Templating and supersaturation-driven anti-templating: principles of biomineral architecture

The structural synergy between biominerals (CaCO(3), hydroxyapatite) and biosubstrates were examined for the first time. The templating effect of substrate and a newly identified supersaturation-driven interfacial structure mismatch effect were identified in the context of a new nucleation model. It follows that the heterogeneous nucleation which corresponds to a good structural match and synergy between biominerals and substrates will promote an ordered, compact, and tough complex biomineral structure, and occur only at low supersaturations, whereas at high supersaturations the heterogeneous nucleation associated with a poor structural match and synergy between biominerals and substrates will become dominant due to supersaturation-driven interfacial structural mismatch. The latter normally results in a disordered and porous structure. A phenomenon, so-called microgravity-driven homogeneous nucleation, was also examined. It turns out that microgravity will suppress convection and consequently promote homogeneous-like nucleation during biomineralization. This could be responsible for microgravity-induced osteoporousis.     

Novel chiral imidazole cyclophane receptors: synthesis and enantioselective recognition for amino acid derivatives

Novel chiral imidazole cyclophane receptors were synthesized by highly selective N-alkylation of the imadazolyl 1N-position of the bridged histidine diester 2 with the dibromide in the presence of NaH; these receptors exhibit good chiral recognition toward the enantiomers of L- and D-amino acid derivatives (up to KD/KL = 3.52, delta delta G0 = -3.11 kJ mol-1) in CHCl3 at 25.0 degrees C.     

Black Hole Entropy: Membrane Approach

The wall contribution character of the Bekenstein–Hawking entropy in the brick-wall model leads us to propose a new method of computing the entropy of a black hole. In our model, the entropy is attributed to the dynamical degrees of the field covering the two dimensional membranes just outside the horizon. A cutoff different from the model of 't Hooft is necessarily introduced. It can be treated as an increase in horizon because of the space–time fluctuations. It is also shown that our method can be applied to the nonstatic case, such as Vaidya–deSitter space–time, and the final result relies on a time-dependent cutoff different from the brick-wall model.     

Self-starting stretched-pulse fiber laser mode locked and stabilized with slow and fast semiconductor saturable absorbers

A self-starting stretched-pulse mode-locked erbium-doped fiber laser that uses fast and slow semiconductor saturable absorbers is described. By using two absorbers, we obtained reliable operation at a fundamental repetition rate with 250 pJ of pulse energy without multiple-pulse breakup. External chirp compensation was used to compress the highly chirped pulses to durations of 135 fs.     

One-dimensional gallium nitride micro/nanostructures synthesized by a space-confined growth technique

Hexagonal GaN prismatic sub-micro rods and cone nanowires have been synthesized in a large scale by a novel and controllable space-confined growth method. The as-synthesized GaN products are highly crystalline with a wurtzite structure. The prismatic rods have lengths of 15∼20 μm and diameters of 400∼500 nm enclosed by hexagonal smooth side surfaces and a pyramidal end. And the cone nanowires have average diameters of 150∼200 nm and lengths up to several tens of μm with a cone tip. The photoluminescence (PL) studies reveal prominent band-gap UV emission properties of GaN products and narrow FWHM, indicating the excellent luminescent performance and high crystal quality. For field emission characteristic of GaN nanowires, the turn-on field is about 9.5 V/μm and the current density reaches 1.0 mA/cm² at an electric field of 18 V/ μm. The contrast experiments indicate a novel growth control can be achieved by using a graphite tube as reaction vessel. The sealed graphite tube combined with metallic initiator is greatly responsible for large-scale and uniform preparation of GaN prismatic rods and cone nanowires. Highly symmetric GaN hexagonal micropyramids are grown on a bare Si substrate. The growth mechanism and the control function of the graphite tube are demonstrated. These low-dimensional structures not only enrich semiconducting GaN family, but also are good building blocks for optoelectronic devices. PACS 81.10.Bk; 81.07.-b; 81.05.Ea     

Investigation of Ti/TiN multilayered films in a reactive mid-frequency dual-magnetron sputtering

Influence of the process parameters like (i) sputtering gas pressure, (ii) target current, (iii) substrate bias voltage and (iv) substrate temperature of a reactive mid-frequency dual-magnetron sputtering on (a) surface defects and (b) mechanical properties of Ti/TiN multilayered films was investigated. The forming mechanisms of the observed droplets and craters were analyzed. Results showed when: (1) pressure of Ar/N₂ gases PAr/N₂ was at 0.31 Pa and substrate temperature was in certain range, the size and the density of the surface defects on the TiN films tended to decrease with increasing the target current and the pulsed bias voltage; (2) the optimal deposition parameters for accomplishing fewer surface defects were used, increasing the thickness of the Ti buffer layer decreased the microhardness in certain level, and the adhesion was firstly increased and then decreased as thickness reaching and/or beyond a critical value. Results also showed that selection of optimized process parameters evidently minimized the surface defects and improved the mechanical properties of the film.     

Dangling bond-induced graphitization process on the (111) surface of diamond nanoparticles

The intrinsic mechanism of graphitization occurring on the (111) surface of nanodiamonds (NDs) during the transformation from NDs into bucky diamonds are explored using density functional theory (DFT) computations in conjunction with density functional based tight-binding simulations. The DFT results indicate that dangling bonds (DBs) on the ND surfaces play an important role in the graphitization process, and the orientation of the DBs on different ND surfaces determines whether there will be a graphitization process or not. Moreover, a criterion is proposed to estimate rupturing of the C-C bonds between different layers on the [111] direction in the NDs and is verified to be applicable to illustrate the phase transformation from sp(3) into sp(2) bonding structures. The energy contributions of the four-coordinated carbon atoms located at different positions on the (111) surface are exhibited for the first time and discussed in detail to gain a clear picture for the transition from NDs into bucky diamonds. The outcome may provide a deeper understanding on the influence of DBs upon the transformation from sp(3) into sp(2) bonding structures.     

Theoretical studies on the mechanism of acid-promoted hydrolysis of N-formylaziridine in comparison with formamide

[reaction: see text] We present an ab initio study of the acid-promoted hydrolysis reaction mechanism of N-formylaziridine in comparison with formamide. Since the rate of amide hydrolysis reactions depends on the formation of the tetrahedral intermediate, we focused our attention mainly on the reactant complex, the tetrahedral intermediate, and the transition state connecting these two stationary points. Geometries were optimized using the density functional theory, and the energetics were refined using ab initio theory including electron correlation. Solvent effects were investigated by using polarizable continuum method calculations. The proton-transfer reaction between the O-protonated and N-protonated amides was investigated. In acidic media, despite that the N-protonated species is more stable than the O-protonated one, it is predicted that both N-protonated and O-protonated pathways compete in the hydrolysis reaction of N-formylaziridine.     

A general and efficient 2-amination of pyridines and quinolines

Pyridine N-oxides were converted to 2-aminopyridines in a one-pot fashion using Ts2O-t-BuNH2 followed by in situ deprotection with TFA. The amination proceeded in high yields, excellent 2-/4-selectivity, and with good functional group compatibility. 2-Amino (iso)quinolines were also obtained in the same manner. Combined with the simple oxidation of pyridines to pyridine N-oxides, this method provides a general and efficient way for amination of 2-unsubstituted pyridines.