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Fluorides are well-known as wood preservatives. One of the limitations of fluoride-based wood preservatives is their high leachability. Alternative to current fluoride salts such as NaF used in wood protection are low water-soluble fluorides. However, impregnation of low water-soluble fluorides into wood poses a challenge. To address this challenge, low water-soluble fluorides like calcium fluoride (CaF2) and magnesium fluoride (MgF2) were synthesized as nanoparticles via the fluorolytic sol−gel synthesis and then impregnated into wood specimens. In this study, the toxicity of nano metal fluorides was assessed by termite mortality, mass loss and visual analysis of treated specimens after eight weeks of exposure to termites, Coptotermes formosanus. Nano metal fluorides with sol concentrations of 0.5 M and higher were found to be effective against termites resulting in 100% termite mortality and significantly inhibited termite feeding. Among the formulations tested, the least damage was found for specimens treated with combinations of CaF2 and MgF2 with an average mass loss less than 1% and visual rating of “1”. These results demonstrate the efficacy of low water-soluble nano metal fluorides to protect wood from termite attack.
In a recent publication the authors have presented theoretical and experimental results indicating that the Jacobson–Stockmayer (JS) theory does not provide a correct description of reversible polycondensations for all polymers and for high conversions (e.g. polycondensation in bulk). In this context reversibility means that all condensation step whether resulting in chain growth or in cyclization are reversible and thus, part of an equilibrium. The first two sections of that paper were focused on the demonstration that small, and above all, large cycles can be formed by end-to-end (ete) cyclization in reversible like in irreversible polycondensations. A significant contribution of ete-cyclization to the course of reversible polycondensations was denied by J + S apparently as a contribution to Florýs dogma, that the end groups of long polymer chains will never meet.
Monodisperse iron oxide nanoparticles as reference material candidate for particle size measurements
(2020)
In order to utilize and rationally design materials at the nanoscale the reliable characterization of their physico-chemical properties is highly important, especially with respect to the assessment of their environmental or biological impact. Furthermore, the European Commission’s REACH Regulations require the registration of nanomaterials traded in quantities of at least 1 ton. Powders or dispersions where 50% (number distribution) of the constituent particles have sizes ≤ 100 nm in at least one dimension are defined as nanomaterials. This creates a need for industrial manufacturers and research or analytical service facilities to reliably characterize potential nanomaterials. Currently, BAM is developing reference nanoparticles, which shall expand the scarce list of worldwide available nano reference materials certified for particle size distribution and will also target other key parameters like shape, structure, porosity or functional properties. In this respect, materials like iron oxide or titanium dioxide are considered as candidates to complement the already available silica, Au, Ag, and polystyrene reference nanoparticles.
The thermal decomposition of iron oleate precursors in high boiling organic solvents can provide large quantities of iron oxide nanoparticles that can be varied in size and shape.[1, 2] The presence of oleic acid or other hydrophobic ligands as capping agents ensures stable dispersion in nonpolar solvents. Such monodisperse, spherical particles were synthesized at BAM and pre-characterized by electron microscopy (TEM, SEM including the transmission mode STEM-in-SEM) and dynamic light scattering comparing cumulants analysis and frequency power spectrum.
1. REACH regulations and nanosafety concerns create a strong need for nano reference materials with diverse properties.
2. Iron oxide nanoparticles are under development as new candidate reference material at BAM.
3. Narrow particle size distribution confirmed by light scattering and electron microscopy.
The concept of direct mass-spectrometric analysis, especially exploited by ambient desorption/ionization (ADI) methods, provides numerous means for convenient sample analysis. While many simple and versatile ionization sources have been developed, challenges lay in achieving efficient sample introduction. In previous work, a sample introduction method employing direct current corona discharge (CD) coupled to a surface acoustic wave nebulization (SAWN) device enhanced sampling performance for both polar and nonpolar analytes by up to 4 orders of magnitude. In fact, the SAWN-CD method generated a multiply charged peptide ion signal comparable to that of conventional ESI. Unfortunately, the high cost of the SAWN devices themselves limits their accessibility. Herein, we report on an analogous implementation of CD with an inexpensive ultrasonic nebulizer (USN) on the basis of a commercial room humidifier demonstrating equivalent exemplary performance. We subsequently compare the two methods of SAWN-CD and USN-CD in a screening application of milk for the detection of two antibiotic drugs, ciprofloxacin and ampicillin. Finally, we further investigate the relative softness of these CD-coupled acoustic nebulization methods in comparison to that of ESI using a survival yield study of the thermometer ion nitrobenzylpyridinium.
In recent years, we have come to appreciate the astounding intricacy of the processes leading to the formation of minerals from ions in aqueous solutions. The original, and rather naive, ‘textbook’ image of these phenomena, stemming from the adaptation of classical nucleation and growth theories, has increased in complexity due to the discovery of a variety of precursor and intermediate species. These include solute clusters (e.g. prenucleation clusters, PNCs), liquid(-like) phases, as well as amorphous and nanocrystalline solids etc.. Does it, however, mean that all the minerals grow through intermediate phases, following a non-classical pathway?
In general, the precursor or intermediate species constitute different, often short-lived, points along the pathway from dissolved ions to the final solids (typically crystals in this context). In this regard synchrotron-based scattering (SAXS/WAXS/total scattering) appears to be the perfect tool to follow in situ and in a time-resolved manner the crystallization pathway because of the temporal and spatial length scales that can be directly accessed with these techniques. In this presentation we show how we used scattering to probe the crystallisation mechanisms of calcium sulfate, This system contains minerals that are widespread in diverse natural environments, but they are also important in various industrial settings. Our data demonstrate that calcium sulfate precipitation involves formation and aggregation of sub-3 nm anisotropic primary species. The actual crystallisation and formation of imperfect single crystals of calcium sulfate phases, takes place from the inside of the in itial aggregates. Hence, calcium sulfate follows a non-classical pathway.
We studied the dissolution behavior of β NaYF4:Yb(20%), Er(2%) UCNP of two different sizes in biologically relevant media i.e., water (neutral pH), phosphate buffered saline (PBS), and Dulbecco’s modified Eagle medium (DMEM) at different temperatures and particle concentrations. Special emphasis was dedicated to assess the influence of different surface functionalizations, particularly the potential of mesoporous and microporous silica shells of different thicknesses for UCNP stabilization and protection. Dissolution was quantified electrochemically using a fluoride ion selective electrode (ISE) and by inductively coupled plasma optical emission spectrometry (ICP OES). In addition, dissolution was monitored fluorometrically. These experiments revealed that a thick microporous silica shell drastically decreased dissolution. Our results also underline the critical influence of the chemical composition of the aqueous environment on UCNP dissolution. In DMEM, we observed the formation of a layer of adsorbed molecules on the UCNP surface that protected the UCNP from dissolution and enhanced their fluorescence. Examination of this layer by X ray photoelectron spectroscopy (XPS) and mass spectrometry (MS) suggested that mainly phenylalanine, lysine, and glucose are adsorbed from DMEM. These findings should be considered in the future for cellular toxicity studies with UCNP and other nanoparticles and the design of new biocompatible surface coatings.
Relaxation phenomena observed in the electrical low-frequency range (approximately 1 mHz-10 kHz) of natural porous media like sandstones is often assumed to be directly related to the dominant (modal) pore throat sizes measured, for instance, with mercury intrusion porosimetry. Attempts to establish a universally valid relationship between pore size and peak Spectral Induced Polarization (SIP) relaxation time have failed, considering sandstones from very different origins and featuring great variations in textural and chemical compositions as well as in geometrical pore space properties. In addition working with characteristic relaxation times determined in Cole-Cole or Debye decomposition fits to build the relationship have not been successful. In particular, samples with narrow pore throats are often characterized by long SIP relaxation times corresponding to long “characteristic length scales” in these media, assuming that the diffusion coefficients along the electrical double layer were constant. Based on these observations, three different types of SIP relaxation can be distinguished. We present a new way of assessing complex pore spaces of very different sandstones in a multi-methodical approach to combine the benefits of mercury intrusion porosimetry, micro-computed tomography, and nuclear magnetic resonance. In this way, we achieve much deeper insight into the pore space due to the different resolutions and sensitivities of the applied methods to both pore constrictions (throats) and wide pores (pore bodies). We experimentally quantify pore aspect ratios and volume distributions within the two pore regions. We clearly observe systematic differences between three SIP relaxation types identified previously and can attribute the SIP peak relaxation times to measured characteristic length scales within our materials. We highlight selected results for a total of nine sandstones. It seems that SIP relaxation behavior depends on the size difference of the narrow pore throats to the wide pore bodies, which increases from SIP Type 1 to Type 3.
Since its introduction mass spectrometric techniques like Matrix-assisted Laser Desorption/ionization (MALDI) and Electrospray Ionization (ESI) have become indispensable for synthetic polymer analyses. Ideally, various polymer properties (monomer structure, masses, mass distribution, end groups) can be determined simultaneously. However, in real life these experiments are always affected by important structural parameters and instrumental limitations.
A short introduction focussing on latest findings with respect to ionisation principles and mechanisms will be given. Recent results from our group will be presented and efforts to avoid common drawbacks of polymer mass spectrometry will be discussed. In this regard, MALDI - Imaging mass spectrometry and the 2D hyphenation of MS with different chromatographic separation techniques were especially useful, since they can provide additional information and reduce the complexity of polymer analyses.
Multidrug solids have a potential use to efficiently treat and control a superfluity of medical conditions.
To address the current drawbacks of drug development in R&D, it was targeted to achieve new pharmaceutical solid forms of fenamic acids having improved solubility and thermal stability. Subsequently, five new multicomponent solids consisting of three salt hydrates of trimethoprim (TMP) with mefenamic acid (TMP-MFA-H2O), tolfenamic acid (TMP-TFA-H2O) and flufenamic acid (TMP-FFA-H2O), and two cocrystals of sulfamethazine (SFZ) with flufenamic acid (SFZ-FFA) and niflumic acid (SFZ-NFA) were prepared by liquid assisted grinding. Looking at the structures of active pharmaceutical ingredient (API) molecules, it was quite expected that a wide range of supramolecular synthons would lead to cocrystallization.
New forms were characterized thoroughly by various solid-state techniques, including single crystal X-ray diffraction (SCXRD), which provided details of hydrogen bonding, molecular packing and interactions between drug and coformer. Kinetic solubility at pH 7.4 buffer study has been carried out and a comparison is made with respect to the parent drugs. A significant enhancement of NSAIDs solubility was observed in all salt hydrate systems of TMP. Thus with increasing physicochemical properties such as improved solubility further leads to the enhancement of bioavailability, which has implications to overcoming the formulation related problems of active pharmaceutical ingredients (APIs).
Our aim is to develop a simple and inexpensive method for full field X-ray fluorescence imaging.We combine an energy-dispersive array detector with a coded aperture to obtain high resolution images. To obtain the information from the recorded image a reconstruction step is necessary. The reconstruction methods we have developed, were tested on simulated data and then applied to experimental data. The first tests were carried out at the BAMline @ BESSY II. This method enables the simultaneous detection of multiple elements, which is important e.g. in the field of catalysis.
The successful off-line coupling of asymmetrical flow field flow fractionation (AF4) and capillary electrophoresis (CE) for Separation of nanoparticles (NPs) with different surface coatings was shown.
Two mixtures of polystyrene nanoparticles (PS-NPs) with comparable core sizes (20 nm and 50 nm) but different coatings (no coating/carboxyl-coated) were studied. Separation in either method resulted in non-baseline resolved or non-separated peaks. In contrast, two-dimensional off-line coupling of AF4 and CE resulted in clearly separated regions in their 2 D plots and can obviouly improve separation resolution.
Imaging with X-rays is a challenging field, due to the optical properties of X-rays. The fabrication of appropriate optics is usually expensive and requires an elaborate manufacturing process. One simpler and less expensive possibility of imaging high energy radiation is coded aperture imaging, a technique well established in astrophysics and also used in nuclear medicine or radiation detection, e.g., for nuclear decommissioning. Our aim is to adapt coded aperture imaging for X-ray fluorescence spectroscopy in the nearfield. In this work we show theoretical considerations and preliminary simulations of Image formation through a coded aperture and three different reconstruction methods to prepare the experiments. We used a new mask based on an inverted modified uniformly redundant array (MURA) that could be used for the construction of a decoding mask for all investigated geometrical arrangements.
The most commonly used reconstruction method, convoluting the detected image with a Decoding mask, does not always deliver satisfactory results. This is more noticeable for small distances between the object, mask and detector. Hence, we developed two new reconstruction methods, one based on iterative algebraic optimization and another one based on a genetic algorithm. Both show good performance even in those cases where the convolution method fails. This provides a basis for further investigations of the ideal parameters for near field coded aperture imaging and refinements of the algorithms. We performed first measurements with a coded aperture at the BAMline at BESSY II and could successfully reconstruct a test object from the obtained recorded images.
The analysis of pollen chemical composition is important to many fields, including agriculture, plant physiology, ecology, allergology, and climate studies. Here, the potential of a combination of different spectroscopic and spectrometric methods regarding the characterization of small biochemical differences between pollen samples was evaluated using multivariate statistical approaches. Pollen samples, collected from three populations of the grass Poa alpina, were analyzed using Fourier-transform infrared (FTIR) spectroscopy, Raman spectroscopy, surface enhanced Raman scattering (SERS), and matrix assisted laser desorption/ionization mass spectrometry (MALDI-TOF MS). The variation in the sample set can be described in a hierarchical framework comprising three populations of the same grass species and four different growth conditions of the parent plants for each of the populations. Therefore, the data set can work here as a model system to evaluate the classification and characterization ability of the different spectroscopic and spectrometric methods. ANOVA Simultaneous Component Analysis (ASCA) was applied to achieve a separation of different sources of variance in the complex sample set. Since the chosen methods and sample preparations probe different parts and/or molecular constituents of the pollen grains, complementary information about the chemical composition of the pollen can be obtained. By using consensus principal component analysis (CPCA), data from the different methods are linked together. This enables an investigation of the underlying global information, since complementary chemical data are combined. The molecular information from four spectroscopies was combined with phenotypical information gathered from the parent plants, thereby helping to potentially link pollen chemistry to other biotic and abiotic parameters.
Numerous new tin catalysts that enable the synthesis of cyclic polylactides with broad variation in their molecular mass were recently developed. The abundance of cyclics in matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectra is, however, frequently reported to greatly exceed that of linears. Thus, the MALDI ionization behavior of various end-capped linear poly(L-lactide)s and one cyclic poly(L-lactide) was investigated and compared.
Neat compounds and various blends of cyclic and linear species were prepared and studied under identical conditions with regard to sample preparation and instrumental condition, except for the laser power. For this purpose, two different MALDI-TOF mass spectrometers were applied.
Our results reveal that cyclics indeed show a slightly better ionization in MALDI, although their ionization as a neat compound seems to be less effective than that of linear polylactides. The ionization of most linear polylactides investigated does not depend on the end group structure. However, linear polylactides containing 12-bromododecyl end groups reveal an unexpected saturation effect that is not caused by fragmentation of the polymer or the end group, or by electronic saturation of the detector digitizer. Furthermore, polylactides with a 2-bromoethyl end group did not show such a saturation effect.
An overestimation of cyclic species in MALDI-TOF mass spectra of poly(L-lactide)s must be considered, but the commonly assumed peak suppression of linear polymers in mixtures of both structures can be excluded.
X-ray absorption spectroscopy (XAS), in its various modalities, has gained exponential attention and applicability in the field of biological and biomedical systems. Particularly in this field, challenges like low concentration of analyte or proneness to radiation damage have certainly settle the basis for further analytical developments, when using X-ray based methods. Low concentration calls for higher sensitivity—by increasing the detection limits (DL); while susceptibility for radiation damage requires shorter measurement times and/or cryogenic sample environment possibilities. This manuscript reviews the latest analytical possibilities that make XAS more and more adequate to investigate biological or biomedical systems in the last 5 years.
Iron-based catalysts have been reported manifold and studied as platinum group metal (PGM) free alternatives for the catalysis of the oxygen reduction reaction (ORR). However, their sustainable preparation by greener synthesis approaches is usually not discussed. In this work, we propose a new method for the sustainable preparation of such catalysts by using a mechanochemical approach, with no solvents and non-toxic chemicals. The materials obtained from low temperature carbonization (700 °C) exhibit considerable and stable catalytic performance for ORR in alkaline medium. A catalyst obtained
from iron hydroxide, tryptophan, dicyandiamide, and ammonium nitrate shows the best electrocatalytic Performance with an overpotential of 921 mV vs. RHE at 0.1 mA/cm2 and an electron transfer number of 3.4.
The oxygen reduction reaction (ORR) – an important reaction in electrochemical devices, such as fuel cells - is characterized by its sluggish kinetics and therefore requires catalysis. The industry currently relies on platinum as a catalyst, although it is scarce and expensive, hindering the commercial breakthrough of fuel cells in automotive applications. Platinum-free catalysts on basis of nitrogen- and metal doped carbons (NMCs) and fluorinated carbons are promising materials to replace platinum-based catalysts for the ORR. In this work we prepared six metal-organic frameworks (MOFs) by mechanical ball mill grinding and studied their formation by in-situ powder X-ray diffraction. Furthermore, the samples were carbonized under controlled conditions (900°C, 1h, N2-atmosphere) to yield carbon materials, that were employed in ORR-electrocatalysis. The effect of Co-doping and fluorination was systematically studied and outstanding ORR activity was found for the catalyst prepared from the Co-doped fluorinated ZIF-8.
The influence of several precipitation parameters on the crystal morphology and size of transition metal struvite is poorly investigated. We reveal the effect of different reaction conditions on the crystal shape and crystallite size of M-struvites (NH4MPO4∙6H2O, M = Mg2+, Ni2+, Co2+). Furthermore, we characterize the coordination environment of the crystalline end products and their related phases [Co-dittmarite (COD) NH4CoPO4∙H2O and Co(II)phosphate octahydrate (CPO) Co3(PO4)2∙8H2O]. Mg- and Ni-struvite are stable in multiple concentrations of the educts and metal/phosphorus (M/P) ratios in contrast to Co-struvite which forms below M/P ratios of 0.4. A high M/P ratio with high concentrations of the educts decrease the crystallite size and idiomorphism of the crystals while low M/P ratios with low concentrations of the educts increase the crystallite size and the euhedral formation of the crystal planes. In the (Ni, Co)-solid solutions Ni and Co are homogenously distributed in the crystals with similar Ni# as in the aqueous solutions indicating no elemental fractionation in crystallization. Ni and Co-struvite exhibit a more centrosymmetric coordination environment compared to their related phases of COD and CPO determined by EXAFS. The CoO6 octahedron expands slightly the ideal size of the struvite structure and decomposes to Co-dittmarite. It is suggested that the crystallization of Ni- and Co-struvites follow a non-classical crystallization theory which consists of multiple nanophases on the way to the final crystal.
The recycling of critical elements has crucial importance to maintain sustainable use of raw materials. Phosphorus(P) is a sought-after limited natural resource due to its wide use in modern agriculture mainly as P-fertilizers. But it causes major problems for the environment such as eutrophication of ecosystems. In the future it could be depleted due to the high demand and declining natural phosphorite ore deposits. Therefore, the phosphorus recovery from agricultural waste waters will be an important factor in preservation of the global consumption. The precipitation of M-struvite (NH4MPO4·6H2O, M2+= Mg2+, Ni2+, Co2+, Zn2+, Cu2+ etc.) from agricultural and mine waste waters is a promising P-recovery route. Besides avoidance of eutrophication due to extraction of excess phosphates and the restoration of the phosphorus resources the recovered M-struvites may be potentially be up-cycled for industrial applications e.g. Co and Ni-phosphate show excellent electrochemical properties for batteries or supercapacitors.
The precipitation processes of M-struvites are strongly dependent on the degree of supersaturation, pH and on the exchange ions M2+.The impact of transition metals on the crystallization of M-struvite has been investigated only to a limited extent. An optimization of the reaction conditions could lead to more efficient M-struvite precipitation and significantly improved P-recovery method. In addition, these materials form transitional amorphous colloidal nanophases on the way to the crystalline product indicating a non-classical crystallization pathway. By interfering the crystallization process a potential highly reactive amorphous precursor material can be preserved for electrocatalysis.
Here, we present hints on the crystallization mechanism and the kinetics of precipitation through analysis of the transitional phases. Furthermore, we reveal the effect of different reaction conditions on the crystal shape and crystallite size of M-struvites (NH4MPO4∙6H2O, M = Mg2+, Ni2+, Co2+). In addition, we could evaluate the stability of crystalline M-struvites and their related phases through characterization of the coordination environment [Co-dittmarite (COD) NH4CoPO4∙H2O and Cobalt(II)phosphate octahydrate (CPO) Co3(PO4)2∙8H2O].Due to the low solubility product and their controlled precipitation through adjusting the reaction conditions (c(educts), pH, multi metal solutions) M-struvite is a promising recovery material as it could extract NH4+, PO43- and heavy metals at the same time out of agricultural and mine waste waters.
The recycling of critical elements has crucial importance to maintain sustainable use of raw materials. Phosphorus(P) is a sought-after limited natural resource due to its wide use in modern agriculture mainly as P-fertilizers. But it causes major problems for the environment such as eutrophication of ecosystems. In the future it could be depleted due to the high demand and declining natural phosphorite ore deposits. Therefore, the phosphorus recovery from mine and agricultural waste waters will be an important factor in preservation of the global consumption. The precipitation of M-struvite (NH4MPO4·6H2O, M2+= Mg2+, Ni2+, Co2+) from waste waters is a promising P-recovery route. Besides avoidance of eutrophication due to extraction of excess phosphates and the restoration of the phosphorus resources the recovered M-struvites may be potentially be up-cycled for industrial applications e.g. Co and Ni-phosphate show excellent electrochemical properties for batteries or supercapacitors.
The precipitation process of M-struvites is strongly dependent on the degree of supersaturation, pH and on the exchange ions M2+.The influence of these precipitation parameters on the crystal morphology and size of transition metal struvite has been investigated only to a limited extent. An optimization of the reaction conditions could lead to more efficient M-struvite precipitation and significantly improved P-recovery method.
We reveal the effect of different reaction conditions on the crystal shape and crystallite size of M-struvites (NH4MPO4∙6H2O, M = Mg2+, Ni2+, Co2+). Furthermore, we characterize the coordination environment of the crystalline end products and their related phases [Co-dittmarite (COD) NH4CoPO4∙H2O and Co(II)phosphate octahydrate (CPO) Co3(PO4)2∙8H2O]. Due to the presence of various amorphous phases pH is changing significantly in the different systems. Mg- and Ni-struvite are stable in multiple concentrations of the educts and metal/phosphorus (M/P) ratios in contrast to Co-struvite which forms below M/P ratios of 0.4. A high M/P ratio with high concentrations of the educts decrease the crystallite size and idiomorphism of the crystals while low M/P ratios with low concentrations of the educts increase the crystallite size and the euhedral formation of the crystal planes. In the (Ni, Co)-solid solutions Ni and Co are homogenously distributed in the crystals with similar Ni# as in the aqueous solutions indicating no elemental fractionation in crystallization. Ni and Co-struvite exhibit a more centrosymmetric coordination environment compared to their related phases of COD and CPO determined by EXAFS. The CoO6 octahedron expands slightly the ideal size of the struvite structure and decomposes to Co-dittmarite. From TEM analysis and pH measurements it is suggested that the crystallization of Ni- and Co-struvite follows a non-classical crystallization theory which consists of multiple nanophases, crystalline or amorphous, on the way to the final crystalline product.