Chemical characterisation of a new estuarine pollutant (2,4-Dichloro-6-Nitrophenol) and assessment of the acute toxicity of its quinoid form for Artemia salina

It is known that the compound 2,4-dichloro-6-nitrophenol (2,4DC6NP) is formed upon nitration of 2,4-dichlorophenol, which in turn is a transformation intermediate of the herbicide dichlorprop. However, the chemical and spectroscopic characteristics of 2,4DC6NP, as well as its toxicity, are poorly known. This work shows that 2,4DC6NP behaves as a diprotic acid in aqueous solutions, with pK_a values of 3.0?±?0.9 and 4.9?±?0.5. At pH?<?3, 2,4DC6NP would undergo protonation. The absorption spectra suggest that anionic 2,4DC6NP, which prevails at pH?>?5 would have an ortho-quinoid structure that is responsible for the absorption peak centred at 428?nm. Considering that 2,4DC6NP has been detected in the brackish lagoons of the Rhône delta (southern France), where its levels are comparable to those of the parent herbicide, it is necessary to examine the possible effects of 2,4DC6NP on the species living in that environment. For this reason, the acute toxicity of the anionic form of 2,4DC6NP was assessed for the brine shrimp Artemia salina, a zooplankton species that lives both in brackish and in saline aquatic environments. The toxicity test yielded a LC₂₀ value of 8?±?2?mg?L^?1 and a LC₅₀ value of 18.7?±?0.8?mg?L^?1. Such values are safely higher than the maximum detected concentration of 2,4DC6NP in the Rhône delta lagoons. Further studies should be concentrated on the long-term effects of 2,4DC6NP, and in particular on its potential genotoxicity.     

New ternary germanides La4Mg5Ge6 and La4Mg7Ge6: crystal structure and chemical bonding

The synthesis, structural characterization, and chemical-bonding peculiarities of the two new polar lanthanum-magnesium germanides La(4)Mg(5)Ge(6) and La(4)Mg(7)Ge(6) are reported. The crystal structures of these intermetallics were determined by single-crystal X-ray diffraction analysis. The La(4)Mg(5)Ge(6) phase crystallizes in the orthorhombic Gd(4)Zn(5)Ge(6) structure type [Cmc2(1), oS60, Z = 4, a = 4.5030(7) ?, b = 20.085(3) ?, c = 16.207(3) ?, wR2 = 0.0451, 1470 F(2) values, 93 variables]. The La(4)Mg(7)Ge(6) phase represents a new structure type with a monoclinic unit cell [C2/m, mS34, Z = 2, a = 16.878(3) ?, b = 4.4702(9) ?, c = 12.660(3) ?, β = 122.25(3)°, wR2 = 0.0375, 1466 F(2) values, 54 variables]. Crystallographic analysis together with linear muffin-tin orbital band structure calculations reveals the presence of strongly bonded 3D polyanionic [Mg-Ge] networks balanced by positively charged La atoms in both stoichiometric compounds. The La(4)Mg(5)Ge(6) compound is related to Zintl phases, showing a prominent density of states pseudogap at the Fermi level. A distinctive feature of the La(4)Mg(5)Ge(6) structure is the presence of Ge-Ge covalent dumbbells; in La(4)Mg(7)Ge(6), the higher Mg content generates a polyanionic network consisting exclusively of Mg-Ge heterocontacts. Nevertheless, the frameworks of the two phases are structurally similar, as is highlighted in this work.     

Site-specific conjugation of ScFvs antibodies to nanoparticles by bioorthogonal strain-promoted alkyne-nitrone cycloaddition

Particularly suitable: An N-terminal serine mutant of anti-HER2 scFv antibody was conjugated to polymer-coated magnetofluorescent nanoparticles by strain-promoted alkyne-nitrone cycloaddition. The resulting nanoparticles (see scheme) proved effective in targeting and labeling HER2-positive breast cancer cells.     

Hierarchised luminescent organic architectures: design, synthesis, self-assembly, self-organisation and functions

This critical review aims at highlighting the prevailing supramolecular approaches employed nowadays in the preparation of luminescent hierarchised materials. Specifically, it has the ambition to illustrate how progresses in the control of the supramolecular interaction toolbox ultimately led to the development of spectacular luminescent nano- and micro-architectures, through a combination of molecular self-assembly and self-organisation processes involving organic π-conjugated molecules. The reader will be guided through a systematic exploration of the most common avenues to prepare and characterise luminescent self-assembled/self-organised materials embedded into one-, two- or three-dimensional networks, accompanied by a critical discussion of their main advantages and limitations. Key representative examples of this research field will be thoroughly described, with a particular focus on those systems displaying potential on the device application scene. Particular attention will be devoted to the design and synthetic approaches aimed at the preparation of the primary π-conjugated molecular modules, the chemical, structural and electronic properties of which dramatically influence the fate and the features of the self-assembled/self-organised material (215 references).     

Synthesis and characterization of graphene‐containing thermoresponsive nanocomposite hydrogels of poly(N‐vinylcaprolactam) prepared by frontal polymerization

Thermoresponsive poly(N‐vinylcaprolactam) nanocomposite hydrogels containing graphene were successfully prepared by frontal polymerization. High concentration of graphene (5.0 mg/mL) was obtained by direct graphite sonication in the self‐same liquid monomer, thus avoiding any chemical manipulation and obtaining “real” graphene as nanofiller instead of one of its more or less oxidized derivative, which is what generally reported in published reports. Furthermore, the corresponding nanocomposites were obtained without using any solvent to be eventually removed. The materials were fully characterized by RAMAN, SEM, and TEM, and their swelling behavior and rheological properties were investigated. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Depth profile analysis of various titanium based coatings on steel and tungsten carbide using laser ablation inductively coupled plasma –“time of flight” mass spectrometry

A homogenized 193 nm ArF* laser ablation system coupled to an inductively coupled plasma-”Time of Flight”-mass spectrometer (LA-ICP-TOFMS) was tested for depth profiling analysis on different single-layer Ti based coatings on steel and W carbides. Laser parameters, such as repetition rate, pulse energy and spatial resolution were tested to allow optimum depth related calibration curves. The ablation process using a laser repetition rate of 3 Hz, 120 μm crater diameter, and 100 mJ output energy, leads to linear calibration curves independent of the drill time or peak area used for calibrating the thickness of the layer. The best depth resolution obtained (without beam splitter) was 0.20 μm per laser shot. The time resolution of the ICP-TOFMS of 102 ms integration time per isotope was sufficient for the determination of the drill time of the laser through the coatings into the matrix with better than 2.6% RSD (about 7 μm coating thickness, n = 7). Variation of the volume of the ablation cell was not influencing the depth resolution, which suggests that the depth resolution is governed by the ablation process. However, the application on the Ti(N,C) based single layer shows the potential of LA-ICP-TOFMS as a complementary technique for fast depth determinations on various coatings in the low to medium μm region.     

Cobalt blood levels after total hip replacement (THR): a new follow-up study in Trieste (Italy)

Cobalt and chromium release in patients undergone a metal-on-metal total hip replacement (THR) is a matter recently discussed and whose we do not have enough information about it yet. In literature there is little data and not completely indicative, in the biological fluids and organs the amounts of released metals are different. This is also due to the fact that cobalt and chromium blood levels can change depending on physical and working activity, individual feeding and metabolism. The results obtained confirm the presence of an increase of cobalt inthe blood of patients after total hip replacement, while the chromium levels are almost alike: average values in patients operated are 4.1 +/- 1.5 microg/L for cobalt (0.3 +/- 0.1 microg/L in the control group) and 4.5 +/- 2.9 microg/L for chromium (4.7 +/- 2.4 microg/L in the control group). In spite of the cobalt values stand below the concentration generally considered dangerous, the difference between the two examined groups points out that a risk exists for the health of these patients. These results must be confirmed by further studies, providing better information and more reliable and biocompatible materials.     

Synthesis, characterization, and DFT/TD-DFT calculations of highly phosphorescent blue light-emitting anionic iridium complexes

Highly phosphorescent blue-light-emitting anionic iridium complexes (C4H9)4N[Ir(2-phenylpyridine)2(CN)2] (1), (C4H9)4N[Ir(2-phenyl-4-dimethylaminopyridine)2(CN)2] (2), (C4H9)4N[Ir(2-(2,4-difluorophenyl)-pyridine)2(CN)2] (3), (C4H9)4N[Ir(2-(2,4-difluorophenyl)-4-dimethylaminopyridine)2(CN)2] (4), and (C4H9)4N[Ir(2-(3,5-difluorophenyl)-4-dimethylaminopyridine)2(CN)2] (5) were synthesized and characterized using NMR, UV-vis absorption, and emission spectroscopy and electrochemical methods. In these complexes color and quantum yield tuning aspects are demonstrated by modulating the ligands with substituting donor and acceptor groups on both the pyridine and phenyl moieties of 2-phenylpyridine. Complexes 1-5 display intense photoluminescence maxima in the blue region of the visible spectrum and exhibit very high phosphorescence quantum yields, in the range of 50-80%, with excited-state lifetimes of 1-4 micros in acetonitrile solution at 298 K. DFT and time dependent-DFT calculations were performed on the ground and excited states of the investigated complexes to provide insight into the structural, electronic, and optical properties of these systems.     

Heterodimers based on CoPt3-Au nanocrystals with tunable domain size

We describe an approach to synthesize colloidal nanocrystal heterodimers composed of CoPt(3) and Au. The growth is based on the nucleation of gold domains on preformed CoPt(3) nanocrystals. It is a highly versatile methodology which allows us to tune independently the size of the two domains in each dimer by varying several reaction parameters. The statistical analysis of the distribution of the domain sizes in the dimers and the compositional mapping achieved by dark field imaging and energy dispersive spectroscopy confirm that the two domains in each dimer are indeed made of CoPt(3) and Au, respectively. Structural characterization by high-resolution transmission electron microscopy shows that the two domains, both having cubic fcc Bravais lattice, can share a common {111}, {100}, or {110} facet, depending on the size of the initial CoPt(3) seeds. The magnetization measurements evidence a ferromagnetic CoPt(3) phase with a relatively low anisotropy as a consequence of their disordered crystalline structure, regardless of the presence of a Au tip. We believe that this prototype of nanocrystal dimer, which can be manipulated under air, can find several applications in nanoscience, as the Au section can be exploited as the preferential anchor point for various molecules, while the CoPt(3) domain can be used for magnetic detection.