESI-MS and its application to fibrin N-glycans

Analysis of the numerous possible, often isobaric structures of protein-bound oligosaccharides calls for a high-performance two-dimensional method that combines liquid chromatography's ability to separate isomers and mass spectrometry's ability to determine glycan composition. Here we investigate the usefulness of porous graphitic carbon columns coupled to ESI-MS for the separation of N-glycans with two or more sialic acids. Internal standards helped to rectify retention time fluctuations and thus allowed elution times to play an essential role in the structural assignment of peaks. For generation of a retention time library, standards representing the possible isomers of diantennary non-, mono-, and disialylated N-glycans, differing in the linkage of galactose and sialic acids as well as isobaric hybrid-type N-glycans, were produced using recombinant glycosyltransferases. Once the retention times library was established, isomers could be identified by LC-ESI-MS in the positive mode without additional MS/MS experiments. The method was applied for the detailed structural analysis of fibrin(ogen) N-glycans from various species (human, cow, pig, mouse, rat, cat, dog, Chinese hamster, horse, sheep, and chicken). All fibrins contained diantennary N-glycans. They differed in the occurrence of beta1,3-linked galactose, alpha2,3-linked sialic acids, and N-glycolylneuraminic acid, in the mono/diantennary glycan ratio, and in the O-acetylation of neuraminic acids. The separation system's potential for analyzing tri- and tetrasialylated N-glycans was demonstrated.     

Polymer on Top: Current Limits and Future Perspectives of Quantitatively Evaluating Surface Grafting

Well‐defined polymer strands covalently tethered onto solid substrates determine the properties of the resulting functional interface. Herein, the current approaches to determine quantitative grafting densities are assessed. Based on a brief introduction into the key theories describing polymer brush regimes, a user's guide is provided to estimating maximum chain coverage and—importantly—examine the most frequently employed approaches for determining grafting densities, i.e., dry thickness measurements, gravimetric assessment, and swelling experiments. An estimation of the reliability of these determination methods is provided via carefully evaluating their assumptions and assessing the stability of the underpinning equations. A practical access guide for comparatively and quantitatively evaluating the reliability of a given approach is thus provided, enabling the field to critically judge experimentally determined grafting densities and to avoid the reporting of grafting densities that fall outside the physically realistic parameter space. The assessment is concluded with a perspective on the development of advanced approaches for determination of grafting density, in particular, on single‐chain methodologies.     

Imprinting localized plasmons for enhanced solar cells

Imprinted silver nanovoid arrays are investigated via angle-resolved reflectometry to demonstrate their suitability for plasmonic light trapping. Both wavelength-?and subwavelength-scale nanovoids are imprinted into standard solar cell architectures to achieve nanostructured metallic electrodes which provide enhanced absorption for improving solar cell performance. The technique is versatile, low-cost and scalable and can be applied to a wide range of organic semiconductors. Absorption features which are independent of incident polarization and weakly dependent on incident angle reveal localized plasmonic modes at the structured interface. Metallic nanostructure-PCPDTBT:PCBM samples demonstrate absorption enhancements of up to 40%. The structured interface provides light trapping, which boosts absorption at wavelengths where the semiconductors absorb poorly.     

Quadrature frequency resolved spectroscopy of upconversion photoluminescence in GeGaS:Er<Superscript>3+</Superscript>: I. Determination of energy transfer upconversion parameter

The article presents the formulas of quadrature frequency resolved spectroscopy (QFRS) on the upconversion photoluminescence (UCPL) of rare-earth (RE) doped materials on the general M-level model. The formulas are derived in matrix-equation form with the first-order perturbation on the rate equations at the M energy-levels of RE ion. The QFRS spectra for three different UCPL processes, i.e., the excited state absorption (ESA), energy transfer upconversion (ETU) and photon avalanche (PA) via cross relaxation process (CRP) in a particular case of M?=?3 are demonstrated with the respective salient features of the excitation power dependence. We have measured the QFRS on the UCPL (⁴ S _3/2 → ⁴ I _15/2) by systematically varying Er-doping in Ge_28.1Ga_6.3S_65.6 chalcogenide glass from 0.01 to 0.5 at.% as well as 975 nm excitation power. Thereby the relaxation rates k ₁ at the intermediate level ⁴ I _11/2, k ₂ at the top level ⁴ S _3/2 and ETU parameter w are determined as a function of Er concentration. The UCPL dynamics on the basis of the formulas for the 3-level model is interpreted in terms of the determined parameters.     

Intersublevel Spectroscopy on Single InAs-Quantum Dots by Terahertz Near-Field Microscopy

Using scattering-type near-field infrared microscopy in combination with a free-electron laser, intersublevel transitions in buried single InAs quantum dots are investigated. The experiments are performed at room temperature on doped self-assembled quantum dots capped with a 70 nm GaAs layer. Clear near-field contrast of single dots is observed when the photon energy of the incident beam matches intersublevel transition energies, namely the p-d and s-d transition of conduction band electrons confined in the dots. The observed room-temperature line width of 5-8 meV of these resonances in the mid-infrared range is significantly below the inhomogeneously broadened spectral lines of quantum dot ensembles. The experiment highlights the strength of near-field microspectroscopy by demonstrating signals from bound-to-bound transitions of single electrons in a probe volume of the order of (100 nm)(3).     

Real-time, on-line characterization of diesel generator air toxic emissions by resonance-enhanced multiphoton ionization time-of-flight mass spectrometry

The laser-based resonance-enhanced multiphoton ionization time-of-flight mass spectrometry (REMPI-TOFMS) technique has been applied to the exhaust gas stream of a diesel generator to measure, in real time, concentration levels of aromatic air toxics. Volatile organic compounds, as well as several polycyclic aromatic hydrocarbons were detected in the concentration range of 10-200 ppb in the steady-state diesel generator exhaust. The results were verified and compared with conventional extractive sampling and analytical techniques using gas chromatography/mass spectrometry (GC/MS). The high isomer selectivity of the REMPI-TOFMS instrument provided data for individual xylene isomers that are otherwise (partially) coeluting in standard GC/MS analyses. Good agreement was observed between results for volatile and semivolatile organic compounds obtained with REMPI-TOFMS and conventional extractive sampling. Transient events, such as cold start-ups of the diesel generator, resulted in sharp (less than 15 s) peak emissions that were, for benzene, up to a factor of 90 higher than the predominately constant concentrations observed during steady-state operation; warm restarts resulted in lower peak concentrations by a factor of 2.5. These fast transient emissions are only detectable using a real-time approach (1-s resolution) as demonstrated here using REMPI-TOFMS.     

Innovative focused ultrasound-based sealing method of flexible packaging films—Principles and characteristics

A key process to package goods is the closure procedure. It ensures the good protection against the environment and vice versa. Ultrasonic sealing presents the advantage of converting locally ultrasound into heat, which is optimal for temperature sensitive goods. The disadvantages remain, however, the equipment cost, the noise generation, and the process sensitivity to materials. It is necessary to develop a sealing process to decrease the acquisition cost of the sealing equipment and cover a wide range of polymer films. This paper focuses on a new sealing method based on high-intensity focused ultrasound. The principles and characteristics of this process are discussed and underpinned with experimental results. Both the acoustic and thermal effects of the sealing process are summarized. A study of the process parameter impact on the seam strength in static and dynamic operating is proposed. Low-density polyethylene films with a carrier layer of bi-oriented polypropylene and polyethylene terephthalate are used. A first test bench generates point-shaped seam. The heat generation is recorded with an infrared thermography system. A second test bench, a horizontal form fill and seal machine, produces longitudinal seams. The seam quality is controlled by tensile test and tightness test. A quick heating of the polymer films is found. Point seams and longitudinal seams are successfully generated. The seams behave similarly to the ones generated with ultrasonic sealing process. However, the sealing velocity is limited to 3 m/min. This work provides a summary of the characteristics and principles of the new sealing method in packaging applications.