Reactions of N-silylphosphoranimines with alcohols: synthesis and structure of cyclotriphosphazenes with nongeminal methyl and phenyl substituents

The reactions of Me(3)SiN=P(OR")RR'(R" = Ph, CH(2)CF(3); R, R' = Me, Ph) with alcohols were investigated. With nonequivalent amounts of CF(3)CH(2)OH, the reactions produced high yields of the cyclic phosphazene (Me(2)PN)(3) and both the cis and trans isomers of nongeminally substituted [(Ph)(Me)PN](3). The isomers of this new cyclic phosphazene were separated by column chromatography and characterized by NMR and IR spectroscopy, elemental analysis, and X-ray crystallography. Crystals of the cis isomer 6a have a monoclinic crystal system, while the trans isomer 6b has a triclinic crystal system with two different molecules in an asymmetric unit. The bond lengths and bond angles are very similar to those of the simpler cyclic trimers (Me(2)PN)(3) and (Ph(2)PN)(3.) A likely pathway for the formation of these compounds is discussed.     

Efficient resolution of racemic 1,1'-bi-2-naphthol with chiral selectors identified from a small library

Efficient resolution of racemic 1,1'-bi-2-naphthol, a well-studied analyte in chiral separation, was achieved using selectors developed from a small library. Separation factors (up to 7.2) obtained are significantly higher than the ones reported previously for this analyte. The library consists of 121 members and it does not contain the pi deficient 3,5-dinitrobenzoyl (Dnb) group. These highly efficient stationary phases may lead to the practical large-scale chromatographic resolution of enantiomers of 1,1'-bi-2-naphthol, which are widely used as chiral auxiliaries and ligands in asymmetric synthesis.     

Versatile cobalt complexes for initiating immortal ring‐opening polymerization (ROP) of lactide (LA), mediating living radical polymerization of t‐butyl acrylate (tBA) and catalyzing copolymerization of LA and tBA by combination of ROP and organometallic‐mediated radical polymerization

Low‐cost, highly active and versatile amino‐bis(phenolate) cobalt complexes are developed. The cobalt complexes can control living polymerization of different categories of monomers including lactide (LA) by immortal ring‐opening polymerization in argon and even in air and acrylate via living radical polymerization (LRP). The cobalt‐based catalysts were used for copolymerization of LA and acrylate. The immortal polymerization of LA using the cobalt complexes as initiators proceeds in argon and even in air and without the requirement for extensive drying techniques or inert atmosphere whilst retaining end‐group fidelity. The cobalt complexes are used to mediate LRP of t‐butyl acrylate (tBA) in methanol. The block copolymerization of LA and tBA catalyzed by single‐site cobalt organometallic catalyst is also reported for the first time. This cobalt system offers a versatile and green way to produce homopolymers and block copolymers.     

Modeling fatigue of ascending stair evacuation with modified fine discrete floor field cellular automata

Fatigue even increases the complexity of the pedestrian dynamics which is regarded as a kind of nonlinear system, and might have a significant negative impact on the crowd evacuation. However, it has never been investigated completely and properly. Thus, the fine discrete floor field cellular automata model is modified by integrating the fatigue function to explore the influence of fatigue on the crowd ascending evacuation. The simulation fits well with the empirical data and the observations quantitatively and qualitatively, indicating the model captures the main features of evacuation considering fatigue impact. As a prediction, without merging streams, compared with the case of walking in constant speed, when fatigue is considered, it takes 71.4% longer for all persons to enter the stairs and 87.2% longer to evacuate. With merging streams, fatigue has little impact on the inflow, while it makes the total evacuation time 84.2% longer.     

Amperometric nonenzymatic determination of glucose based on a glassy carbon electrode modified with nickel(II) oxides and graphene

We have developed a stable and sensitive nonenzymatic glucose sensor by modifying a glassy carbon electrode (GCE) with a composite incorporating nickel(II) oxides and reduced graphene. The oxides were generated by directly electrodepositing nickel on the GCE with a graphene modifier using a multi-potential pulse process, and then oxidizing nickel to nickel(II) oxides by potential cycling. In comparison to the conventional nickel(II) oxides-modified GCE, this new nickel(II) oxides-graphene modified GCE (NiO-GR/GCE) has an about 1.5 times larger current response toward the nonenzymatic oxidation of glucose in alkaline media. The response to glucose is linear in the 20 μM to 4.5 mM concentration range. The limit of detection is 5 μM (at a S/N of 3), and the response time is very short (<3 s). Other beneficial features include selectivity, reproducibility and stability. A comparison was performed on the determination of glucose in commercial red wines by high-performance liquid chromatography (HPLC) and revealed the promising aspects of this sensor with respect to the determination of glucose in real samples.

An efficient one-pot asymmetric synthesis of biaryl compounds via Diels-Alder/retro-Diels-Alder cascade reactions

[reaction: see text] A single-step chirality transfer method for the synthesis of axially chiral biaryl compounds by construction of the second aromatic ring via a Diels-Alder/retro-Diels-Alder cascade reaction is reported. This methodology should find broad application in the synthesis of natural products and asymmetric catalysts.     

Limit cycle bifurcations near a double homoclinic loop with a nilpotent saddle of order m

In this paper, we study the explicit expansion of the first order Melnikov function near a double homoclinic loop passing through a nilpotent saddle of order m in a near-Hamiltonian system. For any positive integer $m(m\ge 1)$, we derive the formulas of the coefficients in the expansion, which can be used to study the limit cycle bifurcations for near-Hamiltonian systems. In particular, for $m=2$, we use the coefficients to consider the limit cycle bifurcations of general near-Hamiltonian systems and give the existence conditions for 10, 11, 13, 15 and 16 (11, 13 and 16, respectively) limit cycles in the case that the homoclinic loop is of cuspidal type (smooth type, respectively) and their distributions. As an application, we consider a near-Hamiltonian system with a nilpotent saddle of order 2 and obtain the lower bounds of the maximal number of limit cycles.     

激光二极管相对于铯饱和吸收D2线的无调制扰动三次谐波锁频

将频率调制加在声光调制器上 ,用三次谐波探测法获得了铯原子D2 线的三阶微分饱和光谱。采用这种激光器无调制扰动方案结合三次谐波锁频技术 ,实现了 85 2nm的分布布拉格反射器半导体激光器相对于 6S1/2 F =4- 6P3 /2 F′ =5超精细跃线的频率锁定。由锁定后的频率误差信号估算 ,10s内激光频率起伏小于± 35 0kHz ,相对频率稳定度约 1× 10 -9。这种无调制扰动方案可以消除一般的饱和吸收稳频方法中由于直接对激光器进行频率调制而带来的额外频率噪声 ;三次谐波锁频技术的应用 ,还可有效地降低铯原子饱和吸收谱中剩余多普勒背景的影响     

Excited state structural dynamics and Herzberg–Teller coupling of tetraphenylporphine explored via resonance Raman spectroscopy and density functional theory calculation

Resonance Raman spectra of free-base tetraphenylporphine (TPP) were obtained with 397.9, 416, and 435.7 nm excitation wavelengths and density functional calculations were done to elucidate the electronic transitions and the resonance Raman spectra (RRs) of TPP. The RRs indicate that the Franck–Condon region photodynamics for S₀ → S₄ electronic state is predominantly along the C_m–ph stretch while that for S₀ → S₃ electronic state is predominantly along the porphin ring C_βC_β stretch. Non-totally symmetric vibrational modes were regularly presented in resonance Raman spectra: the shorter the excitation wavelengths were, the stronger intensity the modes had, which can be interpreted in terms of electric dipole transition moments caused by Franck–Condon and Herzberg–Teller coupling.Four non-total symmetry vibrational mode υ_52, υ₆₄, υ₉₇ and υ₁₃₀ in A₂ irreducible representative of TPP were observed in 397.9, 416 and 435.7 nm resonance Raman spectrum. With the shorter wavelength laser excitations at 416 or 397.9 nm, the A₂ vibrational modes show more enhanced Raman intensity by comparison with those in the TPP spectrum excited at 435.7 nm.