Synthesis and Characterization of Ferrocene Derived Cyclic Carbaphosphazenes

Dialkylamino substituted cyclic carbaphosphazenes, (R 2 NCN) 2 (NPCl 2 ) were prepared and reacted with the ferrocene derived hydroxymethyl phosphine sulfide FcCH(CH 3 )P(S)(CH 2 OH) 2 after dilithiation to yield a series of new spirocyclic derivatives of cyclic carbaphosphazenes having ferrocenyl pendant groups. To confirm the formation of six membered spirocycles and to compare their spectral features, transesterification reactions of FcCH(CH 3 )P(S)(CH 2 OH) 2 also were carried out with P(NR 2 ) 3 , yielding the six membered heterocycles FcCH 2 P(S)(CH 2 O) 2 PNR 2 (R = Me, Et). The compounds were characterized by 1 H, 31 P, 13 C NMR, mass spectra, and elemental analysis.     

Determination of neutron flux parameters in PUSPATI TRIGA Mark II Research Reactor, Malaysia

In standardization NAA, it is necessary to characterize the neutron spectrum parameters such as epithermal neutron flux shape factor (α), thermal to epithermal neutron flux ratio (f), thermal neutron flux (φ _th) and epithermal neutron flux (φ _epi) in the irradiation facility to determine the concentration of an element in the sample using absolute and k ₀ standardization methods. The α and f were determined using Cd-ratio multi monitor method using experimental data obtained in PUSPATI TRIGA Mark II research reactor at four irradiation positions (10, 20, 30 and 40) of the rotary rack. The calculated values of α and f ranged from 0.006 to 0.0281 and 18.56 to 19.12 respectively. The average values of φ _th and φ _epi were found as 2.33 × 10¹² and 1.23 × 10¹¹ n cm^?2 s^?1 respectively. Moreover, a comparison of the neutron flux parameters in the present study shows an acceptable level of consistency with those of previous studies.     

A Versatile Long‐Wavelength‐Absorbing Scaffold for Eu‐Based Responsive Probes

Coumarin‐sensitized, long‐wavelength‐absorbing luminescent Eu^III‐complexes have been synthesized and characterized. The lanthanide binding site consists of a cyclen‐based chelating framework that is attached through a short linker to a 7‐hydroxycoumarin, a 7‐B(OH)₂‐coumarin, a 7‐O‐(4‐pinacolatoboronbenzyl)‐coumarin or a 7‐O‐(4‐methoxybenzyl)‐coumarin. The syntheses are straightforward, use readily available building blocks, and proceed through a small number of high‐yielding steps. The sensitivity of coumarin photophysics to the 7‐substituent enables modulation of the antenna‐absorption properties, and thus the lanthanide excitation spectrum. Reactions of the boronate‐based functionalities (cages) with H₂O₂ yielded the corresponding 7‐hydroxycoumarin species. The same species was produced with peroxynitrite in a ×10⁶–10⁷‐fold faster reaction. Both reactions resulted in the emergence of a strong ≈407 nm excitation band, with concomitant decrease of the 366 nm band of the caged probe. In aqueous solution the methoxybenzyl caged Eu‐complex was quenched by ONOO^?. We have shown that preliminary screening of simple coumarin‐based antennae through UV/Vis absorption spectroscopy is possible as the changes in absorption profile translate with good fidelity to changes in Eu^III‐excitation profile in the fully elaborated complex. Taken together, our results show that the 7‐hydroxycoumarin antenna is a viable scaffold for the construction of turn‐on and ratiometric luminescent probes.     

Investigate the capability of INAA absolute method to determine the concentrations of 238U and 232Th in rock samples

This work aimed to study the capability of INAA absolute method in determining the elemental concentration of ²³⁸U and ²³²Th in the rock samples. The INAA absolute method was implemented in PUSPATI TRIGA Mark II research reactor, Malaysian Nuclear Agency (NM). The accuracy of INAA absolute method was performed by analyzing the IAEA certified reference material (CRM) Soil-7. The analytical results showed the deviations between experimental and certified values were mostly less than 10 % with Z-score in most cases less than 1. In general, the results of analysed CRM Soil-7 show a good agreement between certified and experimental results which mean that the INAA absolute method can be used accurately for elemental analysis of uranium and thorium in various types of samples. The concentration of ²³⁸U and ²³²Th ranged from 1.77 to 24.25 and 0.88 to 95.50 ppm respectively. The highest value of ²³⁸U and ²³²Th was recorded for granite rock sample G17 of ²³⁸U and sample G9 of ²³²Th, whereas the lower value was 1.77 ppm of ²³⁸U recorded in sandstone rock and 0.88 ppm of ²³²Th for gabbro. Moreover, a comparison of the ²³⁸U and ²³²Th results obtained by the INAA absolute method shows an acceptable level of consistency with those obtained by the INAA relative method.     

Reactivity of Aliphatic and Phenolic Hydroxyl Groups in Kraft Lignin towards 4,4′ MDI

Several efforts have been dedicated to the development of lignin-based polyurethanes (PU) in recent years. The low and heterogeneous reactivity of lignin hydroxyl groups towards diisocyanates, arising from their highly complex chemical structure, limits the application of this biopolymer in PU synthesis. Besides the well-known differences in the reactivity of aliphatic and aromatic hydroxyl groups, experimental work in which the reactivity of both types of hydroxyl, especially the aromatic ones present in syringyl (S-unit), guaiacyl (G-unit), and p-hydroxyphenyl (H-unit) building units are considered and compared, is still lacking in the literature. In this work, the hydroxyl reactivity of two kraft lignin grades towards 4,4′-diphenylmethane diisocyanate (MDI) was investigated. ³¹P NMR allowed the monitoring of the reactivity of each hydroxyl group in the lignin structure. FTIR spectra revealed the evolution of peaks related to hydroxyl consumption and urethane formation. These results might support new PU developments, including the use of unmodified lignin and the synthesis of MDI-functionalized biopolymers or prepolymers.     

A Rechargeable Hydrogen Battery Based on Ru Catalysis

Apart from energy generation, the storage and liberation of energy are among the major problems in establishing a sustainable energy supply chain. Herein we report the development of a rechargeable H₂ battery which is based on the principle of the Ru‐catalyzed hydrogenation of CO₂ to formic acid (charging process) and the Ru‐catalyzed decomposition of formic acid to CO₂ and H₂ (discharging process). Both processes are driven by the same catalyst at elevated temperature either under pressure (charging process) or pressure‐free conditions (discharging process). Up to five charging–discharging cycles were performed without decrease of storage capacity. The resulting CO₂/H₂ mixture is free of CO and can be employed directly in fuel‐cell technology.     

Synthesis of Soluble,Alkyne‐Substituted Trideca‐ and Hexadeca‐Starphenes

Two literature‐known TIPS‐ethynyl‐dibromoacenes were prepared and employed to synthesize cyclotrimers by using Yamamoto coupling conditions. Two large, well‐soluble starphenes were isolated in good yields. Crystallographic characterization verifies the triangular shape and shows significant differences in crystal packing.     

GC–MS with photoionization of cold molecules in supersonic molecular beams—Approaching the softest ionization method

A new type of photoionization ion source was developed for the ionization of cold molecules in supersonic molecular beams (named Cold PI). The system was based on a GC–MS with supersonic molecular beams and its fly‐through EI of cold molecules ion source (Cold EI) plus quadrupole mass analyzer. A continuously operated deuterium VUV photoionization lamp was added and placed above and between the supersonic nozzle and skimmer whereas the Cold EI ion source served only as a portion of the ion transfer ion optics. The supersonic nozzle and skimmer were voltage biased and the VUV light crossed the supersonic expansion about 10 mm from the nozzle. We obtained over three orders of magnitude enhancement in the relative abundance of the molecular ion of squalane in Cold PI versus in photoionization of this compound as a thermal compound. Accordingly, we also proved that standard photoionization is not as soft ionization method as previously perceived for large compounds. We found that Cold PI is as soft as and possibly softer than field ionization; thus, it could be the softest known ionization method. The ionization yield was about 200–300 times weaker than with Cold EI yet our limit of detection was about 200 femtogram in SIM mode for cholesterol and pyrene which is reasonable. Practically, all hydrocarbons gave only molecular ions with rather uniform response whereas alcohols gave some molecular ions plus major fragment ions particularly with a loss of water (similarly to field ionization). We tested Cold PI in the GC–MS analysis of diesel fuels and analyzed the time averaged data for group type information. We also found that we can analyze the diesel fuels by fast under 20‐s flow injection analysis in which the generated averaged mass spectrum of molecular ions only could serve for the characterization of fuels.