Simultaneous determination of three dipeptides (JBP485, Gly–Sar and JBP923) in the cell lysates by liquid chromatography‐tandem mass spectrometry: application to identify the function of the PEPT1 transfected cell

A simple and rapid liquid chromatography–tandem mass spectrometry (LC‐MS/MS) method for the simultaneous determination of JBP485, Gly–Sar and JBP923 in the cell lysates using methanol as a deproteinization solvent was developed and validated. Detection was performed by turbo ionspray ionization in multiple reaction monitoring mode using the transitions of m/z 147.1 → m/z 90.1 for Gly–Sar, m/z 201.1 → m/z 86.1 for JBP485, m/z 219.1 → m/z 86.1 for JBP923 and m/z 152.0 → m/z 110.0 for paracetamol (internal standard). The analytes were separated on a Hypersil ODS C₁₈ HPLC column using isocratic elution mode with a mobile phase containing 0.1% formic acid in water–methanol (97:3, v/v) at a flow rate of 0.2 mL/min. The calibration curves were demonstrated to be linear over the concentration range of 5.00?5000 nm with coefficient of 0.9968 for Gly–Sar, 0.9975 for JBP485 and 0.9952 for JBP923. The intra‐ and inter‐day precisions were <10.2% for each quality contro; level, and the accuracy was within ±5.6% for each analyte. The matrix effect, the extraction recovery and stabilities of LC‐MS/MS analysis were also investigated. This validated method was successfully applied to the simultaneous determination of JBP485, Gly–Sar and JBP923 in the cell lysates for identification of stably transfected HeLa cells with human PEPT1. Copyright © 2014 John Wiley & Sons, Ltd.     

Reactivity of Oxygen Radical Anions Bound to Scandia Nanoparticles in the Gas Phase: CH Bond Activation

The activation of C?H bonds in alkanes is currently a hot research topic in chemistry. The atomic oxygen radical anion (O^?.) is an important species in C?H activation. The mechanistic details of C?H activation by O^?. radicals can be well understood by studying the reactions between O^?. containing transition metal oxide clusters and alkanes. Here the reactivity of scandium oxide cluster anions toward n‐butane was studied by using a high‐resolution time‐of‐flight mass spectrometer coupled with a fast flow reactor. Hydrogen atom abstraction (HAA) from n‐butane by (Sc₂O₃)_NO^? (N=1–18) clusters was observed. The reactivity of (Sc₂O₃)_NO^? (N=1–18) clusters is significantly sizedependent and the highest reactivity was observed for N=4 (Sc₈O₁₃^?) and 12 (Sc₂₄O₃₇^?). Larger (Sc₂O₃)_NO^? clusters generally have higher reactivity than the smaller ones. Density functional theory calculations were performed to interpret the reactivity of (Sc₂O₃)_NO^? (N=1–5) clusters, which were found to contain the O^?. radicals as the active sites. The local charge environment around the O^?. radicals was demonstrated to control the experimentally observed size‐dependent reactivity. This work is among the first to report HAA reactivity of cluster anions with dimensions up to nanosize toward alkane molecules. The anionic O^?. containing scandium oxide clusters are found to be more reactive than the corresponding cationic ones in the C?H bond activation.     

Phenylene‐Coated Magnetic Nanoparticles that Boost Aqueous Asymmetric Transfer Hydrogenation Reactions

Phenylene‐coated organorhodium‐functionalized magnetic nanoparticles are developed through co‐condensation of chiral 4‐(trimethoxysilyl)ethyl)phenylsulfonyl‐1,2‐diphenylethylene‐diamine and 1,4‐bis(triethyoxysilyl)benzene onto Fe₃O₄ followed complexation with [{Cp*RhCl₂}₂]. This magnetic catalyst exhibits excellent catalytic activity and high enantioselectivity in asymmetric transfer hydrogenation in aqueous medium. Such activity is attributed to the high hydrophobicity and the confined nature of the chiral organorhodium catalyst. The magnetic catalyst can be easily recovered by using a small external magnet and it can be reused for at least 10 times without loss of its catalytic activity. This characteristic makes it an attractive catalyst for environmentally friendly organic syntheses.     

An improved cell membrane chromatography method for the simultaneous screening of two epidermal growth factor receptor antagonists from radix scutellariae

A high‐expression epidermal growth factor receptor cell membrane chromatography using the silica gel with the average particle size of 3 μm as the stationary phase carrier coupled with high‐performance liquid chromatography and mass spectrometry was established for the online screening of epidermal growth factor receptor antagonists from Radix Scutellariae (Huang Qin in Chinese), a traditional Chinese medicine. In this study, the growth factor receptor cell membrane chromatography model using the smaller particle size carrier showed a higher efficiency for simultaneous screening baicalein, another one of the potential epidermal growth factor receptor antagonists from Radix Scutellariae extract besides wogonin, which was found in our previous work. The molecular docking result showed the occupancy site and binding mode of baicalein and wogonin with epidermal growth factor receptor tyrosine kinase were similar to gefitinib. The result of the assay for the in vitro inhibitory activity showed that baicalein and wogonin inhibited the growth of the high‐expression epidermal growth factor receptor cell in a dose‐dependent manner and even achieved a better inhibition effect than gifitinib in the low‐dosage range.     

Sr_2CeO_4:Nd~(3+)纳米粒子的合成和近红外发光

采用甘氨酸-硝酸盐燃烧法制备了Sr2CeO4和Sr2CeO4:Nd3+发光纳米粒子。样品的结构及性质采用XRD,TEM,荧光光谱及荧光衰减曲线等进行表征。在1200℃煅烧1h能够得到均匀的类球形Sr2CeO4:Nd3+纳米粒子,其粒径大小为20~40nm,并具有良好的分散性和高效的近红外发光特性。Nd3+合适掺杂浓度为0.15%(摩尔分数)。对Sr2CeO4:Nd3+近红外发光的机制分析表明:通过基质Sr2CeO4吸收紫外光,基团CeO4发生了电荷转移达到激发态,并将激发态能量传递给了Nd3+,从而使Sr2CeO4:Nd3+产生了特征的近红外发射。     

Biocatalytic Synthesis of the Anti‐diabetes Agent‐corosolic Acid by Whole Cells of Microorganisms

Diabetes is one of the most prevalent and costly global diseases. For diabetes, frequent insulin treatment and synthetic drugs are very expensive and may cause unwanted side effects. Corosolic acid (CA), a natural product, was reported to be efficient in the treatment of diabetes, meanwhile without induction of anti‐insulin antibodies and obesity. The preparation of CA attracted many researchers in the world. This study investigated the biocatalytic synthesis method of CA from ursolic acid by Streptomyces griseus subsp. griseus 4.18. LC? MS analysis demonstrated that 5 day, 125 μg/mL substrate, pH=9 and 10% strain concentration were the appropriate conditions. It is estimated that biocatalysis will contribute to the development of green and sustainable synthetic processes with less time‐consuming and more environmentally friendly.     

Chiral Separations in Normal‐phase Liquid Chromatography: Updating a Screening Strategy with a Chlorine‐containing Polysaccharide‐based Selector

The screening conditions of an existing column and mobile phase selection strategy for chiral compounds in normal‐phase high performance liquid chromatography (NP‐HPLC) were tested for their applicability on Chiralpak IC, which is a chiral stationary phase (CSP) made by immobilising cellulosic tris (3,5‐dichlorophenyl‐carbamate) on silica gel. In this study, the applicability of the optimization steps of the existing separation strategy was examined using 36 compounds representing the three possible resolution situations that occur after screening. The cumulative number of separated compounds is 27 (75.0 %), and the cumulative number of baseline separated compounds is 19 (52.8 %).     

Assemblies of a new flexible multicarboxylate ligand and d10 metal centers toward the construction of homochiral helical coordination polymers: structures, luminescence, and NLO-active properties

Hydro(solvo)thermal reactions between a new flexible multicarboxylate ligand of 2,2',3,3'-oxydiphthalic acid (2,2',3,3'-H(4)ODPA) and M(NO(3))(2).xH(2)O (M = Zn, x = 6; M = Cd, x = 4) in the presence of 4,4'-bipyridine (bpy) afford two novel homochiral helical coordination polymers [[Zn(2)(2,2',3,3'-ODPA)(bpy)(H(2)O)(3)].(H(2)O)(2) for 1 and [Cd(2)(2,2',3,3'-ODPA)(bpy)(H(2)O)(3)].(H(2)O)(2) for 2]. Though having almost the same chemical formula, they have different space groups (P2(1)2(1)2(1) for 1 and P2(1) for 2) and different bridging modes of the 2,2',3,3'-ODPA ligand. Two kinds of homochiral helices (right-handed) are found in both 1 and 2, each of which discriminates only one kind of crystallographical nonequivalent metal atom. 1 has a 2D metal-organic framework and can be seen as the unity of two parallel homochiral Zn1 and Zn2 helices, in which the nodes are etheric oxygen atoms. In contrast, 2 has a 3D metal-organic framework and consists of two partially overlapped homochiral Cd1 and Cd2 helices in the two dimensions. Moreover, metal-ODPA helices give a 2D chiral herringbone structural motif in both 1 and 2 in the two dimensions, which are further strengthened by the second ligand of bpy. Bulk materials for 1 and 2 all have good second-harmonic generation activity, approximately 1 and 0.8 times that of urea.     

A novel method for time-resolved fluorimetric determination and imaging of the activity of peroxidase, and its application to an enzyme-linked immunosorbent assay

A new type of fluorescence assay for the determination of peroxidase (POx) activity is presented. The assay is based on the indication of the enzymatic consumption of H(2)O(2) (HP), using a fluorescent europium-tetracycline (Eu(3)TC) complex as indicator. On addition of HP, this complex forms a highly fluorescent adduct (Eu(3)TC-HP), which is decomposed in the presence of POx to form the weakly fluorescent europium-tetracycline (Eu(3)TC). Hence, the activity of the enzyme can be directly determined by means of the luminescent Eu(3)TC complex as indicator. The POx assay demonstrated herein was elaborated starting from a spectral characterization of the complex systems involved. Due to the long lifetime of lanthanide luminescence, both steady-state and time-resolved luminescence assays can easily be performed. The time-resolved assay can quantify POx in the range from 4.0 x 10(-5) to 5.9 x 10(-3) U mL(-1), with a limit of detection of 1.0 x 10(-5) U mL(-1). The effects of POx inhibitors such as cyanide, hydroxylamine, and azide have also been studied. In addition, a time-resolved fluorescent detection method for a POx-based enzyme-linked immunosorbent assay (ELISA) has been developed, which is demonstrated in a sandwich model assay with bovine IgG serving as analyte. Furthermore, a time-resolved fluorescent imaging method is demonstrated that makes use of a straightforward imaging set-up adjusted to the optical properties of the europium reagent.     

Efficient and Mild Protocol for the Synthesis of 4(3)-Substituted 3(4)-Nitro-1H-pyrroles and 3-Substituted 4-Methyl-2-tosyl-1 H-pyrroles from Nitroolefins and Tosylmethyl Isocyanide in Ionic Liquids

A mild and convenient method for the synthesis of 4(3)‐substituted 3(4)‐nitro‐1H‐pyrroles and 3‐substituted 4‐methyl‐2‐tosyl‐1H‐pyrroles from nitroolefins and tosylmethyl isocyanide (TosMIC) in ionic liquid 1‐butyl‐3‐methylimidazolium bromide ([bmIm]Br) was developed. The reactions were performed at room temperature with KOH as base with good yields in a short time (about 2 h). Some tough conditions, such as absolutely anhydrous organic solvents, low temperature, hazardous and expensive strong base or organic base, were not needed. The yields of 4(3)‐substituted 3(4)‐nitro‐1H‐pyrroles were moderate, but excellent yields were achieved for the preparation of 3‐substituted 4‐methyl‐2‐tosyl‐1H‐pyrroles. This strategy was quite general and it worked in a broad range of nitroolefins with aromatic, aliphatic or heterocyclic substituents. The recovered ionic liquid could be reused as solvent for several times without significant decrease of reaction yields.