Formation of bamboo-shaped carbon nanotubes on carbon black in a fluidized bed

For the first time, bamboo-shaped multiwalled carbon nanotubes, having diameter of the order of 50 nm, have been grown on carbon black in a fluidized bed in bulk amount. The activation energy for the synthesis of the product was found out to be around 33 kJ/mol in the temperature range of 700−900 °C. The carbon nanotubes were separated from the carbon black by preferential oxidation of the later, the temperature of which was determined by thermogravimetry. The transmission electron microscopy revealed different features of the nanotubes such as “Y” junction, bend, and catalyst filling inside the nanotubes. Small angle neutron scattering was performed on the nanotubes synthesized at different temperatures. The data were fitted into a suitable model in order to find out the average diameter, which decreases with increase in synthesis temperature. The Monte Carlo simulation predicts the same behavior. Based on the above observations, a possible growth mechanism has been predicted. The oscillation in carbon saturation value inside the catalyst in the fluidized bed has been indicated as the responsible factor for the bamboo-shaped structure.     

Stepwise Self-assembly of a Tripeptide from Molecular Dimers to Supramolecular β-sheets in Crystals and Amyloid-like Fibrils in the Solid State

The terminally protected tripeptide Boc–Ala(1)–Leu(2)–Ala(3)–OMe 1 forms antiparallel hydrogen-bonded dimers of two different conformers in the asymmetric unit and the individual dimers then self-associate to form supramolecular β-sheet structures in crystals and amyloid-like fibrils in the solid state.     

Reduced field-of-view diffusion-weighted imaging of the brain at 7 T

Ventral and rostral regions of the brain are of emerging importance for the MRI characterization of early dementia, traumatic brain injury and epilepsy. Unfortunately, standard single-shot echo planar diffusion-weighted imaging of these regions at high fields is contaminated by severe imaging artifacts in the vicinity of air–tissue interfaces. To mitigate these artifacts and improve visualization of the temporal and frontal lobes at 7 T, we applied a reduced field-of-view strategy, enabled by outer volume suppression (OVS) with novel quadratic phase radiofrequency (RF) pulses, combined with partial Fourier and parallel imaging methods. The new acquisition greatly reduced the level of artifacts in six human subjects (including four patients with early symptoms of dementia).     

New Fluorinated Poly(imide siloxane) Random and Block Copolymers with Variation of Siloxane Loading

Several new random and block copoly(imide siloxane)s have been prepared by the solution polycondensation of commercially available 4,4′-oxydianiline (ODA) and amino-propyl terminated polydimethylsiloxane (APPS) with 4,4′-(hexafluoro-isopropylidene)diphthalic anhydride (6FDA). The siloxane loading was kept to 10, 20, 30, 40 and 50 wt% in the copolymers. The random copolymers were prepared by a one pot solution imidization technique, and two pot solution imidization technique was adopted for the synthesis of the block copolymers. The diamine ODA and the dianhydride 6FDA composed the hard block segment, while APPS and 6FDA composed the soft block segment. The hard block length was kept constant while the soft block lengths were varied by varying the siloxane loading. Accordingly, block copoly(imide siloxane)s were prepared on increasing the soft block lengths (DP) from 3 to 6, 10, 18 and 36 for fixed hard block length of 22. The resulting polymers have been well characterized by IR, NMR and GPC techniques. Thermal and mechanical properties of the random and block copolymers were compared with the already reported homopolyimide without siloxane moiety.     

Copper(II) Complexes of 3,4,5‐Trisubstituted Pyrazolates: In Situ Formation of Pyrazole Rings from Different Carbon Centers

The synthesis and characterization of two pyrazolate‐bridged dicopper(II) complexes, [Cu₂(L¹)₂(H₂O)₂](ClO₄)₂ ( 1 , HL¹=3,5‐dipyridyl‐4‐(2‐keto‐pyridyl)pyrazole) and [Cu₂(L²)₂(H₂O)₂](ClO₄)₂ ( 2 , HL²=3,5‐dipyridyl‐4‐benzoylpyrazole), are discussed. These copper(II) complexes are formed from the reactions between pyridine‐2‐aldehyde, 2‐acetylpyridine (for compound 1 ) or acetophenone (for compound 2 ), and hydrazine hydrate with copper(II) perchlorate hydrate under ambient conditions. The single‐crystal X‐ray structure of compound 1? 2 H₂O establishes the formation of a pyrazole ring from three different carbon centers through C? C bond‐forming reactions, mediated by copper(II) ions. The free pyrazoles (HL¹ and HL²) are isolated from their corresponding copper(II) complexes and are characterized by using various analytical and spectroscopic techniques. A mechanism for the pyrazole‐ring synthesis that proceeds through C? C bond‐forming reactions is proposed and supported by theoretical calculations.     

Magnesium Methoxide-Assisted Synthesis of 2,4,6-Triaryl Pyridines

A new three-component reaction of chalcones, ketones, and ammonia assisted by magnesium methoxide is described. The corresponding 2,4,6-triaryl pyridines (Kröhnke pyridines) are formed in fair to good yields (34–76%) within 3 h. The method also provides a facile way to synthesize 2(6)-difluoromethyl pyridines via an interesting mechanism.     

A ligand free copper(II) catalyst is as effective as a ligand assisted Pd(II) catalyst towards intramolecular C–S bond formation via C–H functionalization

Copper(I) catalysts are usually ineffective on the other hand Pd(II) catalysts are quite effective in promoting intramolecular sp² C–H functionalization (C–S bond formation). Herein, we have developed a ligand assisted Pd(II) catalyzed C–S bond formation via C–H activation from arylthioureas leading to the formation of 2-aminobenzothiazoles for substrates bearing electron donating (EDG) groups in the aryl ring. However without the assistance of ligand this Pd(II) catalyzed reaction is quite unproductive particularly for thioureas possessing strongly electron donating groups in the aryl rings. Interestingly, the ligand free Cu(II) catalyzed oxidative cyclization of arylthioureas are equally effective both for arylthioureas possessing electron donating as well as electron withdrawing groups in the aryl rings.