pH‐Dependent Coordination of AgI Ions by Histidine: Experiment,Theory, and a Model for SilE

Artificial implants and biomaterials lack the natural defense system of our body and, thus, have to be protected from bacterial adhesion and biofilm formation. In addition to the increasing number of implanted objects, the resistance of bacteria is also an important problem. Silver ions are well‐known for their antimicrobial properties, yet not a lot is known about their mode of action. Silver is expected to interact on many levels, thus the development of silver resistance is very difficult. Nevertheless, some bacteria are able to resist silver, even at higher concentrations. One such defense mechanism of bacteria against heavy‐metal intoxication includes an efflux system. SilE, a periplasmic silver‐binding protein that is involved in this defense mechanism, has been shown to possess numerous histidine functions, which strongly bind to silver atoms, as demonstrated by ourselves previously. Herein, we address the question of how histidine binds to silver ions as a function of pH value. This property is important because the local proton concentration in cells varies. Thus, we solved the crystal structures of histidine–silver complexes at different pH values and also investigated the influence of the amino‐acid configuration. These results were completed by DFT calculations on the binding strength and packing effects and led to the development of a model for the mode of action of SilE.     

Dehydrogenation of Amine?Borane Me2NH⋅BH3 Catalyzed by a Lanthanum?Hydride Complex

The rare‐earth‐metal? hydride complexes [{(1,7‐Me₂TACD)LnH}₄] (Ln=La 1 a , Y 1 b ; (1,7‐Me₂TACD)H₂=1,7‐dimethyl‐1,4,7,10‐tetraazacyclododecane, 1,7‐Me₂[12]aneN₄) were synthesized by hydrogenolysis of [{(1,7‐Me₂TACD)Ln(η³‐C₃H₅)}₂] with 1 bar H₂. The tetrameric structures were confirmed by ¹H NMR spectroscopy and single‐crystal X‐ray diffraction of compound 1 a . Both complexes catalyze the dehydrogenation of secondary amine? borane Me₂NH ? BH₃ to afford the cyclic dimer (Me₂NBH₂)₂ and (Me₂N)₂BH under mild conditions. Whilst the complete conversion of Me₂NH ? BH₃ was observed within 2 h with lanthanum? hydride 1 a , the yttrium homologue 1 b required 48 h to reach 95 % conversion. Further reactions of compound 1 a with Me₂NH ? BH₃ in various stoichiometric ratios gave a series of intermediate products, [{(1,7‐Me₂TACD)LaH}₄](Me₂NBH₂)₂ ( 2 a ), [(1,7‐Me₂TACDH)La(Me₂NBH₃)₂] ( 3 a ), [(1,7‐Me₂TACD)(Me₂NBH₂)La(Me₂NBH₃)] ( 4 a ), and [(1,7‐Me₂TACD)(Me₂NBH₂)₂La(Me₂NBH₃)] ( 5 a ). Complexes 2 a , 3 a , and 5 a were isolated and characterized by multinuclear NMR spectroscopy and single‐crystal X‐ray diffraction studies. These intermediates revealed the activation and coordination modes of “Me₂NH ? BH₃” fragments that were trapped within the coordination sphere of a rare‐earth‐metal center.     

Synthesis of substituted 1-trifluoromethyl and 1-perfluoroalkyl-3-(arylamino)prop-2-en-1-one: advances in the mechanism of Combes 2-trifluoromethyl and 2-perfluoroalkyl quinolines synthesis

We report a new synthesis and our study of the mechanism of formation of substituted 1-trifluoromethyl and 1-perfluoroalkyl-3-(phenylamino)prop-2-en-1-one starting from 3-(R-phenoxy)-3-perfluoroalkyl-prop-2-enals and arylamines. Reactivity study of the intermediates confirmed that 3-perfluoroalkyl-N,N′-diphenyl-1,5-diazapentadienes are the synthetic intermediates of the synthesis of 2-perfluoroalkylquinolines. The mechanism of the reaction of 1-trifluoromethyl and 1-perfluoroalkyl-3-(phenylamino)prop-2-en-1-one with POCl₃ was studied. To our knowledge this is the first detection and isolation of N,N′-diaryldiazapentadiene derivatives as intermediates in the Combes F-alkyl substituted quinoline synthesis starting from enaminoketones. Finally, we succeeded isolating and identifying unsymmetrically substituted 2-perfluorolakyldiazapentadiene.     

Synthesis and characterization of a new lanthanide based MRI contrast agent,potential and versatile tracer for multimodal imaging

In the present work a modular pathway towards the synthesis of a new versatile MRI contrast agent is reported and its physico-chemical properties are described. Two different functional groups were attached on two arms of the gadolinium 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetate (DOTA) in order to get a platform able to bind one probe designed to target specific biological marker and a fluorescent molecule likely to be used for optical imaging. The nuclear magnetic relaxation dispersion (NMRD) profile, the oxygen-17 relaxometric NMR study and stability assessment versus transmetalation of the Gd-complex show that this new contrast agent has a relaxivity and transmetalation stability similar to Gd–DOTA.     

Method development and inter-laboratory comparison about the determination of titanium from titanium dioxide nanoparticles in tissues by inductively coupled plasma mass spectrometry

Nanosized titanium dioxide (TiO₂) is one of the most interesting and valuable nanomaterials for the construction industry but also in health care applications, food, and consumer goods, e.g., cosmetics. Therefore, the properties associated with this material are described in detail. Despite its widespread use, the analytical determination and characterization of nanosized metal oxides is not as straightforward as the comparatively easy-to-detect metallic nanoparticles (e.g., silver or gold). This study presents the method development and the results of the determination of tissue titanium (Ti) levels after treatment of rats with the nanosized TiO₂. Total Ti levels were chosen to evaluate the presence and distribution of TiO₂ nanoparticles. A procedure consisting of incubation with a mixture of nitric acid (HNO₃) and hydrofluoric acid (HF), and heating was developed to digest tissues and TiO₂ nanomaterials in order to determine the total Ti content by inductively coupled plasma mass spectrometry (ICPMS). For the inter-laboratory comparison, altogether four laboratories analyzed the same samples upon digestion using the available ICPMS equipment. A major premise for any toxicokinetic study is the possibility to detect the chemical under investigation in biological samples (tissues). So, the study has to be performed with a dose high enough to allow for subsequent tissue level measurement of the chemical under investigation. On the other hand, dose of the chemical applied should not induce over toxicity in the animal as this may affect its absorption, distribution, metabolism, and excretion. To determine a non-toxic TiO₂ dosage, an acute toxicity study in rats was performed, and the organs obtained were evaluated for the presence of Ti by ICPMS. Despite the differences in methodology and independent of the sample preparation and the ICPMS equipment used, the results obtained for samples with Ti concentrations >4 μg Ti/g tissue agreed well.

Biomimetic Mussel Adhesive Inspired Anchor to Design ZnO@Poly(3‐Hexylthiophene) Hybrid Core@Corona Nanoparticles

The functionalization of zinc oxide (ZnO) nanoparticles by poly(3‐hexylthiophene) (P3HT) brush is completed by the combination of a mussel inspired biomimetic anchoring group and Huisgen cyclo‐addition “click chemistry.” Herein, the direct coupling of an azide modified catechol derivative with an alkyne end‐functionalized P3HT is described. This macromolecular binding agent is used to access core@corona ZnO@P3HT with a stable and homogeneous conjugated organic corona. Preliminary photoluminescence measurement proves an efficient electron transfer from the donor P3HT to the acceptor ZnO nanoparticles upon grafting, thus demonstrating the potential of such a combination in organic electronics.

     

Ion chromatograph with three-dimensional printed absorbance detector for indirect ultraviolet absorbance detection of phosphate in effluent and natural waters

An ion chromatography system employing a low-cost three-dimensional printed absorbance detector for indirect ultraviolet detection towards portable phosphate analysis of environmental and industrial waters has been developed. The optical detection cell was fabricated using stereolithography three-dimensional printing of nanocomposite material. Chromatographic analysis and detection of phosphate were carried out using a CS5A 4 × 250 mm analytical column with indirect ultraviolet detection using a 255 nm light-emitting diode. Isocratic elution using a 0.6 mM potassium phthalate eluent combined with 1.44 mM sodium bicarbonate was employed at a flow rate of 0.75 mL/min. A linear calibration range of 0.5 to 30 mg/L PO₄³⁻ applicable to environmental and wastewater analysis was achieved. For retention time and peak area repeatability, relative standard deviation values were 0.68 and 4.09%, respectively. Environmental and wastewater samples were analyzed with the optimized ion chromatography platform and the results were compared to values obtained by an accredited ion chromatograph. For the analysis of environmental samples, relative errors of <14 % were achieved. Recovery analysis was also carried out on both freshwater and wastewater samples and recovery results were within the acceptable range for water analysis using standard ion chromatography methods.     

Dendrimers Functionalized with Palladium Complexes of N-, N,N-, and N,N,N-Ligands

Pyridine, pyridine imine, and bipyridine imine ligands functionalized by a phenol have been synthesized and characterized, in many cases by X-ray diffraction. Several of these N-, N,N-, and N,N,N,-ligands have been grafted onto the surface of phosphorhydrazone dendrimers, from generation 1 to generation 3. The complexation ability of these monomers and dendrimers towards palladium(II) has been assayed. The corresponding complexes have been either isolated or prepared in situ. In both cases, the monomeric and dendritic complexes have been tested as catalysts in Heck couplings and in Sonogashira couplings. In some cases, a positive dendritic effect has been observed, that is, an increase of the catalytic efficiency proportional to the dendrimer generation.