Determination of the inhibitory effect of green tea extract on glucose‐6‐phosphate dehydrogenase based on multilayer capillary enzyme microreactor

Natural herbal medicines are an important source of enzyme inhibitors for the discovery of new drugs. A number of natural extracts such as green tea have been used in prevention and treatment of diseases due to their low‐cost, low toxicity and good performance. The present study reports an online assay of the activity and inhibition of the green tea extract of the Glucose 6‐phosphate dehydrogenase (G6PDH) enzyme using multilayer capillary electrophoresis based immobilized enzyme microreactors (CE‐IMERs). The multilayer CE‐IMERs were produced with layer‐by‐layer electrostatic assembly, which can easily enhance the enzyme loading capacity of the microreactor. The activity of the G6PDH enzyme was determined and the enzyme inhibition by the inhibitors from green tea extract was investigated using online assay of the multilayer CE‐IMERs. The Michaelis constant (K_m) of the enzyme, the IC₅₀ and K_i values of the inhibitors were achieved and found to agree with those obtained using offline assays. The results show a competitive inhibition of green tea extract on the G6PDH enzyme. The present study provides an efficient and easy‐to‐operate approach for determining G6PDH enzyme reaction and the inhibition of green tea extract, which may be beneficial in research and the development of natural herbal medicines. Copyright © 2016 John Wiley & Sons, Ltd.     

Sensing and photocatalytic properties of nanosized Cu(I)CN organotin supramolecular coordination polymer based on pyrazine

Orange prismatic crystals of the supramolecular coordination polymer (SCP) _∞³[Cu(CN)₂(Me₃Sn)(Pyz)], SCP 1 , were synthesized using a self‐assembly method under ambient conditions. Nanosized 1 was obtained using the same molar ratio in water by ultrasonic irradiation. SCP 1 was characterized using single‐crystal X‐ray diffraction, elemental analysis, thermal analysis and Fourier transform infrared spectroscopy. SCP 1 and its nanosized 1 particles were also examined using powder X‐ay diffraction and scanning electron microscopy. The luminescence emission of SCP 1 was studied as well as its use as a sensor for the detection of common organic solvents and metal ions. Also, the catalytic activities of nanosized 1 towards various organic dyes were investigated under ambient conditions, UV irradiation and ultrasonic irradiation. Nanosized 1 as a heterogeneous nanoparticle catalyst exhibits high catalytic activity for the degradation of eosin‐Y and acid blue dyes. The mechanism of degradation investigated using various scavenger techniques is proposed and discussed. The catalytic oxidation process is mainly caused by ?OH radicals.     

An Aldehyde Responsive,Cleavable Linker for Glucose Responsive Insulins

A glucose responsive insulin (GRI) that responds to changes in blood glucose concentrations has remained an elusive goal. Here we describe the development of glucose cleavable linkers based on hydrazone and thiazolidine structures. We developed linkers with low levels of spontaneous hydrolysis but increased level of hydrolysis with rising concentrations of glucose, which demonstrated their glucose responsiveness in vitro. Lipidated hydrazones and thiazolidines were conjugated to the LysB29 side-chain of HI by pH-controlled acylations providing GRIs with glucose responsiveness confirmed in vitro for thiazolidines. Clamp studies showed increased glucose infusion at hyperglycemic conditions for one GRI indicative of a true glucose response. The glucose responsive cleavable linker in these GRIs allow changes in glucose levels to drive the release of active insulin from a circulating depot. We have demonstrated an unprecedented, chemically responsive linker concept for biopharmaceuticals.     

Joint optimal fair cooperative spectrum sensing and transmission in cognitive radio

Since the sensing power consumption of cooperative spectrum sensing (CSS) will decrease the throughput of secondary users (SU) in cognitive radio (CR), a joint optimal model of fair CSS and transmission is proposed in this paper, which can compensate the sensing overhead of cooperative SUs. The model uses the periodic listen-before-transmission method, where each SU is assigned a portion of channel bandwidth, when the primary user (PU) is estimated to be free by the coordinator. Then, a joint optimization problem of local sensing time, number of cooperative SUs, transmission bandwidth and power is formulated, which can compensate the sensing overhead of cooperative SUs appropriately through choosing suitable compensating parameter. The proposed optimization problem can be solved by the Polyblock algorithm. Simulation results show that compared with the traditional model, the total system throughput of the fairness cooperation model decreases slightly, but the total throughput of the cooperative SUs improves obviously.     

Thermal measurements using ultrasonic acoustical pyrometry

Reflections from geometric discontinuities can be used with ultrasonic energy to predict the temperature of an interface where classical temperature measurement techniques are impractical because of physical access limitations or harsh environmental conditions. Additionally, these same ultrasonic measurements can be used with inversion methods commonly applied to ill-posed heat transfer problems to increase the accuracy of the measurement of surface temperature or heat flux at the surface of interest. Both methods for determining surface temperature are presented, along with a comparison of results both from a verification example and using data gathered in a field test of the methods. The results obtained with these two methods are shown to be in good agreement with an empirical relationship used in the design of large caliber guns.     

Biological applications of amide and amino acid containing synthetic macrocycles

ABSTRACT

Amino acid derived macrocycles with elaborate well-defined stereochemistry are a unique class of compounds that have been isolated from natural sources. Macrocycles like cyclosporine, octreotide, and valinomycin have been used in multiple applications, like drugs or ion sensors. Chemists have long been fascinated by the unique molecular recognition capabilities of these macrocycles and tried to design synthetic analogs with similar functions. This article is focused on reviewing current research on amide and amino acid containing macrocycles that have been developed in research laboratories for biological recognition, specifically for anion sensing, ion transport, carbohydrate sensing, and peptide sensing.     

Hexanuclear 3d − 4f metal–organic cages assembled from a carboxylic acid‐functionalized tris‐triazamacrocycle for highly selective fluorescent sensing of picric acid

Two Ln^III ions are sandwiched by dinuclear Co^II building blocks derived from a tris‐triazamacrocyclic ligand bearing pendant carboxylic acid functionality, 1,3,5‐tris((4,7‐bis(2‐carboxyethyl)‐1,4,7‐triazacyclonon‐1‐yl)methyl)‐benzene (H₆L), giving rising to two nanoscale heterometallic metal–organic cages formulated as [Co₄Ln₂(LH_2.5)₂(H₂O)₄]·(ClO₄)₆·NO₃·nH₂O [Ln = Dy, n = 12 ( 1 ); Ln = Yb, n = 9 ( 2 )], whose internal cavity accommodates a guest NO₃^? anion. Their hexanuclear cage‐like architectures are maintained both in solution and solid states as confirmed by mass spectrum as well as X‐ray diffraction experiments. These two cages display ligand‐based fluorescence emissions and therefore both were chosen to be operated as fluorescent chemosensors for the detection of nitroaromatic compounds. Attractively, these metal–organic cages allow highly selective and sensitive detection of picric acid (PA) over other nitroaromatics in solution and suspension, and the fluorescence resonance energy transfer (FRET) between the cage probes and PA is mainly responsible for the remarkable detection efficiency.     

一种新的磁共振图像处理流水线的设计与实现

磁共振图像的重建、后处理及可视化是磁共振成像（MRI）系统的重要组成部分.本文开发了一个新的用于磁共振图像重建、后处理及可视化的开源框架YAP（Yet Another Pipeline），利用此框架可以方便地构建图像处理流水线.与现有的一些其他开源框架相比，本文开发的框架具有如下特点：（1）采用基于接口的设计，可使用基于接口的插件对流水线的功能进行扩展；（2）允许用户使用编写脚本的方式构建图像处理流水线，编辑与修改流水线都很方便；（3）支持带有分支结构的流水线，便于流水线的构建与调试.目前，该框架已经在商用系统中获得了应用.     

Highly sensitive and selective detect of p‐arsanilic acid with a new water‐stable europium metal–organic framework

The p‐arsanilic acid (p‐ASA), as an aromatic organoarsenic compounds, had received considerable concerns for their potential toxicity and carcinogenic properties. It was essential to detect p‐ASA with a facile method. In this paper, an europium based fluorescent metal–organic framework (MOF) [Eu₂(clhex)·2H₂O)]·H₂O ( BUC‐69 ) was successfully prepared under hydrothermal conditions with 1,2,3,4,5,6‐cyclohexanehexacarboxylic acid (H₆clhex) as organic linker. BUC‐69 displayed superior fluorescence capability to achieve selective and sensitive detection toward p‐ASA in water, which presented the first example of a MOF‐based sensor to detect p‐ASA. BUC‐69 showed excellent chemical stability in solutions under pH ranging from 4 to 12, which makes it be a potential sensor both in acidity and alkalinity condition. Significantly, BUC‐69 performed well in fluorescent sensing of p‐ASA at a low concentration (10^?6 M) in the simulated wastewater prepared with real lake water, and the results were comparable to the values detected by Inductively Coupled Plasma Optical Emission Spectrometer (ICP‐OES). The corresponding mechanism of fluorescent sensing toward p‐ASA with BUC‐69 was proposed and affirmed.     

Redox-Active Supramolecular Heteroleptic M4L2L′2 Assemblies with Tunable Interior Binding Site

Three Pt₄L₂L′₂ heteroleptic rectangles ( 1 – 3 ), containing ditopic redox-active bis-pyridine functionalized perylene bisimide (PBI) ligands PBI-pyr₂ ( L ) are reported. Co-ligand L′ is a dicarboxylate spacer of varying length, leading to modified overall size of the assemblies. ¹H NMR spectroscopy reveals a trend in the splitting and upfield chemical shift of the PBI-hydrogens in the rectangles with respect to free PBI, most pronounced with the largest strut length ( 3 ) and least with the smallest strut length ( 1 ). This is attributed to increased rotational freedom of the PBI-pyr ₂ ligand over its longitudinal axis (N_py-N_py), due to increased distance between the PBI-surfaces, which is corroborated by VT-NMR measurements and DFT calculations. The intramolecular motion entails desymmetrization of the two PBI-ligands, in line with cyclic voltammetry (CV) data. The first (overall two-electron) reduction event and re-oxidation for 1 display a subtle peak-to-peak splitting of 60 mV, whilst increased splitting of this event is observed for 2 and 3 . The binding of pyrene in 1 is probed to establish proof of concept of host-guest chemistry enabled by the two PBI-motifs. Fitting the binding curve obtained by ¹H NMR titration with a 1:1 complex formation model led to a binding constant of 964±55 m ⁻¹. Pyrene binding is shown to directly influence the redox-chemistry of 1 , resulting in a cathodic and anodic shift of approximately 46 mV on the first and second reduction event, respectively.