We studied the genetic polymorphism of beta-lactoglobulin (β-Lg) whey protein in Gangatiri zebu cows for this Research Communication. The polymorphic nature of milk protein fractions and their association with milk production traits, composition and quality has attracted several efforts in evaluating the allelic distribution of protein locus as a potential dairy trait marker. Genetic variants of β-Lg have highly significant effects on casein number (B > A) and protein recovery (B > A) and also determine the yield of cheese dry matter (B > A). Molecular techniques of polyacrylamide gel electrophoresis and high-resolution accurate mass-spectroscopy were applied to characterize the β-Lg protein obtained from the Gangatiri breed milk. Sequence analysis of β-Lg showed the presence of variant B having UniProt database accession number P02754, coded on the PAEP gene. Our study can provide reference and guidance for the selection of superior milk (having β-LgB) from this indigenous breed that could potentially give a good yield of β-Lg for industrial applications.

Plastics generally play a very important role in a plethora of industries, fields and our everyday lives. In spite of their cheapness, availability and important contributions to lives, they however, pose a serious threat to the environment due to their mostly non-biodegradable nature. Recycling into useful products can reduce the amount of plastic waste. Thermal degradation (Pyrolysis) of plastics is becoming an increasingly important recycling method for the conversion of plastic materials into valuable chemicals and oil products. In this work, waste Polyethylene terephthalate (PET) water bottles were thermally converted into useful gaseous and liquid products. A simple pyrolysis reactor system has been used for the conversions with the liquid product yield of 65 % at a temperature range of 400°C to 550°C. The chemical analysis of the pyrolytic oil showed the presence of functional groups such as alkanes, alkenes, alcohols, ethers, carboxylic acids, esters, and phenyl ring substitution bands. The main constituents were 1-Tetradecene, 1-Pentadecene, Cetene, Hexadecane, 1-Heptadecene, Heptadecane, Octadecane, Nonadecane, Eicosane, Tetratetracontane, 1-Undecene, 1-Decene). The results are promising and can be maximized by additional techniques such as hydrogenation and hydrodeoxygenation to obtain value-added products.

Using the data obtained by Knudsen effusion mass spectrometry, the standard formation thermodynamic properties of La2Hf2O7, Nd2Hf2O7, and Gd2Hf2O7 were calculated in the present study at high temperatures. Based on the results obtained, it was shown that the standard formation Gibbs energies of La2Hf2O7, Nd2Hf2O7, and Gd2Hf2O7 from the elements at the temperature 2445 K were consistent with the empirical rule concerning decrease of stability of pyrochlore hafnate phase with decrease in lanthanoid ionic radius. The La2Hf2O7 and Gd2Hf2O7 heat capacities were obtained in the present study by differential scanning calorimetry. These data were used along with those found earlier to evaluate the standard formation Gibbs energies of La2Hf2O7 and Gd2Hf2O7 from the elements at the temperature 298 K, which equal (−3937 ± 10) kJ/mol and (−3895 ± 10) kJ/mol, respectively. The thermodynamic properties of La2Hf2O7, Nd2Hf2O7, and Gd2Hf2O7 estimated in a wide temperature range allowed consideration of reliability of data available in the literature.

Pulsed coherent extreme ultraviolet (EUV) radiation is a potential alternative to pulsed near-ultraviolet (NUV) wavelengths for atom probe tomography. EUV radiation has the benefit of high absorption within the first few nm of the sample surface for elements across the entire periodic table. In addition, EUV radiation may also offer athermal field ion emission pathways through direct photoionization or core-hole Auger decay processes, which are not possible with the (much lower) photon energies used in conventional NUV laser-pulsed atom probe. We report preliminary results from what we believe to be the world’s first EUV radiation-pulsed atom probe microscope. The instrument consists of a femtosecond-pulsed, coherent EUV radiation source interfaced to a local electrode atom probe tomograph by means of a vacuum manifold beamline. EUV photon-assisted field ion emission (of substrate atoms) has been demonstrated on various insulating, semiconducting, and metallic specimens. Select examples are shown.

Porphyrins are vital pigments involved in biological energy transduction processes. Their abilities to absorb light, then convert it to energy, have raised the interest of using porphyrin nanoparticles as photosensitizers in photodynamic therapy. A recent study showed that self- assembled porphyrin-silica composite nanoparticles can selectively destroy tumor cells, but detection of the cellular uptake of porphyrin-silica composite nanoparticles was limited to imaging microscopy. Here we developed a novel method to rapidly identify porphyrin-silica composite nanoparticles using Atmospheric Solids Analysis Probe-Mass Spectrometry (ASAP-MS). ASAP-MS can directly analyze complex mixtures without the need for sample preparation. Porphyrin-silica composite nanoparticles were vaporized using heated nitrogen desolvation gas, and their thermo-profiles were examined to identify distinct mass- to-charge (M/Z) signatures. HeLa cells were incubated in growth media containing the nanoparticles, and after sufficient washing to remove residual nanoparticles, the cell suspension was loaded onto the end of ASAP glass capillary probe. Upon heating, HeLa cells were degraded and porphyrin-silica composite nanoparticles were released. Vaporized nanoparticles were ionized and detected by MS. The cellular uptake of porphyrin-silica composite nanoparticles was identified using this ASAP-MS method.

In the safety assessment of a radioactive waste disposal, it is extremely important to assess the migration behavior of long-half-life radionuclides in the disposal environment. The migration behavior in the disposal environment for a radionuclide varies with the chemical form of the nuclide. In particular, C-14 has various chemical forms, and its migration behavior in the disposal environment substantially varies with the chemical forms. It has been reported that hardly soluble C-14 is generated in PWRs. However, the chemical form of this hardly soluble C-14 is little known. In this study, the thermal decomposition behavior of particles containing C-14 and the mass spectra of gases released through thermal decomposition were analyzed in order to examine the chemical form of C-14 generated in PWRs. In this study, the gases released during the thermogravimetric (TG) analysis were partially oxidized to CO2, trapped in an alkaline solution and analysed for C-14. Another part of the gas was analysed directly by mass spectrometry (MS). The residues obtained after TG analysis were also analysed for C-14 by oxidizing the residue to CO2, trapping the CO2 in alkaline solutions and analysing C-14 by LSC. During TG-analysis in inert gas (He) atmosphere, about 90% of C-14 was found in residue, while when air was used during TG-analysis, no C-14 could be detected in residue. From the MS-analysis of species released during TG-analysis in inert gas, fragments regarded as originating from ion-exchange resins were detected in released gases. Based on this result, it was found that while substances originating from ion-exchange resin were present in radioactive particles generated in a PWR, the main part of C-14 was contained in the residue after heating in the form of thermally stable substances, easy to be oxidized by air at high temperature. It was not possible to determine their exact chemical composition in this work but also, In addition, sorption of insoluble C-14 to cementitious materials was preliminarily examined. As a results, the concentration of insoluble C-14 decreased greatly in 7 days. That means insoluble C-14 tended not to stay in water. Elucidation of the sorption mechanism in the disposal environment of these C-14 is also a future task.

The application of safeguards measures by the International Atomic Energy Agency (IAEA) involves analytical measurements of samples taken during inspections of nuclear facilities. Thus constant development and advancement of analytical techniques is required. For quality control purposes, the IAEA has implemented a dedicated project to enhance its analytical capabilities by producing tailor-made reference materials for the analysis of uranium isotope signatures in (single) particles.

To this end, a particle production set-up was developed and implemented at Forschungszentrum Juelich capable to produce uranium oxide microparticles which are intended to be used as (certified) reference materials for particle analysis methods. A step towards the certification process is the evaluation of consistency of the size distribution and homogeneity. A monodisperse particle size distribution as well as the single phase triuranium octoxide structure was confirmed using SEM, µ-XRD and µ-Raman spectroscopy, respectively. Analysis performed on single uranium oxide microparticles confirmed consistency of the uranium isotopic ratios in comparison to the initial precursor solutions. To improve the homogeneity and particle handling, the particles are transferred into suspensions, for which the stability was investigated with respect to dissolution.

Synthetic organic pigments (SOPS) find wide use in modern and contemporary works of art. These laboratory-made pigments are used in many fields, including industrial and architectural paints, printing inks, plastics, textiles, and artists’ materials. They have been examined by a variety of techniques including spectroscopic methods such as Fourier transform infrared spectroscopy (FTIR), Raman, and X-ray powder diffraction (XRD) as well as chromatographic or mass spectrometric techniques such as pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) and laser desorption ionization mass spectrometry (LDI-MS). Often, a combination of techniques has been used to examine these pigments. Previously, we used a combination of Raman spectroscopy and LDI-MS to characterize commercially available SOPS. However, many pigments, termed “historical” are no longer manufactured, and therefore, may not have been characterized. This paper describes the synthesis of members of several classes of SOPS and their characterization.

Frequently, fundamental scientific and technological issues are related to the chemical structure of a material at the nanometer or even atomistic length scales. This includes, but is not limited to, internal interfaces of complex topology as they appear, for example, in current energy-harvesting applications or advanced microelectronics. Scientific understanding of the underlying physics and chemistry requires advanced characterization tools that provide critical three-dimensional information at the subnanometer length scale. Atom probe tomography (APT) meets such requirements. Today, with remarkable progress in instrumentation and sample preparation, APT has become a very versatile tool to address fundamental questions of materials science. In this issue of MRS Bulletin, the APT technique is introduced, with a particular focus on recent developments and the broadening range of studied material classes and applications.

Desorption of gold ions from liver tissue sections, in which intravenously injected gold nanorods were accumulated, were studied to evaluate properties of gold nanorods as a "mass-tag". Gold ions were sensitively detected by using a conventional MALDI-MS machine. When 50-µm-thick blank sections without gold nanorods were placed on or beneath a sample section, desorption of gold ions was almost suppressed. It was found that the escape depth of gold ions from liver tissue sections was less than 50 µm. It was found that we do not have to take account of the escape depth of gold ions if a section were sliced into 10-20 µm thickness.

Mass spectrometry is one of the primary analysis techniques for biological analysis but there are technological barriers in sampling scale that must be overcome for it to be used to its full potential on the size scale of single cells. Current mass spectrometry imaging methods are limited in spatial resolution when analyzing large biomolecules. The goal of this project is to use atomic force microscope (AFM) tip enhanced laser ablation to remove material from cells and tissue and capture it for subsequent mass spectrometry analysis. The laser ablation sample transfer system uses an AFM stage to hold the metal-coated tip at a distance of approximately 10 nm from a sample surface. The metal tip acts as an antenna for the electromagnetic radiation and enables the ablation of the sample with a spot size much smaller than a laser focused with a conventional lens system. A pulsed nanosecond UV or visible wavelength laser is focused onto the gold-coated silicon tip at an angle nearly parallel with the surface, which results in the removal of material from a spot between 500 nm and 1 µm in diameter and 200 and 500 nm deep. This corresponds to a few picograms of ablated material, which can be captured on a metal surface for MALDI analysis. We have used this approach to transfer small peptides and proteins from a thin film for analysis by mass spectrometry as a first step toward high spatial resolution imaging.

We present herein a joint physical/physico-chemical study and, more specifically, the first application of Matrix Assisted Laser Desorption Ionization coupled with Time of Flight Mass Spectrometry (MALDI-TOF-MS) to analyze small-sized ZnO quantum dots (QDs) (2.8-3.1 nm diameter range) synthesized by sol-gel chemistry and stabilized through an aminosilane coating. A careful investigation of the stability of ZnO QDs was initiated once these dots were dispersed in different media (water, biological buffer) for a period up to 3 weeks. Positive ion mode mass spectra MALDI-TOF-MS combined with optical spectrometry was used to monitor the stability of ZnO QDs when aging. Such a unique combination of MALDI-TOF-MS and physico-chemical techniques is likely to bring new insights into the structure analysis, the stability and consequently the potential toxicity of QDs.

The solvation of cations and anions in a lithium-containing electrolyte was studied using electrospray ionization mass spectrometry (ESI-MS) combined with nuclear magnetic resonance (NMR) and electrochemical testing. The purpose of these experiments was to develop an understanding of the solvation of the small, hard Li+ cation and the more cryptic nature of the solvation of poorly-coordinating anions such as PF6- and BF4-. It has long been held that the passivation of graphitic anodes in lithium ion batteries is a solvation-driven process, meaning that whatever solvent molecules surround the Li+ cation will provide the raw material for the formation of the solid electrolyte interphase (SEI) layer. Because the SEI is a critical component, and because a binary solvent system is normally used in lithium batteries, it is necessary to understand the competitive nature of lithium solvation. Conversely, the anion can be chemically active even if poorly coordinating; therefore, it was desired to see if a competitive solvation condition exists for the anion as well. Results indicate that Li+ has a strong preference for cyclic carbonates like ethylene carbonate (EC) over linear carbonates, where the anions had a mixed preference. It is thought that anion solvent preference might dictate oxidative chemistry that occurs on the cathode, while the anion also significantly participates in the formation of SEI on the anode.

Because of the high energy density, easy ignition, and good storability, mechanically alloyed Al·Mg powder has the potential to improve the performance characteristics of various energetic and gas-generating materials. Here, the use of this powder in combustible mixtures for generation of oxygen and hydrogen is explored. The mixtures for oxygen generation consisted of sodium chlorate, nanoscale cobalt oxide catalyst, and Al·Mg powder, while those for hydrogen generation included water, polyacrylamide as a gellant, and Al·Mg powder. To increase hydrogen yield, ammonia borane (NH3BH3) was also added to Al·Mg − water mixtures. Combustion experiments were conducted in an argon environment, using laser ignition. The thermal wave propagation over the oxygen-generating mixtures was studied using infrared video recording. It has been shown that mechanically alloyed Al·Mg material is a promising alternative to currently used iron because significantly smaller amounts of this additive are needed for a steady propagation of the combustion wave. The hydrogen generation experiments have shown that mixtures of mechanically alloyed Al·Mg powder with 10−60 wt% gelled water are combustible, with the front velocities exceeding the values obtained for the mixtures of water with nanoscale Al. Hydrogen yield was measured using mass-spectrometry. In the mixtures that included ammonia borane, D2O was used instead of H2O. Measurements of H2, D2, and HD concentrations in the product gas provided insight into the reaction mechanisms. The isotopic tests have shown that AB participates in two parallel processes − thermolysis and hydrolysis, thus increasing hydrogen yield.

A combination of FTIR, normal Raman, SERS, Py-GC/MS and XRF was used to analyze commercial bistre samples to determine specific biomarkers that will allow for a rapid identification of the pigment in works of art. The results of the XRF analysis showed that potassium, calcium and iron are the main elements present. Characteristic bands belonging to phenolic components of lignin were observed in the FTIR spectra. The SERS analysis provided a fingerprint that may originate in the polymerization of the phenolic components catalyzed by the presence of the nanostructured silver surface under alkaline conditions. The Py-GC/MS analysis revealed the presence of lignin and cellulose biomarkers and a series of polycyclic aromatic hydrocarbons. The similarities observed between the commercial samples studied suggest that both originate in the same raw material, hardwood. The results demonstrate the potential of the multi-technique approach used for the characterization of this complex black-brown pigment.

Optical biosensor for monitoring proteolytic activity is constructed by DNA-directed immobilization of enzymes onto porous Silicon nanostructures. This sensor configuration allows both protease recycling and easy surface regeneration for subsequent biosensing analysis by means of mild dehybridization conditions. We demonstrate real-time analysis of minute quantities of proteases paving the way for substrate profiling and the identification of cleavage sites. The biosensor is compatible with common proteomic methods and allows for a successful downstream mass spectrometry analysis of the reaction products.

A T-Jump/Time-of-Flight Mass Spectrometer (T-Jump/TOFMS) is used to probe the decomposition of several aminotetrazole containing energetic materials under very high heating rates of 105-106 K/s. Subtle differences between materials in functional group placement and anion composition allow for further understanding of the decomposition pathway of the tetrazole structure and various anions. Two decomposition pathways for the tetrazole ring are observed, which result in the primary formation of HN3 or N2. Further analysis is performed using a rapid-heating μ-DSC device, which revealed lower activation energies than previously reported.

Gold nanorods (NRs) were fixed on an ITO plate and used for the Surface-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry (SALDI-MS) of oligopeptides (angiotensin I). The SALDI-MS measurements had a high sensitivity to the angiotensin on the ITO plate on which isolated NRs were deposited. Angiotensin molecules in a very diluted solution (1 × 10-11 M) could be detected at m/z = 1297 with a good signal/noise ratio (S/N = 18). In contrast, alternatively deposited NR an ITO plate, which present broad surface plasmon bands, was found to be inactive for SALDI measurements.

Gelatin was functionalized with glycidyl methacrylate and photocrosslinked in the presence of poly(ethylene glycol) dimethacrylate (PEGDMA) or poly(ethylene glycol) monomethacrylate (PEGMA) to create a biopolymer-based system with tailorable properties. These co-networks were hydrolyzed using 6 M HCl and the degradation products were analyzed and identified using matrix-assisted laser desorption/ionization-time of flight (MALDI-TOF) mass spectrometry. This technique successfully identified gelatin-derived peptides such as FLPEPPE, SFLPEPPE, and SFLPEPPEE as well as an accompanying PEG-g-poly(methacrylic acid) component. No oligo- or polymethacrylates were monitored at any molecular weight range above m/z = 500, which indicated that they possessed lower molecular weights. An in vitro hydrolytic degradation experiment performed in pH 7.4 PBS buffer solution at 37 °C showed that these networks, which were prepared without the addition of a potentially toxic photoinitiator, exhibited mass loss of up to 50 wt% at 6 weeks of incubation time. These results provide valuable insight into how these functional gelatin-based co-network biomaterials will perform in a biological setting.

The benefits of using kinetic-energy information to aid ion discrimination in atom probe tomography (APT) are explored. Ion peak interferences in time-of-flight (TOF) mass spectra are categorized by difficulty of discrimination using TOF and kinetic-energy information. Several of these categories, which are intractable interferences when only TOF information is available, may be discriminated when kinetic-energy information also is available. Furthermore, many opportunities for removing noise from composition determinations and three-dimensional images are enabled. Modest kinetic-energy resolving powers (KRPs) of 10 or so should be sufficient to have a major impact on APT. With KRP of about 100, the energy deficits in voltage pulsing may be resolved to enable peak discrimination in straight-flight-path instruments. Real examples and simulated mass spectra are used to illustrate the benefits of kinetic-energy discrimination. Many of the conclusions are applicable generally in TOF spectroscopy. Current detectors do not provide the kinetic energy of incoming ions, but there are realistic prospects for building such detectors and these are discussed. A program to develop these detectors should be pursued.