燃料电池铂钴锰合金催化剂的制备及性能

为提高PtCo/C合金催化剂的电化学性能,采用微波法合成铂钴锰催化剂前驱体,经高温热处理形成合金,最后通过酸处理得到铂钴锰合金催化剂(PtCoMn/C)。电化学测试结果表明:适量锰的添加可提升PtCo/C催化剂的活性和耐久性。PtCoMn/C催化剂在 0.9 V(vs RHE)电压下的质量比活性(MA)达到 0.666 A·mg_Pt^-1,是传统 Pt/C 的 2.66 倍,是 PtCo/C 催化剂的 1.30 倍。在30 000圈催化剂加速耐久性测试中,PtCoMn/C合金催化剂的电化学活性面积(ECSA)和质量比活性(MA)仅下降6.9%和27.1%,均远低于Pt/C催化剂。     

Asymmetric Synthesis of Novel Axially Chiral 2,2'-Bipyridine N,N'-Dioxides Bearing α-Amino Acid Residues and Their Applications in Enantioselective Allylation of Aromatic Aldehydes with Allyltrichlorosilane

A series of novel axially chiral 2,2′‐bipyridine N,N′‐dioxides bearing C₁ or C₂‐symmetry have been synthesized by the use of enantiopure α‐amino acids as chiral sources. The absolute stereochemistry of the axial chirality of these organocatalysts has been clearly assigned by means of CD measurements together with literature protocols. The reactivities and enantioselectivities of these organocatalysts have been examined in the reactions of aromatic aldehydes with allyltrichlorosilane, thus providing the desired products with moderate yields and enantioselectivies.     

金属-半导体异质结构纳米晶的可控制备和光谱调控

本文简要综述了金属-半导体异质结构纳米晶的设计、可控制备和物性研究的相关工作.设计了异相成核与生长、选择硫化和种子介导液相外延生长3种不同的方法并以此制备了多种金属-半导体异质结构纳米晶,对其中所涉及的反应机制进行了论述,并简要探讨了金属-半导体异质结构纳米晶的热稳定性、表面等离子共振活性、荧光特性以及异质界面的电荷转移和保持能力.     

SPE–HPLC–MS/MS method for the trace analysis of tobacco‐specific N‐nitrosamines and 4‐(methylnitrosamino)‐1‐(3‐pyridyl)‐1‐butanol in rabbit plasma using tetraazacalix[2]arene[2]triazine‐modified silica as a sorbent

Tobacco‐specific N‐nitrosamines (TSNAs), including N′‐nitrosonornicotine, 4‐(methylnitrosamino)‐1‐(3‐pyridyl)‐1‐butanone, N′‐nitrosoanatabine, and N′‐nitrosoanabasine, have been implicated as a source of carcinogenicity in tobacco and cigarette smoke. We present a rapid and effective method comprising SPE based on tetraazacalix[2]arene[2]triazine‐modified silica as sorbent and analysis with HPLC–MS/MS for the determination of TSNAs and 4‐(methylnitrosamino)‐1‐(3‐pyridyl)‐1‐butanol (NNAL), a metabolite of 4‐(methylnitrosamino)‐1‐(3‐pyridyl)‐1‐butanone, in rabbit plasma. The linear dynamic ranges were 10–2000 pg/mL for NNAL and 4–2000 pg/mL for the four TSNAs with good correlation coefficients (>0.9965). The LODs were in the range of 0.9–3.7 pg/mL, and the LOQs were between 2.9 and 12.3 pg/mL. The accuracies of the method were also evaluated and found to be in the range of 90.1–113.3%. This method is promising to be applied to the preconcentration and determination of TSNAs and NNAL in smoke and human body fluids.     

Reversal of elution order of N‐(2,4‐dinitrophenyl)‐proline and N‐(2,4‐dinitrophenyl)‐serine in HPLC by BSA chiral stationary phase

N‐(2,4‐dinitrophenyl)‐proline and N‐(2,4‐dinitrophenyl)‐serine were enantiomerically resolved on the BSA chiral stationary phase by HPLC in reversed‐phase mode. Effects of chromatographic conditions on enantioseparation and elution order have been investigated in detail. For these two samples, reversal of enantiomer elution order was observed by changing buffer pH, the content of acetonitrile, or alcohol modifiers in mobile phase, which is firstly reported in the BSA chiral stationary phase studies. More interestingly, combined effect between buffer pH and the content of acetonitrile was also observed. In addition, coelution range of enantiomers varied along with the content of acetonitrile in mobile phase.     

Ligand‐Functionalization of BPEI‐Coated YVO4:Bi3+,Eu3+ Nanophosphors for Tumor‐Cell‐Targeted Imaging Applications

In this study, surface‐functionalized, branched polyethylenimine (BPEI)‐modified YVO₄:Bi³⁺,Eu³⁺ nanocrystals (NCs) were successfully synthesized by a simple, rapid, solvent‐free hydrothermal method. The BPEI‐coated YVO₄:Bi³⁺,Eu³⁺ NCs with high crystallinity show broad‐band excitation in the λ=250 to 400 nm near‐ultraviolet (NUV) region and exhibit a sharp‐line emission band centered at λ=619 nm under excitation at λ=350 nm. The surface amino groups contributed by the capping agent, BPEI, not only improve the dispersibility and water/buffer stability of the BPEI‐coated YVO₄:Bi³⁺,Eu³⁺ NCs, but also provide a capability for specifically targeted biomolecule conjugation. Folic acid (FA) and epidermal growth factor (EGF) were further attached to the BPEI‐coated YVO₄:Bi³⁺,Eu³⁺ NCs and exhibited effective positioning of fluorescent NCs toward the targeted folate receptor overexpressed in HeLa cells or EGFR overexpressed in A431 cells with low cytotoxicity. These results demonstrate that the ligand‐functionalized, BPEI‐coated YVO₄:Bi³⁺, Eu³⁺ NCs show great potential as a new‐generation biological luminescent bioprobe for bioimaging applications. Moreover, the unique luminescence properties of BPEI‐coated YVO₄:Bi³⁺,Eu³⁺ NCs show potential to combine with a UVA photosensitizing drug to produce both detective and therapeutic effects for human skin cancer therapy.     

Porous V2O5-SnO2/CNTs composites as high performance cathode materials for lithium-ion batteries

Vanadium pentoxide (V₂O₅) exhibits high theoretical capacities when used as a cathode in lithium ion batteries (LIBs), but its application is limited by its structural instability as well as its low lithium and electronic conductivities. A porous composite of V₂O₅-SnO₂/carbon nanotubes (CNTs) was prepared by a hydrothermal method and followed by thermal treatment. The small particles of V₂O₅, their porous structure and the coexistence of SnO₂ and CNTs can all facilitate the diffusion rates of the electrons and lithium ions. Electrochemical impedance spectra indicated higher ionic and electric conductivities, as compared to commercial V₂O₅. The V₂O₅-SnO₂/CNTs composite gave a reversible discharge capacity of 198 mAh·g^?1 at the voltage range of 2.05–4.0 V, measured at a current rate of 200 mA·g^?1, while that of the commercial V₂O₅ was only 88 mAh·g^?1, demonstrating that the porous V₂O₅-SnO₂/CNTs composite is a promising candidate for high-performance lithium secondary batteries.     

An ultrasensitive quantum dots fluorescent polarization immunoassay based on the antibody modified Au nanoparticles amplifying for the detection of adenosine triphosphate

In this work, an ultrasensitive fluorescent polarization immunoassay (FPIA) method based on the quantum dot/aptamer/antibody/gold nanoparticles ensemble has been developed for the detection of adenosine triphosphate (ATP). DNA hybridization is formed when ATP is present in the PBS solution containing the DNA-conjugated quantum dots (QDs) and antibody-AuNPs. The substantial sensitivity improvement of the antibody-AuNPs-enhanced method is mainly attributed to the slower rotation of fluorescent unit when QDs-labeled oligonucleotides hybridize with antibody modified the gold nanoparticle. As a result, the fluorescent polarization (FP) values of the system increase significantly. Under the optimal conditions, a linear response with ATP concentration is ranged from 8 × 10⁻¹² M to 2.40 × 10⁻⁴ M. The detection limit reached as low as 1.8 pM. The developed work provides a sensitive and selective immunoassay protocol for ATP detection, which could be applied in more bioanalytical systems.     

Three New C19‐Diterpenoid Alkaloids from Aconitum forrestii

A further study of the alkaloid constituents of Aconitum forrestii led to the isolation of three new C₁₉‐diterpenoid alkaloids, named 14‐acetoxy‐8‐O‐methylsachaconitine ( 1 ), 14‐acetoxyscaconine ( 2 ), and 8‐O‐ethylcammaconine ( 3 ). Their structures were determined by UV, IR, and MS, 1D‐ and 2D‐NMR analyses.     

Ab‐Initio study of Helium‐small carbon cage systems

The traditional method for opening the electron shells of noble gas atoms involves a strong electronegative atom or group. However, this approach is limited to only heavy noble‐gas atoms, such as Kr and Xe. In this paper, we performed accurate calculations of He@C₈H₈ and He@C10H16 and showed the possibility of opening the electron shell of a light noble‐gas atom. © 2012 Wiley Periodicals, Inc.