Flow injection-mini-column technique with ICP-AES detection for the isolation and preconcentration of the fast reactive aluminium fraction in waters

A flow injection mini-column system based on short reaction times with 8-hydroxyquinoline (oxine) with ICP-AES detection is described for the isolation and preconcentration of the “fast reactive” or “toxic” aluminium fraction in water samples. Using a 3 s reaction time with oxine (5 × 10^–4 mol/l) at pH 5.0, the “fast reactive” aluminium fraction is shown not to include the non-toxic AlF²⁺ species at low F^–: Al³⁺ molar ratios (0.3 : 1). The complexed aluminium is isolated in a stable and recoverable form on mini-columns of Amberlite XAD-2 (0.3 cm × 5.0 cm, resin particle size range 0.08 mm–0.16 mm)). The retained aluminium is recovered by “back-flushing” the analytical column with 1 mol/l HCl for final element specific detection by ICP-AES. Detection limits (after preconcentration) of 2 μg/l, a linear range of 0–500 μg/l, and possible preconcentration factors of up to 18 times are demonstrated with the present system. Implications for the possible solution of sample stability problems encountered with labile aluminium species analysis and the development of a “field sampling” technique are discussed, where the desired Al fraction is quantitatively retained in a stable form on mini-columns.     

Experimental Determination of the Isotherm at 15°C of the System Mg2+/Cl?, SO42–H2O

 The diagram of the ternary system Mg²⁺/Cl⁻, SO₄ ²⁻–H₂O was established at 15°C by means of analytical and conductimetric measurements. Three compounds were found in this diagram, which are MgSO₄·6H₂O, MgSO₄·7H₂O, and MgCl₂·6H₂O. The solubility field of MgSO₄·7H₂O is important whereas those of MgSO₄·6H₂O and MgCl₂·6H₂O are small. The compositions (mass-%) of the two invariant points determined by the two methods are: MgSO₄:MgCl₂=2.73:33.80 and MgSO₄: MgCl₂=3.38:28.91. Both the measured and the calculated isotherm at 15°C have been used for modelling of the diagram Mg²⁺/Cl⁻, SO₄ ²⁻–H₂O between 0 and 35°C. The polythermal invariant point was approximately located between 15 and 10°C.     

Structural and process controls of AIEgens for NIR-II theranostics

Aggregation-induced emission (AIE) is a cutting-edge fluorescence technology, giving highly-efficient solid-state photoluminescence. Particularly, AIE luminogens (AIEgens) with emission in the range of second near-infrared window (NIR-II, 1000–1700 nm) have displayed salient advantages for biomedical imaging and therapy. However, the molecular design strategy and underlying mechanism for regulating the balance between fluorescence (radiative pathway) and photothermal effect (non-radiative pathway) in these narrow bandgap materials remain obscure. In this review, we outline the latest achievements in the molecular guidelines and photophysical process control for developing highly efficient NIR-II emitters or photothermal agents with aggregation-induced emission (AIE) attributes. We provide insights to optimize fluorescence efficiency by regulating multi-hierarchical structures from single molecules (flexibilization) to molecular aggregates (rigidification). We also discuss the crucial role of intramolecular motions in molecular aggregates for balancing the functions of fluorescence imaging and photothermal therapy. The superiority of the NIR-II region is demonstrated by fluorescence/photoacoustic imaging of blood vessels and the brain as well as photothermal ablation of the tumor. Finally, a summary of the challenges and perspectives of NIR-II AIEgens for in vivo theranostics is given.

Structural and process controls of NIR-II AIEgens realize manipulating of radiative (R) and nonradiative (NR) decay for precise theranostics.     

Limitations and perspectives in the determination of carbofuran with various liquid chromatography-mass spectrometry interfacing systems

Column liquid chromatography with mass spectrometric detection (LC-MS) has been widely accepted as the preferred technique for the identification and quantification of polar and thermally labile compounds at trace levels. Over the last decade many different types of LC-MS interfacing techniques have been used for the determination of carbamate pesticides and especially for the N-methylcarbamate carbofuran. This article addresses the difficulties encountered with the various types of LC-MS interface and discusses recent alternatives for the determination of carbofuran. With thermospray and particle beam interfaces the quantification of carbofuran is affected by both the ion source pressure and temperature, whereas quantification using the recently developed atmospheric pressure ionization interfaces, atmospheric pressure chemical ionization, electrospray, and ionspray, is less dependent on these parameters.     

草酰胺桥联大环二羰四胺铜(Ⅱ)-钴(Ⅱ)异双核配合物的合成、结构、表征和电化学性质

合成了一种具有草酰胺桥联大环二羰四胺结构的 Cu( ) -Co( )异双核配合物 ,用红外光谱、电子光谱、摩尔电导、热重分析、室温磁矩、循环伏安等对其进行了表征 .初步推定 Cu( ) -Co( )异双核配合物具有草酰胺桥联大环二羰四胺结构 .室温磁矩测定表明 ,通过草酰胺桥联配体金属离子间有一定的反铁磁性自旋偶合作用 .循环伏安法测定了配合物的半波电位 ,实验表明 ,此类配合物能够稳定高价态 Cu( ) ,外延桥基配位对大环内腔 Cu( )离子的氧化还原过程无影响 .单核配合物 X射线晶体衍射研究表明 ,其为单斜晶系 ,空间群 P2 1 /c,a=0 .73 861 (1 5 ) nm,b=2 .1 2 1 1 (4 ) nm,c=0 .95 2 5 0 (1 9) nm,β=94.70 (3 )°,R1 =0 .0 5 1 3 ,w R2 =0 .1 1 77,Z=4.Cu( )处于大环四胺平面正方中心上方 0 .0 3 nm,并具有外延草酰胺桥     

Characterisation of botulinum toxins type C, D, E, and F by matrix-assisted laser desorption ionisation and electrospray mass spectrometry

In a follow-up of the earlier characterisation of botulinum toxins type A and B (BTxA and BTxB) by mass spectrometry (MS), types C, D, E, and F (BTxC, BTxD, BTxE, BTxF) were now investigated. Botulinum toxins are extremely neurotoxic bacterial toxins, likely to be used as biological warfare agent. Biologically active BTxC, BTxD, BTxE, and BTxF are comprised of a protein complex of the respective neurotoxins with non-toxic non-haemagglutinin (NTNH) and, sometimes, specific haemagglutinins (HA). These protein complexes were observed in mass spectrometric identification. The BTxC complex, from Clostridium botulinum strain 003-9, consisted of a 'type C1 and D mosaic' toxin similar to that of type C strain 6813, a non-toxic non-hemagglutinating and a 33 kDa hemagglutinating (HA-33) component similar to those of strain C-Stockholm, and an exoenzyme C3 of which the sequence was in full agreement with the known genetic sequence of strain 003-9. The BTxD complex, from C. botulinum strain CB-16, consisted of a neurotoxin with the observed sequence identical with that of type D strain BVD/-3 and of an NTNH with the observed sequence identical with that of type C strain C-Yoichi. Remarkably, the observed protein sequence of CB-16 NTNH differed by one amino acid from the known gene sequence: L859 instead of F859. The BTxE complex, from a C. botulinum isolated from herring sprats, consisted of the neurotoxin with an observed sequence identical with that from strain NCTC 11219 and an NTNH similar to that from type E strain Mashike (1 amino acid difference with observed sequence). BTxF, from C. botulinum strain Langeland (NCTC 10281), consisted of the neurotoxin and an NTNH; observed sequences from both proteins were in agreement with the gene sequence known from strain Langeland. As with BTxA and BTxB, matrix-assisted laser desorption/ionisation (MALDI) MS provided provisional identification from trypsin digest peptide maps and liquid chromatography-electrospray (tandem) mass spectrometry (LC-ES MS) afforded unequivocal identification from amino acid sequence information of digest peptides obtained in trypsin digestion.     

Nonclassical titanocene silyl hydrides

The titanocene silyl hydride complexes [Ti(Cp)2(PMe3)(H)(SiR3)] [SiR3=SiMePhCl (6), SiPh2Cl (7), SiMeCl2 (8), SiCl3 (9)] were prepared by HSiR3 addition to [Ti(Cp)2(PMe3)2] and were studied by NMR and IR spectroscopy, X-ray diffraction (for 6, 8, and 9), and DFT calculations. Spectroscopic and structural data established that these complexes exhibit nonclassical Ti-H-Si-Cl interligand hypervalent interactions. In particular, the observation of silicon-hydride coupling constants J(Si,H) in 6-9 in the range 22-40 Hz, the signs of which we found to be negative for 8 and 9, is conclusive evidence of the presence of a direct Si-H bond. The analogous reaction of [Ti(Cp)2(PMe3)2] with HSi(OEt)3 does not afford the expected classical silyl hydride complex [Ti(Cp)2(PMe3)(H)[Si(OEt)3]], and instead NMR-silent titanium (apparently TiIII) complex(es) and the silane redistribution product Si(OEt)4 are formed. The structural data and DFT calculations for the compounds [Ti(Cp)2(PMe3)(H)(SiR3)] show that the strength of interligand hypervalent interactions in the chlorosilyl complexes decreases as the number of chloro groups on silicon increases. However, in the absence of an Si-bound electron-withdrawing group trans to the Si-H moiety, a silane sigma complex is formed, characterized by a long Ti-Si bond of 2.658 A and short Si-H contact of 1.840 A in the model complex [Ti(Cp)2(PMe3)(H)(SiMe3)]. Both the silane sigma complexes and silyl hydride complexes with interligand hypervalent interactions exhibit bond paths between the silicon and hydride atoms in Atoms in Molecules (AIM) studies. To date a classical titanocene phosphane silyl hydride complex without any Si-H interaction has not been observed, and therefore titanocene silyl hydrides are, depending on the nature of the R groups on Si, either silane sigma complexes or compounds with an interligand hypervalent interaction.     

Synthesis, Structure and Conductivity of the New Charge-transfer Salt (ET)_2(CH_2=CH-CH_2-SO_3)·H_2O

ET is one of the most famous electron-donor molecules, which forms charge-transfer complexes (abbr. CT-complexes) with various types of counterions. These complexes have received intense attention because a wide range of physical properties such as conductivity and superconductivity1, ferromagnetism2-4 and nonlinear optical properties5 was found in these materials. Although the majority of the ET-based CT-complexes were prepared by combining with inorganic counterions, CT-complexes with o…     

The unimolecular chemistry of [1,2-propanediol]+˙: a rationale in terms of hydrogen-bridged radical cations

By combining results from a variety of mass spectrometric techniques (metastatle ion, collisional activation, collision-induced dissociative ionization, neutralization–reionization spectrometry and appearance energy measurements) and the classical method of isotopic labelling, a unified mechanism is proposed for the complex unimolecular chemistry of ionized 1,2-propanediol. The key intermediates involved are the stable hydrogen-bridged radical cations [CH₂?C(H)? H…?O…?O(H)CH₃]⁺˙, which were generated independently from [4-methoxy, 1-butanol]⁺˙ (loss of C₂H₄) and [1-methoxyglycerol]⁺˙ (loss of CH₂O), [CH₃? C?O…?H…?O(H)CH₃]⁺˙ and the related ion-dipole complex [CH₂?C(OH)CH₃/H₂O]⁺˙. The latter species serves as the precursor for the loss of CH³˙ and in this reaction the same non-ergodic behaviour is observed as in the loss of CH³˙ from the ionized enol of acetone.