To improve the key properties of nonlinear optical crystals assembled with tetrahedral functional building units

Nonlinear optical (NLO) crystals assembled with conventional non-π-conjugated tetrahedral functional building units (FBUs), generally referring to [PO₄] and [BO₄], usually exhibit weak nonlinearity and poor birefringence. It is currently proposed that partially substituting oxygen atoms with fluoride atoms in these FBUs could enhance these crucial properties. Hence, we investigated for the first time the NLO-related properties of NH₄BAsO₄F (ABAF), which was constructed from tetrahedral [BO₃F] and [AsO₄] FBUs, and enhancements of these properties were observed in this material, that is large second-harmonic generation (SHG) response (2 × KDP) and improved birefringence (0.03 at 1064 nm). Notably, both SHG coefficient and birefringence of ABAF exceeded those of a great majority of phosphates, sulfates, or boron phosphates and achieved a preferable balance. It is interesting that ABAF shows vast structural similarities to the typical NLO crystals Sr₂Be₂B₂O₇ (SBBO) and KBe₂BO₃F₂ (KBBF), which might be the partial reason why it showed improvement in these vital properties. This work may afford some inspiration for enhancing the key performances of NLO crystals assembled with non-π-conjugated tetrahedra.

We report a new nonlinear optical crystal assembled exclusively with tetrahedral functional building units in which enhanced birefringence (Δn) and second-harmonic generation (d_eff) were observed.     

One-step hexaplex immunoassays by on-line paper substrate-based electrospray ionization mass spectrometry for combined cancer biomarker screening

Mass spectrometry (MS) is attractive as a multiplexed immunoassay readout benefiting from its high sensitivity, speed and mass resolution. Here, a simple paper-based hexaplex immunoassay with an on-line MS readout was proposed, using functionalized paper as the immune substrates, along with rhodamine-based mass tags assembled on gold nanoparticles prepared as the mass probes (MPs). Simultaneous immune capture and labeling were conducted in one step on paper substrates in 96-well plates with a high throughput within 30 minutes, and the on-line efficient dissociation of the mass tags highly facilitated the hexaplex readout of the immune signals by a newly established on-line paper substrate-based electrospray ionization-MS setup. Six MPs were synthesized for the simultaneous quantification of six important cancer protein markers (cancer antigen 15-3, cancer antigen 19-9, carcinoma embryonic antigen, cancer antigen 125, human epididymis protein 4, and alpha fetoprotein) using only 10 μL serum, presenting satisfactory sensitivity, accuracy and specificity. This platform was further tested in screening for the six biomarkers in serum samples of patients with breast, liver and gastric cancers, showing its high potential for sensitive and specific early cancer diagnosis.

On-line paper substrate based electrospray ionization mass spectrometry for hexaplex immunoassays.     

在线分离光度法测定痕量金的研究

本提出了一种泡沫塑料柱在线分离富集／β－环糊精－十二烷基苯磺酸钠溶液在线洗脱／硫代米蚩酮光度法测定痕量金的新方法。方法的检测出限是３×１０＾－＾８ｇＡｕ，线性范围是５×１０＾－＾７－８×１０＾－＾６Ａｕ，对于１．０μｇＡｕ进行１１次测定，相对标准偏差小于３．０％。     

New perylene polyimides containing p‐n diblocks for sensitization in TiO2 solar cells

Three novel perylene polyimides (PPIs) containing p‐n diblock units were designed and synthesized for use in dye‐sensitized mesoporous TiO₂ solar cells. They all dissolve in m‐cresol and N‐methyl‐2‐pyrrolidone (NMP). Their visible light absorption, electrochemical and photoelectrochemical properties were systematically studied. The polyimides have band gap energies of 2.16, 2.19 and 2.25 eV deduced from ultraviolet–visible absorption spectra, and electron affinity (E_a) and ionization potential (IP) of ?3.93 and 6.10 eV for PPI1, ?3.94 and 6.13 eV for PPI2, ?3.93 and 6.59 eV for PPI3, respectively, deduced from cyclic voltammogram. Experimental data show that introduction of 4,4′‐bisaminetriphenylamine cannot only greatly enhance optic‐electro conversion efficiency, but also enhance the dissolubility which in favorable for making the devices. The relationship of structure and properties of PPI is discussed and the mechanism of photocurrent generation is explained. Copyright © 2004 John Wiley & Sons, Ltd.     

偏最小二乘-速差动力学分光光度法同时测定杀虫剂残杀威和异丙威两组分

采用速差动力学分光光度法对氨基甲酸脂类杀虫剂残杀威和异丙威进行同时测定，这两种化 的能在碱性条件下水解生成酚盐，进而与对氨基苯酚及高碘酸钾的反应产物醌亚胺发生偶联反应，生成蓝色化合物。反应的速率适中，可用于动力学分析。实验采集了多个时间点下538－700nm间的动力学－吸光度数据，构成量测矩阵，并采用偏最小二乘（PLS）法对量测数据进行解析。本文还对合成样品和环境水样中的残杀威和异丙威含量进行测定，获较好的结果。     

Lewis-acid assisted cross metathesis of acrylonitrile with functionalized olefins catalyzed by phosphine-free ruthenium carbene complex

The exchange of the PPh3 ligand in the complex [1,3-bis(2,6-dimethylphenyl)4,5-dihydroimidazol-2-ylidene](PPh3)(Cl)2Ru=CHPh (7) for a pyridine ligand at ambient temperature leads to the formation of the stable phosphine-free carbene ruthenium complex [1,3-bis(2,6-dimethylphenyl)4,5-dihydroimidazol-2-ylidene](C5H5N)2(Cl)2 Ru=CHPh (8). The resulted ruthenium complex exhibits highly catalytic activity for the cross metathesis of acrylonitrile with various functionalized olefins under mild conditions, and its activity can be further improved by the addition of a Lewis acid such as Ti(OiPr)4. In the mixture products, the Z-isomer predominates.     

High performance organic field-effect transistors based on amphiphilic tris(phthalocyaninato) rare earth triple-decker complexes

LB films of three amphiphilic tris(phthalocyaninato) rare earth triple-decker complexes with crown-ethers as hydrophilic heads and long alkyl chains as hydrophobic tails have been prepared and found to display very well ordered layer structures, as proved by pi-A isotherms, UV-vis and polarized absorption spectra, X-ray diffraction experiments, and microscopic morphology characterization. These LB films have been fabricated into field-effect transistor (FET) devices, which show carrier mobilities as high as 0.24-0.60 cm2 V-1 s-1, among the highest mobilities achieved thus far for all LB film-based OFETs.     

Kilogram-scale synthesis of carbon quantum dots for hydrogen evolution,sensing and bioimaging

A facile, low-cost, green, kilogram-scale synthesis of high quality CQDs were synthesized. The throughput of CQDs is 1.4975 kg in one pot and the as-prepared CQDs have a highly crystalline hexagonal structure with remarkable solubility, stability, and biocompatibility. It showed outstanding electrocatalytic activity, Fe³⁺ sensitivity and good biocompatibility.     

Monitoring of the conversion from triptolide to tripchlorolide in Triptergium wilfordii by micellar electrokinetic caillary chromatography

A novel concocting method to convert Triptolide (T) into Tripchlorolide (T(4)) in the traditional Chinese herb Tripterygium wilfordii Hook F. and a micellar electrokinetic capillary chromatographic (MEKC) approach by which the conversion of Triptolide (T) and Tripchlorolide (T(4)) was identified and determined had been established. Investigations of the influence of different pH values of boric acid and borax buffer and of sodium dodecyl sulfate (SDS) and organic additive concentrations had been carried out, and the optimum separation for T and T(4) was achieved using boric acid and borax of pH 7.0 with 30 mM SDS and 20% (volume ratio) methanol as the running buffer. It was found that MEKC exhibited good accuracy, precision and repeatability and the content of T(4) was greatly increased in the herb that was treated by the new concocting method.