Proficiency test of pH,conductivity and dissolved oxygen concentration field measurements in river water

In 2013, Proftest SYKE organised the first proficiency test (PT) in Finland for field measurements of temperature, conductivity, dissolved oxygen concentration, oxygen saturation and pH value in river water. The aim was to pilot the organisation of an in situ proficiency test—particularly, how to select the test location—and how to assess the homogeneity and stability of the measurement site and the water to be tested. The focus was also to evaluate the suitability of the common field sensors used for water analysis, as well as the comparability of the results between the instruments under field conditions. The overall application of quality assurance procedures was also surveyed. This paper deals with the results, findings and recommendations for the measurement of pH, conductivity and dissolved oxygen concentration. In total, nine participants with 16 sensors took part in the proficiency test. For the evaluation of the performance of each participant, z scores were calculated allowing 3 % to 8 % deviation from the assigned value. The standard deviation of the participant’s results was lower than organiser expected, and 80 % of the results for pH, 79 % for conductivity and 69 % for dissolved oxygen concentration were regarded as satisfactory. According to the results, the most challenging measurement was for dissolved oxygen with a Clark cell-type measurement principle based on electrochemical reaction. All sensors tested in the PT were less than 5 years, old and they were calibrated according to the manufacturer’s instructions. None of the participants had estimated measurement uncertainty for their sensor measurements. In addition, internal and external quality assurance protocols were usually lacking.     

Synthesis of new o-alkyl substituted arylalkylphosphanes: study of their molecular structure and influence on rhodium-catalyzed propene and 1-hexene hydroformylation

A set of new phosphane ligands designed to increase the branched-to-normal ratio of the hydroformylation reaction were prepared in the same way as the previously reported ortho-alkyl substituted arylphosphanes, which have shown increased i/n ratios in the hydroformylation of propene and 1-hexene. In order to determine the relationship between the catalytic behavior and stereoelectronic properties of the ligands, various functional alkyl groups (methyl, isopropyl, cyclohexyl) were placed on the phosphorus atom directly and in the ortho position of the phenyl ring connected to phosphorus. In the hydroformylation reaction of propene and 1-hexene a higher i/n ratio resulted with nearly all the ligands compared with that of triphenylphosphane. Additionally as the ortho-alkyl-substituent became larger, it had a favorable effect on the i-selectivity. Characterization of the ligands was carried out by NMR spectroscopy (mainly ¹H, ³¹P{¹H}, ¹³C{¹H}, HSQC/HETCOR and COSY-90). Properties of the ligands were also studied by quantum mechanical calculations and by synthesizing three Rh(acac)(CO)(PR₃) derivatives. The o-alkyl-substituent was orientated outside the ligands’ cone angle in the X-ray crystal structures of (2-cyclohexylphenyl)dicyclohexylphosphane and (2,5-dimethylphenyl)bis(4-pyridyl)phosphane, and Rh(acac)(CO)(PR₃) complex of (2-methylphenyl)dicyclohexylphosphane.     

Sensitive miniature single-particle immunoassay of prostate-specific antigen using time-resolved fluorescence

The present study describes the development of a quantitative miniaturized single microparticle immunoassay. The main objective of the study was to evaluate the performance of a miniature heterogeneous immunoassay on a single microparticle in respect to assay kinetics, volume, and sensitivity, binding capacity of microparticles and sensitivity using europium(III) nanoparticle labels. The performance of the single microparticle assay of prostate-specific antigen (PSA) was investigated using different-sized microparticles (60-920 μm in diameter) and microtiter well as a solid-phase. Equilibration time of the assay was shown to be dependent in a linear manner on surface-to-volume ratio, i.e. larger surface-to-volume translated to a faster reaction. However, no correlation between PSA binding capacity and equilibration time was observed in these kinetic studies. Only moderate improvement in assay kinetics was found when PSA binding capacity was increased on a microparticle. Using europium(III) nanoparticle labels, 107 nm in diameter, coated with streptavidin a detection sensitivity of 30 ng l⁻¹ (0.1 amol) was achieved in 1 μl total assay volume per microparticle. This was 50-fold higher compared to the same assay performed with intrinsically fluorescent europium(III) labels.     

Streptavidin-coated spot surfaces for sensitive immunoassays using fluorescence surface readout

Direct measurement of time-resolved fluorescence from a washed surface of an immunoassay well constitutes an advantage compared with label development options involving signal generation in solution. Epi-fluorometric detection collects the signal from only a small part of the microtiter well’s bottom surface and it is inadequate for the optimal assay sensitivity when using binding surfaces introduced by large coating volume. This study reports on the use of streptavidin-coated spots intended to condense the binding of the labeled antibodies to coincide with the excitation beam. The spots were generated in special microtiter wells containing 2.5-mm, 3.5-mm, and 4.5-mm diameter indentations by adsorption from liquid droplets containing either native (SAv) or modified high-capacity (GA-SAv) streptavidin. The SAv-coated and GA-SAv-coated spots exhibited maximum Eu–biotin binding densities of 0.080 and 0.47 pmol/mm², respectively. A sandwich-type immunoassay of thyroid-stimulating hormone (TSH) provided a fivefold to sixfold increase in the signal-to-background ratios of the spot assay and an equivalent improvement in the detection limit (DL < 0.01 mU/L) compared with a reference assay. Figure The condensation of the binding area into a spot (right) results in a denser collection of the labeled antibodies and more favorable signal-to-background ratios compared with a regular approach using a large binding area (left)     

Particulate and soluble Eu(III)-chelates as donor labels in homogeneous fluorescence resonance energy transfer based immunoassay

Many well-established homogeneous separation free immunoassays rely on particulate label technologies. Particles generally contain a high concentration of the embedded label and they have a large surface area, which enables conjugation of a large amount of protein per particle. Eu(III)-chelate dyed nanoparticles have been successfully used as labels in heterogeneous and homogeneous immunoassays. In this study, we compared the characteristics of two homogeneous competitive immunoassays using either soluble Eu(III)-chelates or polystyrene particles containing Eu(III)-chelates as donors in a fluorescence resonance energy transfer based assay. The use of the particulate label significantly increased the obtained sensitized emission, which was generated by a single binding event. This was due to the extremely high specific activity of the nanoparticle label and also in some extent the longer Förster radius between the donor and the acceptor. The amount of the binder protein used in the assay could be decreased by 10-fold without impairing the obtainable sensitized emission, which subsequently led to improved assay sensitivity. The optimized assay using particulate donor had the lowest limit of detection (calculated using 3 × S.D. of the 0 nM standard) 50 pM of estradiol in the assay well, which was approximately 20-fold more sensitive than assays using soluble Eu(III)-chelates.     

Tessellation of Chiral‐Nematic Cellulose Nanocrystal Films by Microtemplating

In biological architectures, material properties are optimized by the hierarchical structuring of components with a multiscaled order, from the nano‐ to the macroscales. Such designs enable, for instance, programmed yield points that maximize toughness. However, research efforts in biomimetic materials have focused on the assembly of nano‐ or macrostructures individually. In this study, high strength cellulose nanocrystals (CNCs), assembled into chiral‐nematically ordered structures, are tiled into a higher level, macro‐sized, architecture by topographical templating. As templates, two meshed architectures with distinct feature sizes are evaluated, and the optomechanical properties of the resulting films are compared to featureless, flat, CNC films. Controlling capillary stresses arising during CNC assembly is shown to enable control over the orientation of the chiral‐nematic director across the topography of the template. Tuning the specific reflections and multiscaled fracture propagation is demonstrated for the microtemplated CNC films. The latter phenomenon contributed to enhancing the toughness of the material through a high tortuosity of fracture propagation in all (x, y, z) directions. The presented findings are expected to pave the way towards the incorporation of current research in cellular metamaterials with the research focusing on the generation of nanoscaled biomimetic constructs.     

Multidimensional analytical method based on binary phase shaping of femtosecond pulses

Multidimensional chemical detection and identification based on phase shaped femtosecond laser pulses coupled to mass spectrometry is demonstrated. The method based on binary phase shaping (BPS) takes into account the accuracy and precision standards required by analytical chemistry. It couples multiphoton intrapulse interference of ultrashort laser pulses with time-of-flight mass spectrometry (TOF-MS). We demonstrate that BPS-MS provides a rigorous multidimensional technique for the detection and identification of analogues to chemical agents and mixtures in real time. Experimental results on dimethyl phosphite and pyridine illustrate the new approach toward the real-time accurate detection and identification of chemical compounds including isomers.     

Defect theorems with compatibility relations

We consider words together with a compatibility relation induced by a relation on letters. Unique factorization with respect to two arbitrary word relations R and S defines the (R,S)-freeness of the semigroup considered. We generalize the stability theorem of Schützenberger and Tilson’s closure result for (R,S)-free semigroups. The inner and the outer (R,S)-unique factorization hull and the (R,S)-free hull of a set of words are introduced and we show how they can be computed. We prove that the (R,S)-unique factorization hulls possess a defect effect, which implies a variant of a cumulative defect theorem of word semigroups. In addition, a defect theorem of partial words is proved as a corollary.     

Thermal and X‐ray powder diffraction studies of aliphatic polyester dendrimers

The syntheses and thermal and X‐ray powder diffraction analyses of three sets of aliphatic polyester dendrimers based on 2,2‐bis(hydroxymethyl)propionic acid as a repeating unit and 2,2‐dimethyl‐1,3‐propanediol, 1,5‐pentanediol, and 1,1,1‐tris(hydroxymethyl)ethane as core molecules are reported. These dendritic polyesters were prepared in high yields with the divergent method. The thermal properties of these biodendrimers were evaluated with thermogravimetric analysis and differential scanning calorimetry. The thermal decomposition of the compounds occurred around 250 °C for the hydroxyl‐ended dendrimers and around 150 °C for the acetonide‐protected dendrimers. In addition, the crystallinity of the lower generation dendrimers was evaluated with X‐ray powder diffraction. The highest crystallinity and the highest melting points were observed for the first‐generation dendritic compounds. The higher generation dendrimers showed weaker melting transitions during the first heating scan. Only the glass‐transition temperatures were observed in subsequent heating scans. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5574–5586, 2004