Trace determination of volatile sulfur compounds by solid-phase microextraction and GC-MS

A method was developed for the simultaneous determination of the following nine volatile sulfur compounds in gas samples: carbon disulfide, carbonyl sulfide, ethyl sulfide, ethyl methyl sulfide, hydrogen sulfide, isopropanethiol, methanethiol, methyl disulfide and methyl sulfide. The target compounds were preconcentrated by solid-phase microextraction (SPME) and determined by gas chromatography combined with mass spectrometry. Experimental design was employed to optimize the extraction time and temperature and concurrent detection of the nine compounds was achieved by using an SPME fiber coated with Carboxen-polydimethylsiloxane (75 microns). Detection limits ranged from 1 ppt (v/v) for carbon disulfide to 350 ppt (v/v) for hydrogen sulfide and calibration functions were linear up to 20 ppb (v/v) for all the compounds investigated.     

Network information and connected correlations

Entropy and information provide natural measures of correlation among elements in a network. We construct here the information theoretic analog of connected correlation functions: irreducible N-point correlation is measured by a decrease in entropy for the joint distribution of N variables relative to the maximum entropy allowed by all the observed N-1 variable distributions. We calculate the "connected information" terms for several examples and show that it also enables the decomposition of the information that is carried by a population of elements about an outside source.     

Controlled formation of ag nanoparticles by means of long-chain sodium polyacrylates in dilute solution

A new tool is presented to control formation of Ag nanoparticles. Small amounts of silver ions were added to dilute solutions of long-chain sodium polyacrylates (NaPA). Four NaPA samples covering a molar mass regime of 97 kD < or = Mw < or = 650 kD have been used. With amounts of added Ag(+) as low as 1-2% of the COO(-) groups of the polyanionic chains, significant changes could already be induced in the NaPA coils with 650 kD. If the NaPA concentration was kept below 0.1 g/L, the coils with 650 kD exhibited a significant coil shrinking in stable solutions. At larger NaPA concentrations, addition of Ag+ initiates an aggregation of the polyacrylate coils toward compact structures. Coil shrinking and aggregation was revealed by means of time-resolved static light scattering. If exposed to UV-radiation, small Ag particles formed within the shrunken anionic polyacrylate coils. The Ag nanoparticles were identified by means of an enhanced light scattering and a characteristic plasmon absorption band around 410 nm. No such Ag particle formation could be observed even at 5 times larger concentrations of Ag(+) and NaPA if the two smallest polyacrylate samples have been used under otherwise equal conditions. This molar mass sensitive response of NaPA to Ag(+)-addition suggests an interesting phenomenon: if the coil size of the NaPa chains, which act as Ag(+) collectors, is large enough, local Ag(+) concentration in these coil-shaped Ag(+) containers exceeds a critical value, and irradiation with UV generates Ag nanoparticles.     

A comprehensive analysis in one run – in-depth conformation studies of protein–polymer chimeras by asymmetrical flow field-flow fractionation

Polymer-based protein engineering has enabled the synthesis of a variety of protein–polymer conjugates that are widely applicable in therapeutic, diagnostic and biotechnological industries. Accurate characterizations of physical–chemical properties, in particular, molar masses, sizes, composition and their dispersities are critical parameters that determine the functionality and conformation of protein–polymer conjugates and are important for creating reproducible manufacturing processes. Most of the current characterization techniques suffer from fundamental limitations and do not provide an accurate understanding of a sample''s true nature. In this paper, we demonstrate the advantage of asymmetrical flow field-flow fractionation (AF4) coupled with multiple detectors for the characterization of a library of complex, zwitterionic and neutral protein–polymer conjugates. This method allows for determination of intrinsic physical properties of protein–polymer chimeras from a single, rapid measurement.

Precise characterization of structural parameters and their polydispersities of protein–polymer conjugates is performed with rapid analysis using asymmetrical flow field-flow fractionation coupled with multiple detectors.     

Acoustic Radiation Force Impulse-Imaging for the evaluation of the thyroid gland: a limited patient feasibility study

Purpose

Real-time tissue elastography, a qualitative elastography method, has shown promising results in the diagnostic work up of thyroid nodules. However, to our knowledge no study has evaluated a quantitative elastography method in the thyroid gland. The present study is a feasibility study evaluating Acoustic Radiation Force Impulse-Imaging, a novel quantitative elastography method in the thyroid gland.

Methods

ARFI-imaging involves the mechanical excitation of tissue using short-duration acoustic pulses to generate localized displacements in tissue. The displacements induce a lateral shear-wave propagation which is tracked using multiple laterally positioned ultrasound “tracking“ beams. Inclusion criteria were: thyroid nodules ?1 cm, non-functioning or hypo-functioning on radionuclide scanning, and cytological/histological assessment of thyroid nodule as reference method. All patients received conventional ultrasound, and examination of the thyroid gland including Power Doppler Ultrasound using a 9 MHz linear transducer, in addition real-time elastography (RTE) was performed at 9 MHz frequency and ARFI-imaging was performed at 4 MHz using Siemens (ACUSON S2000) B-mode-ARFI combination transducer.

Results

Sixty nodules in 55 patients were analyzed. Three nodules were papillary carcinoma. The stiffer the tissue the faster the shear wave propagates. The results obtained indicated that the shear wave velocity in thyroid lobes ranged between 0.5 and 4.9 m/s. The median velocity of ARFI-imaging in the healthy nodule-free thyroid gland, as well as in benign and malignant thyroid nodules was 1.98 m/s (range: 1.20-3.63 m/s), 2.02 m/s (range: 0.92-3.97 m/s), and 4.30 m/s (range: 2.40-4.50 m/s), respectively. While no significant difference in median velocity was found between healthy thyroid tissue and benign thyroid nodules, a significant difference was found between malignant thyroid nodules on the one hand and healthy thyroid tissue (p = 0.018) or benign thyroid nodules (p = 0.014) on the other hand. Specificity of ARFI-imaging for the differentiation of benign and malignant thyroid nodules was comparable with RTE (91-95%).

Conclusions

ARFI can be performed in the thyroid tissue with reliable results.     

Electron Transfer between Hydrogen‐Bonded Pyridylphenols and a Photoexcited Rhenium(I) Complex

Two pyridylphenols with intramolecular hydrogen bonds between the phenol and pyridine units have been synthesized, characterized crystallographically, and investigated by cyclic voltammetry and UV/Vis spectroscopy. Reductive quenching of the triplet metal‐to‐ligand charge‐transfer excited state of the [Re(CO)₃(phen)(py)]⁺ complex (phen=1,10‐phenanthroline, py=pyridine) by the two pyridylphenols and two reference phenol molecules is investigated by steady‐state and time‐resolved luminescence spectroscopy, as well as by transient absorption spectroscopy. Stern–Volmer analysis of the luminescence quenching data provides rate constants for the bimolecular excited‐state quenching reactions. H/D kinetic isotope effects for the pyridylphenols are on the order of 2.0, and the bimolecular quenching reactions are up to 100 times faster with the pyridylphenols than with the reference phenols. This observation is attributed to the markedly less positive oxidation potentials of the pyridylphenols with respect to the reference phenols (≈0.5 V), which in turn is caused by proton coupling of the phenol oxidation process. Transient absorption spectroscopy provides unambiguous evidence for the photogeneration of phenoxyl radicals, that is, the overall photoreaction is clearly a proton‐coupled electron‐transfer process.     

Chemosensor for the optical detection of aliphatic amines and diamines

Two new chemosensor dyes with either one or two trifluoroacetophenone recognition moieties have been investigated in terms of reversibly interacting with amines and diamines.     

Titanium-based molecular squares and rectangles: syntheses by self-assembly reactions of titanocene fragments and aromatic N-heterocycles

This paper reports on the potential of titanium compounds as building blocks for supramolecular polygons. Self-assembly reactions of low-valent titanocene units and N-heterocyclic bridging ligands lead to novel titanium-based supramolecular squares. Pyrazine (3), 4,4'-bipyridine (4), and tetrazine (5) were used as bridging ligands, and the acetylene complexes [Cp2Ti{eta2-C2(SiMe3)2}] (1) and [(tBuCp)2Ti{eta2-C2(SiMe3)2}] (2) as sources of titanocene fragments. Molecular rectangles can be synthesized by stepwise reduction of the titanocene dichlorides [Cp(2)TiCl2] and [(tBuCp)2TiCl2] and consecutive coordination of two different bridging ligands. The resulting complexes are the first examples of molecular rectangles containing bent metallocene corner units. Single-crystal X-ray analyses of the tetranuclear compounds revealed the geometric properties of the molecular polygons in the solid state. Comparison of bond lengths and angles in coordinated and free ligands reveals the reduced state of the bridging ligand in the low-valent titanium compounds. The syntheses and properties of these novel, highly air- and moisture-sensitive compounds are discussed.