The Effect of the Spacer of Bis(biurea) Ligands on the Structure of A2L3‐type (A=anion) Phosphate Complexes

By tuning the length and rigidity of the spacer of bis(biurea) ligands L, three structural motifs of the A₂L₃ complexes (A represents anion, here orthophosphate PO₄^3?), namely helicate, mesocate, and mono‐bridged motif, have been assembled by coordination of the ligand to phosphate anion. Crystal structure analysis indicated that in the three complexes, each of the phosphate ions is coordinated by twelve hydrogen bonds from six surrounding urea groups. The anion coordination properties in solution have also been studied. The results further demonstrate the coordination behavior of phosphate ion, which shows strong tendency for coordination saturation and geometrical preference, thus allowing for the assembly of novel anion coordination‐based structures as in transition‐metal complexes.     

离子对反相高效液相色谱法同时测定尿液中复方α-酮酸片的5种有效成分

建立了同时测定尿液中复方α-酮酸片5种有效成分(消旋羟蛋氨酸钙(HMACa)、酮缬氨酸钙(KVCa)、消旋酮异亮氨酸钙(KILCa)、酮亮氨酸钙(KLCa)和酮苯丙氨酸钙(KPACa))的离子对反相高效液相色谱法。分别考察了离子对试剂浓度、缓冲盐浓度和流动相pH值等参数对分离情况的影响。最终采用Waters Symmetry C18色谱柱(250 mm×4.6 mm,5μm);以乙腈和含15 mmol/L四丁基氢氧化铵的20 mmol/L磷酸盐缓冲液(pH 7.0)为流动相进行梯度洗脱,流速为1.0 mL/min;柱温为35℃;检测波长为210 nm。在上述条件下,5种有效成分得到很好的分离,并且不受尿液中内源性基质的干扰,在20~200 mg/L范围内线性关系良好(r≥0.999 0);HMACa、KVCa、KILCa、KLCa和KPACa的检出限(S/N=3)分别为3.0、5.0、3.6、5.7和2.5 mg/L;定量限(S/N=10)分别为9.6、16.7、12.0、19.0和8.3 mg/L;日间、日内精密度均小于7%;平均回收率在86.79%~112.00%之间,RSD小于9%(n=5)。该方法准确,灵敏度高,重现性好,适用于尿液中这5种有效成分的检测。     

Synthesis and Photophysical Properties of a Sc3N@C80‐Corrole Electron Donor–Acceptor Conjugate

Embedding endohdedral metallofullerenes (EMFs) into electron donor–acceptor systems is still a challenging task owing to their limited quantities and their still largely unexplored chemical properties. In this study, we have performed a 1,3‐dipolar cycloaddition reaction of a corrole‐based precursor with Sc₃N@C₈₀ to regioselectively form a [5,6]‐adduct ( 1 ). The successful attachment of the corrole moiety was confirmed by mass spectrometry. In the electronic ground state, absorption spectra suggest sizeable electronic communications between the electron acceptor and the electron donor. Moreover, the addition pattern occurring at a [5,6]‐bond junction is firmly proven by NMR spectroscopy and electrochemical investigations performed with 1 . In the electronically excited state, which is probed in photophysical assays with 1 , a fast electron‐transfer yields the radical ion pair state consisting of the one‐electron‐reduced Sc₃N@C₈₀ and of the one‐electron‐oxidized corrole upon its exclusive photoexcitation. As such, our results shed new light on the practical work utilizing EMFs as building blocks in photovoltaics.     

Eco‐friendly ionic liquid assisted capillary electrophoresis and α‐acid glycoprotein‐assisted liquid chromatography for simultaneous determination of anticancer drugs in human fluids

In the current work, two eco‐friendly analytical methods based on capillary electrophoresis (CE) and reversed phase liquid chromatography (RPLC) were developed for simultaneous determination of the most commonly used anticancer drugs for Hodgkin's disease: methotrexate (MTX), vinblastine, chlorambucil and dacarbazine. A background electrolyte (BGE) of 12.5 mmol/L phosphate buffer at pH 7.4 and 0.1 µmol/L 1‐butyl‐3‐methyl imidazolium bromide (BMImBr) ionic liquid (IL) was used for CE measurements at 250 nm detection wavelength, 20 kV applied voltage and 25 °C. The rinsing protocol was significantly improved to reduce the adsorption of IL on the interior surface of capillary. Moreover, RPLC method was developed on α‐1‐acid glycoprotein (AGP) column. Mobile phase was 10 mmol/L phosphate buffer at pH 6.0 (100% v/v) and flow rate at 0.1 mL/min. As AGP is a chiral column, it was successfully separated l ‐MTX from its enantiomer impurity d ‐MTX. Good linearity of quantitative analysis was achieved with coefficients of determinations (r²) >0.995. The stability of drugs measurements was investigated with adequate recoveries up to 24 h storage time under ambient temperature. The limits of detection were <50 and 90 ng/mL by CE and RPLC, respectively. The using of short‐chain IL as an additive in BGE achieved 600‐fold sensitivity enhancement compared with conventional Capillary Zone Electrophoresis (CZE). Therefore, for the first time, the proposed methods were successfully applied to determine simultaneously the analytes in human plasma and urine samples at clinically relevant concentrations with fast and simple pretreatments. Developed IL‐assisted CE and RPLC methods were also applied to measure MTX levels in patients’ samples over time. Copyright © 2014 John Wiley & Sons, Ltd.     

Recyclable and reusable Pd(OAc)2/PPh3/PEG‐2000 system for homocoupling reaction of arylboronic acids under air without base

A stable and efficient Pd(OAc)₂/PPh₃/PEG‐2000 catalytic system for homocoupling of arylboronic acids has been developed. In the presence of Pd(OAc)₂ and PPh₃, the homocoupling reaction of arylboronic acids was carried out smoothly in PEG‐2000 at 70 °C under air without base to afford a variety of symmetric biaryls in good to excellent yields. The isolation of the products was readily performed by extraction with diethyl ether, and the Pd(OAc)₂/PPh₃/PEG‐2000 system could be easily recycled and reused six times without significant loss of catalytic activity. Copyright © 2014 John Wiley & Sons, Ltd.     

The High Energy X-ray telescope (HE) onboard the Insight-HXMT astronomy satellite

The Insight-Hard X-ray Modulation Telescope(Insight-HXMT) is a broadband X-ray and γ-ray(1-3000 ke V) astronomy satellite. One of its three main telescopes is the High Energy X-ray telescope(HE). The main detector plane of HE comprises 18 Na I(Tl)/Cs I(Na) phoswich detectors, where Na I(Tl) is used as the primary detector to measure ~ 20-250 ke V photons incident from the field of view(FOV) defined by collimators, and Cs I(Na) is used as the active shielding detector to Na I(Tl) by pulse shape discrimination. Additionally, Cs I(Na) is used as an omnidirectional γ-ray monitor. The HE collimators have a diverse FOV,i.e. 1.1°×5.7°(15 units), 5.7°×5.7°(2 units), and blocked(1 unit). Therefore, the combined FOV of HE is approximately5.7°×5.7°. Each HE detector has a diameter of 190 mm resulting in a total geometrical area of approximately 5100 cm2, and the energy resolution is ~15% at 60 ke V. For each recorded X-ray event by HE, the timing accuracy is less than 10 μs and the deadtime is less than 10 μs. HE is used for observing spectra and temporal variability of X-ray sources in the 20-250 ke V band either by pointing observations for known sources or scanning observations to unveil new sources. Additionally, HE is used for monitoring the γ-ray burst in 0.2-3 Me V band. This paper not only presents the design and performance of HE instruments but also reports results of the on-ground calibration experiments.