A New Pulsed Flow Modulation GC × GC–MS with Cold EI System and Its Application for Jet Fuel Analysis

We designed and operated a new system of pulsed flow modulation (PFM) two dimensional comprehensive gas chromatography (GC × GC) mass spectrometry (MS). This system is based on the combination of PFM–GC × GC with a quadrupole mass spectrometer of GC–MS via a supersonic molecular beams interface and its fly-through Cold EI ion source and applied this system for the analysis of JP8 jet fuel. PFM is a simple GC × GC modulator that does not consume cryogenic gases while providing tunable second GC × GC column injection time for enabling the use of quadrupole based mass spectrometry regardless its limited scanning speed. We analyzed JP8 jet fuel with our new PFM–GC × GC–MS with Cold EI system and found that as the second dimension GC elution time is increased the observed molecular ion mass is reduced. This unique observation that helped in improved sample compounds identification under co-elution conditions was enabled via having abundant molecular ions in Cold EI for all the fuel compounds. We named this type of analysis as PFM–GC × GC × MS. We found and discuss in this paper that PFM–GC × GC–MS with Cold EI combines improved separation of GC × GC with Cold EI benefits of tailing-free ultra-fast ion source response time and enhanced molecular ions and mass spectral isomer and isotope information for the provision of increased sample identification information.

     

Magnetomechanical training of single crystalline Ni-Mn-Ga alloy

A 5M Ni-Mn-Ga single crystal was investigated, supplied by Adaptamat Ltd, Finland. Especially low temperature magnetic actuation as well as cyclic tensile-compression tests revealed promising properties, which provide useful insights for training concepts in polycrystalline materials. Successive compressions lead to a significant reduction of the twinning stress by a factor of two.     

ORGANISCHE PHOSPHORVERBINDUNGEN 80 HERSTELLUNG VON TRIAZOLYLMETHYL-PHOSPHONATEN UND VON TRIAZOLYL-METHYLPHOSPHONIUMSALZEN UND DEREN VERWENDUNG IN DER WITTIG-HORNER REAKTION

Abstract

Attempts to prepare 1H-1,2,4-triazol-1-ylmethylphosphonates (4 and 5) by a Mannichtype reaction or by transesterification of 1-hydroxymethyl-1H-1,2,4-triazol 1 with tertiary phosphites failed. On the other hand 4 and 5 are obtained by a Michaelis-Becker reaction from 1-chloromethyl-1H-1,2,4-triazol 3 and sodium phosphites in high yield. The Michaelis-Arbuzov reaction is less suited for the preparation of 4 and 5. 3 is obtained in good yield as a water clear liquid, b.p. 52–54°C/0.2 torr, from the interaction of 1 with thionyl chloride followed by treatment with a base. On standing at 0° or 20°C it decomposes within hours and yields the unsymmetrical methylen-bis(triazol) 3a in addition to other products. However an acetonitrile solution of 3 is stable for months. Heating this solution with tertiary phosphines gives triazolylsubstituted phosphoniumsalts 6 to 8. The Wittig-Horner reaction with 4 to 6 gives the olefinically substituted triazols 9–12 as a Z/E mixture in high yield. Alkylation of 4 with methyl-and ethyl iodide gives the corresponding alkylated diethyl-1H-1,2,4-triazol-1-yl-ethyl-1-and-propyl-1-phosphonates 14 and 15 which on hydrolysis with HCI yield 1H-1,2,4-triazol-1-yl-ethyl-1-and propyl-1-phosphonic acids 17 and 18, respectively. Hydrolysis of 4 gives the unsubstituted 1H-1,2,4-triazol-1-ylmethyl-phosphonic acid, 16.     

ORGANIC PHOSPHORUS COMPOUNDS 70 PREPARATION AND PROPERTIES OF NEW PHOSPHORUS CONTAINING CHELATING AGENTS FOR CALCIUM AND MAGNESIUM IONS

Abstract

Dedicated to Professor Martin Schmeisser on the occasion of his 65th birthday.

Several phosphonic acids of the type H₂O₃PCH₂OCHRCO₂H, R = H, CH₃, CO₂H; [H₂O₃P(CH₂)_x]₂ Y, x = 1, 2; Y = O, S; and [o-H₂O₃P(CH₂)]₂C₆H₄ have been synthesized and their capacity to chelate with calcium has been determined.     

ORGANISCHE PHOSPHORVERBINDUNGEN 791 HERSTELLUNG UND EIGENSCHAFTEN VON α-AMINO-ω-CARBOXYALKYLPHOSPHON-UND-PHOSPHINSÄUREN

Abstract

The synthesis, chemical and spectral properties of α-amino-ω-carboxyalkylphosphonic acids, (HO)₂P(O)CH(NH₂)(CH₂) _x CO₂H, x = 2 to 6, and of α-amino-ω-carboxyalkyl-methylphosphinic acids CH₃(HO)P(O)CH(NH₂)(CH₂) _x CO₂H, x = 2 to 6 are described and the fungicidal activity of some of these derivatives is reported.     

Phosphorus and Energy Recovery from Manure and Digestion Residues

Abstract

Human and animal excrements, in particular manure, stand for a significant and undisputable source of plant nutrients and renewable energy. In Europe, only 36% of P-inputs to soils originate from primary resources (rock phosphate) whereas 63% come from animal and human excretions applied to cropland as manure, digestion residues and sewage sludge. Simultaneously these waste flows represent a potential hazard to human health and aquatic bodies because of pathogens and eutrophication. Management of these waste flows is far from being sustainable, in part due to the lack of efficient processing technologies. A cooperative InnoEnergy—EIT financed KIC Knowledge and Innovation Community—research project pursues development and demonstration of highly efficient technologies to overcome the constraints and to yield renewable phosphate fertilizers and energy from waste flows that may have a combined technical energy potential of 3,600 PJ/year and an annual phosphate recovery potential of 4.5–5.5 million tonnes (as P₂O₅) in Europe.     

2‐Hydroxy‐1,2,3,6‐tetrahydro‐azulen‐6‐carboxylic Acid Ethyl Ester—A Novel Precursor for a New Class of Liquid Crystalline Materials

A novel approach for the syntheses of carbene adduct 4 is reported. A ring-enlargement strategy was employed for the synthesis of precursors 5 and 6 and established the mechanism of the formation of azulene derivative 6. Synthesis of target precursor 13, a novel precursor for the synthesis of new mesogenic materials, and its various halogenated derivatives (14–16) was carried out.     

Molecular Dynamics in 1- and 2-D Confinement as Studied for the Case of Poly(Cis-1,4-Isoprene)

Broadband Dielectric Spectroscopy (BDS) is used to probe the molecular dynamics of Type A polymer, poly(cis-1,4-isoprene), when confined in the 1-dimensional (1D) exploring space of thin layers and the 2-dimensional (2D) constraining geometry of unidirectional anodic aluminum oxide (AAO) nanopores. For both cases, it was observed that the structural relaxation remains bulk-like in its mean relaxation rate, although the distribution of its relaxation times is broadened in 2D confinement. Furthermore, the fluctuation of the end-to-end vector is interrupted, with the 1D case being relatively less pronounced. By this clear-cut comparison, it is demonstrated that the effects of confinement on molecular dynamics depend, inter alia, on the dimensionality of the restricting space.     

Arene Ruthenium(II) Complexes Bearing the κ-P or κ-P,κ-S Ph2P(CH2)3SPh Ligand

Neutral [Ru(η⁶-arene)Cl₂{Ph₂P(CH₂)₃SPh-κP}] (arene = benzene, indane, 1,2,3,4-tetrahydronaphthalene: 2a, 2c and 2d) and cationic [Ru(η⁶-arene)Cl(Ph₂P(CH₂)₃SPh-κP,κS)]X complexes (arene = mesitylene, 1,4-dihydronaphthalene; X = Cl: 3b, 3e; arene = benzene, mesitylene, indane, 1,2,3,4-tetrahydronaphthalene, and 1,4-dihydronaphthalene; X = PF₆: 4a–4e) complexes were prepared and characterized by elemental analysis, IR, ¹H, ¹³C and ³¹P NMR spectroscopy and also by single-crystal X-ray diffraction analyses. The stability of the complexes has been investigated in DMSO. Complexes have been assessed for their cytotoxic activity against 518A2, 8505C, A253, MCF-7 and SW480 cell lines. Generally, complexes exhibited activity in the lower micromolar range; moreover, they are found to be more active than cisplatin. For the most active ruthenium(II) complex, 4b, bearing mesitylene as ligand, the mechanism of action against 8505C cisplatin resistant cell line was determined. Complex 4b induced apoptosis accompanied by caspase activation.     

Ultrafast Fluorescence Spectroscopy via Upconversion and Its Applications in Biophysics

In this review, the experimental set-up and functional characteristics of single-wavelength and broad-band femtosecond upconversion spectrophotofluorometers developed in our laboratory are described. We discuss applications of this technique to biophysical problems, such as ultrafast fluorescence quenching and solvation dynamics of tryptophan, peptides, proteins, reduced nicotinamide adenine dinucleotide (NADH), and nucleic acids. In the tryptophan dynamics field, especially for proteins, two types of solvation dynamics on different time scales have been well explored: ~1 ps for bulk water, and tens of picoseconds for “biological water”, a term that combines effects of water and macromolecule dynamics. In addition, some proteins also show quasi-static self-quenching (QSSQ) phenomena. Interestingly, in our more recent work, we also find that similar mixtures of quenching and solvation dynamics occur for the metabolic cofactor NADH. In this review, we add a brief overview of the emerging development of fluorescent RNA aptamers and their potential application to live cell imaging, while noting how ultrafast measurement may speed their optimization.