Activation of Molecular Hydrogen by Bis(η5,η1‐pentafulvene)‐titanium Complexes – Efficient Formation of Titanium(III)hydrides

The synthesis and crystal structures of two dinuclear titanocene hydride complexes are reported. Both complexes, namely bis(η⁵‐(di‐para‐tolylmethyl)cyclopentadienyl)titanium hydride dimer, [(η⁵‐C₂₀H₁₉)₂Ti(μ‐H)]₂ ( 2a ), and bis(η⁵‐2‐adamantylcyclopentadienyl)‐titanium hydride dimer, [(η⁵‐C₁₅H₁₉)₂Ti(μ‐H)]₂ ( 2b ), are formed via activation of molecular hydrogen by the corresponding bis(η⁵,η¹‐pentafulvene)titanium complexes 1a and 1b at ambient temperatures and pressures in high yields. The hydride complexes 2a and 2b exhibit planar [Ti₂H₂] cores and, as a result of the heterolytic cleavage of molecular hydrogen, substituted Cp Ligands were formed during the reaction.     

A New Look at the Diels–Alder Transition State

The chronology of π-orbital mixing in the Diels–Alder cycloaddition of butadiene and ethylene differs for the two main interactions, the HOMO_diene–LUMO_dieneophile and HOMO_dienophile–LUMO_diene interactions. The C2−C3 π bond of the cycloadduct is already well developed at the level of the transition state, which is reminiscent of a late transition state.     

Reduction of nitriles into aldehydes using a TMDS/V(O)(OiPr)3 reducing system

A simple and convenient method for the chemoselective reduction of nitriles into aldehydes using a 1,1,3,3-tetramethyldisiloxane (TMDS)/triisopropoxyvanadium(V) oxide reducing system is described. Aromatic as well as aliphatic nitriles are reduced into the corresponding aldehydes in moderate to good yields.     

Imines in the Titanium Coordination Sphere – Transformation of Imidoyl Chlorides to Nitrilium Ions

In the reaction of TiCl₄ in benzene as solvent with the imidoyl chloride p‐Tolyl(Cl)C=NPh ( 1 ) the abstraction of the chloride substituent is observed, leading to the nitrilium salt [p‐Tolyl–C≡N–Ph]⁺[Ti₂Cl₉]^– ( 2 ) in quantitative yield. The highly electrophilic salt 2 is characterized by IR‐ and NMR spectroscopy. The observed band for the C≡N stretching mode of 2 clearly indicates the formation of a nitrilium ion. Especially a characteristic line broadening of the ¹³C{¹H}‐NMR signals related to carbon atoms next to the nitrogen is observed. By ¹⁵N,¹H‐HMBC NMR experiments it is shown that the nitrogen signal of 2 is significantly shifted to high‐field in relation to nitriles and imines. The molecular structure of 2 was confirmed by single‐crystal X‐ray diffraction. The C≡N bond length and the linearity of the C–C≡N–C unit in 2 confirm the triple bond character of this bond.     

Emission-tunable microwave synthesis of highly luminescent water soluble CdSe/ZnS quantum dots

Water soluble CdSe/ZnS nanoparticles with emission maxima from 511 nm to 596 nm and quantum efficiencies ranging from 11% to 28% are synthesized in a facile two-step method in ambient atmospheric conditions using a commercially available microwave reactor.     

Nanotextured multicrystalline Al‐BSF solar cells reaching 18% conversion efficiency using industrially viable solar cell processes

We report recent achievements in adapting industrially used solar cell processes on nanotextured surfaces. Nanostructures were etched into c‐Si surfaces by dry exothermic plasma‐less reaction of F species with Si in atmospheric pressure conditions and then modified using a short post‐etching process. Nanotextured multicrystalline wafers are used to prepare Al‐BSF solar cells using industrially feasible solar cell proc‐ essing steps. In comparison to the reference acidic textured solar cells, the nanostructured cells showed gain in short circuit current (J_sc) of up to 0.8 mA/cm² and absolute gain in conversion efficiency of up to 0.3%. The best nanotextured solar cell was independently certified to reach the conversion efficiency of 18.0%. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Examples of scalar-flat hypersurfaces in $${\mathbb{R}^{n+1}}$$

Given a hypersurface M of null scalar curvature in the unit sphere , n ≥ 4, such that its second fundamental form has rank greater than 2, we construct a singular scalar-flat hypersurface in as a normal graph over a truncated cone generated by M. Furthermore, this graph is 1-stable if the cone is strictly 1-stable.     

H-bond relays in proton-coupled electron transfers. Oxidation of a phenol concerted with proton transport to a distal base through an OH relay

Four molecules comprising a phenol moiety and a distal pyridine base connected by an intermediary H-bonding and an H-bonded alcohol group have been synthesized and their electrochemistry has been investigated by means of cyclic voltammetry. The molecules differ by the substituent at the alcohol functional carbon and by methyl groups on the pyridine. The reaction follows a concerted proton-electron transfer pathway as confirmed by the observation of a significant H/D kinetic isotope effect in all four cases. The standard rate constants characterizing each of the four compounds are analyzed in terms of reorganization energy and pre-exponential factor. Intramolecular and solvent reorganization energies appear as practically constant in the series, in which a previously investigated aminophenol is included, whereas significantly different pre-exponential factors are observed. That the latter, which is a measure of the efficiency of proton tunneling concerted with electron transfer, be substantially smaller with the H-bond relay molecules than with the aminophenol is related to the fact that two protons are moved in the first case instead of one in the second. Within the H-bond relay molecules, the pre-exponential factor varies with the substituent present at the alcohol functional carbon in the order CF(3) > H > CH(3), presumably as the result of a fine tuning of the balance between the H-bond accepting and H-bond donating properties of the central OH group. The kinetic H/D kinetic isotope effect increases accordingly in the same order.     

Investigation of Growth Conditions for the Expansion of Porcine Mesenchymal Stem Cells on Microcarriers in Stirred Cultures

The extensive use of mesenchymal stem cells (MCS) in tissue engineering and cell therapy increases the necessity to improve their expansion. Among these, porcine MCS are valuable models for tissue engineering and are classically expanded in static T-flasks. In this work, different processes of stirred cultures were evaluated and compared. First, the effect of glucose, glutamine, antioxidant, and growth factors concentrations on porcine MSC expansion were analyzed in a suitable medium by performing kinetic studies. Results showed that a lower glucose concentration (5.5 mM) enabled to increase maximal cell concentration by 40 % compared with a higher one (25 mM), while addition of 2 to 6 mM of glutamine increased maximal cell concentration by more than 25 % compared with no glutamine supplementation. Moreover, supplementation with 1 μM thioctic acid increased maximal cell concentration by 40 % compared with no supplementation. Using this adapted medium, microcarriers cultures were performed and compared with T-flasks expansion. Porcine MSC were shown to be able to proliferate on the five types of microcarriers tested. Moreover, cultures on Cytodex 1, Cytopore 2, and Cultispher G exhibited a MSC growth rate more than 40 % higher compared with expansion in T-flasks, while MSC metabolism was similar.     

Layer-by-layer self-assembled polyelectrolyte multilayers with embedded liposomes: immobilized submicronic reactors for mineralization

The development of chemical reactions in nanospaces is of paramount importance for the development of active nanodevices, particularly in nanofluidics. It has been shown in a previous paper that phospholipid vesicles can be incorporated without spontaneous bilayer rupture into poly-L-glutamic acid/poly(allylamine) (PGA/PAH) multilayered polyelectrolyte films. The aim of the present study was to use such a system as an "embedded submicronic reactor" able to trigger precipitation of calcium phosphates within closed spaces through an enzymatic reaction, the enzyme also being encapsulated in the vesicle interior. To this aim, large unilamellar vesicles (LUVs) were produced containing calcium ions as active ions in the mineralization process, spermine as an activator of crystal growth, and alkaline phosphatase as a catalyst to convert phosphate esters into phosphates. After stabilization by adding a layer of poly-(D-lysine), these vesicles were embedded in a (PGA-PAH)n film. A paranitrophenyl phosphate containing solution was then put in contact with this film. It is shown by means of infrared spectroscopy in the attenuated total reflection mode that, consecutively to this contact, calcium phosphates are growing inside the embedded vesicles. By using scanning near-field fluorescence microscopy, it is demonstrated that the alkaline phosphatase enzymes are most probably located inside the vesicles after their embedding. In addition, atomic force microscopy was used to show, after chemical removal of the organic top layer of the film, that the inorganic platelets produced after the precipitation reaction are localized in volumes of similar size and shape as that of the vesicles into which the phosphate ester hydrolysis and subsequent precipitation reaction did occur.