A wide range optical pH sensor for living cells using Au@Ag nanoparticles functionalized carbon nanotubes based on SERS signals

p-Aminothiophenol (pATP) functionalized multi-walled carbon nanotubes (MWCNTs) have been demonstrated as an efficient pH sensor for living cells. The proposed sensor employs gold/silver core-shell nanoparticles (Au@Ag NPs) functionalized MWCNTs hybrid structure as the surface-enhanced Raman scattering (SERS) substrate and pATP molecules as the SERS reporters, which possess a pH-dependent SERS performance. By using MWCNTs as the substrate to be in a state of aggregation, the pH sensing range could be extended to pH 3.0～14.0, which is much wider than that using unaggregated Au@Ag NPs without MWCNTs. Furthermore, the pH-sensitive performance was well retained in living cells with a low cytotoxicity. The developed SERS-active MWCNTs-based nanocomposite is expected to be an efficient intracellular pH sensor for bio-applications.     

钌多吡啶配合物与DNA相互作用研究新进展

DNA是携带遗传信息和基因表达的基本物质.因为复杂的生物环境以及外源因素的影响,DNA存在灵活多变的结构,而不同的构型都有其独特的意义和重要的生物学功能,相关研究受到越来越广泛的关注.本文主要针对近年来钌多吡啶化合物与DNA相互作用研究的最新进展做一综述,包括DNA结构的识别,DNA二级、三级结构的调控,DNA光交联以及作为非病毒基因载体,细胞成像以及抗肿瘤等方面的应用.     

Chemical composition and in vitro evaluation of the cytotoxic and antioxidant activities of supercritical carbon dioxide extracts of pitaya (dragon fruit) peel

Background

Hylocereus polyrhizus and Hylocereus undatus are two varieties of the commonly called pitaya fruits, and pitaya fruits have gained popularity in many countries all over the world. However, studies on chemical composition and the nutritional quality of pitaya flesh peel are limited.

Results

Extracts of pitaya (H. polyrhizus and H. undatus) peel were extracted by supercritical carbon dioxide extraction, and analyzed by gas chromatography–mass spectrometry analysis. Their cytotoxic and antioxidant activities were investigated. The main components of H. polyrhizus extract were β-amyrin (15.87%), α-amyrin (13.90%), octacosane (12.2%), γ-sitosterol (9.35%), octadecane (6.27%), 1-tetracosanol (5.19%), stigmast-4-en-3-one (4.65%), and campesterol (4.16%), whereas H. undatus were β-amyrin (23.39%), γ-sitosterol (19.32%), and octadecane (9.25%), heptacosane (5.52%), campesterol (5.27%), nonacosane (5.02%), and trichloroacetic acid, hexadecyl ester (5.21%). Both of the two extracts possessed good cytotoxic activities against PC3, Bcap-37, and MGC-803 cells (IC₅₀ values ranging from 0.61 to 0.73 mg/mL), and the activities of their main components were also studied. Furthermore, these extracts also presented some radical scavenging activities, with IC₅₀ values of 0.83 and 0.91 mg/mL, respectively.

Conclusion

This paper provides evidence for studying the chemical composition of supercritical carbon dioxide extracts of pitaya peel and their biological activity.     

Thermo-responsive gelatin-functionalized PCL film surfaces for improvement of cell adhesion and intelligent recovery of gene-transfected cells

Efficient local gene transfection on a tissue scaffold is dependent on good cell-adhesion characteristics. In this work, the thermo-responsive gelatin-functionalized polycaprolactone (PCL) films were proposed for improvement of cell adhesion and intelligent recovery of gene-transfected cells. Functional copolymer brushes (PCL-g-P(NIPAAm-co-MAAS)) were first prepared via surface-initiated ATRP of N-isopropylacrylamide (NIPAAm) and methacrylic acid sodium salt (MAAS) from the initiator-funcationalized PCL surfaces. The pendant carboxyl end-groups of the PCL-g-P(NIPAAm-co-MAAS) surface were subsequently coupled with gelatin via carbodiimide chemistry to produce the thermo-responsive gelatin-functionalized PCL surface. The thermo-responsive gelatin-functionalized PCL film surface can improve cell adhesion and proliferation above the LCST of P(NIPAAm) without destroying cell detachment properties at lower temperatures. The dense transfected cells can be recovered simply by lowering culture temperature. The thermo-responsive gelatin-functionalized PCL films are potentially useful as intelligent adhesion modifiers for directing cellular functions within tissue scaffolds.     

New Entangled Coordination Networks Based on Charge‐Tunable Keggin‐Type Polyoxometalates

Investigation into a hydrothermal reaction system with transition‐metal (TM) ions, 1,4‐bis(1,2,4‐triazol‐1‐lmethyl)benzene (BBTZ) and various charge‐tunable Keggin‐type polyoxometalates (POMs) led to the preparation of four new entangled coordination networks, [Co^II(HBBTZ)(BBTZ)_2.5][PMo₁₂O₄₀] ( 1 ), [Cu^I(BBTZ)]₅[BW₁₂O₄₀] ? H₂O ( 2 ), [Cu^II(BBTZ)]₃[AsW^V₃W^VI₉O₄₀] ? 10 H₂O ( 3 ), and [Cu^II₅(BBTZ)₇(H₂O)₆][P₂W₂₂Cu₂O₇₇(OH)₂] ? 6 H₂O ( 4 ). All compounds were characterized by using elemental analysis, IR spectroscopy, thermogravimetric analysis, powder X‐ray diffraction, and single‐crystal X‐ray diffraction. The mixed valence of W centers in compound 3 was further confirmed by using XPS spectroscopy and bond‐valence sum calculations. In the structural analysis, the entangled networks of 1 – 4 demonstrate zipper‐closing packing, 3D polythreading, 3D polycatenation, and 3D self‐penetration, respectively. Moreover, with the enhancement of POM negative charges and the use of different TM types, the number of nodes in the coordination networks of 1 – 4 increased and the basic metal–organic building motifs changed from a 1D zipper‐type chain (in 1 ) to a 2D pseudorotaxane layer (in 2 ) to a 3D diamond‐like framework (in 3 ) and finally to a 3D self‐penetrating framework (in 4 ). The photocatalytic properties of compounds 1 – 4 for the degradation of methylene blue under UV light were also investigated; all compounds showed good catalytic activity and the photocatalytic activity order of Keggin‐type species was initially found to be {XMo₁₂O₄₀}>{XW₁₂O₄₀}>{XW_12?nTM_nO₄₀}.     

Energetic Salts Based on an Oxygen‐Containing Cation: 2,4‐Diamino‐1,3,5‐triazine‐6‐one

A family of energetic salts with high thermal stability and low impact sensitivity based on an oxygen‐containing cation, 2,4‐diamino‐1,3,5‐triazine‐6‐one, were synthesized and fully characterized by IR and multinuclear (¹H, ¹³C) NMR spectroscopy, elemental analysis, and differential scanning calorimetry. Insights into their sensitivities towards impact, friction, and electrostatics were gained by submitting the materials to standard tests. The structures of 2,4‐diamino‐1,3,5‐triazine‐6‐one nitrate, 2,4‐diamino‐1,3,5‐triazine‐6‐one sulfate, 2,4‐diamino‐1,3,5‐triazine‐6‐one perchlorate, 2,4‐diamino‐1,3,5‐triazine‐6‐one 5‐nitrotetrazolate were determined by single‐crystal X‐ray diffraction; their densities are 1.691, 1.776, 1.854, and 1.636 g cm^?3, respectively. Most of the salts decompose at temperatures over 180 °C; in particular, the salts 2,4‐diamino‐1,3,5‐triazine‐6‐one nitrate and 2,4‐diamino‐1,3,5‐triazine‐6‐one perchlorate, which decompose at 303.3 and 336.4 °C, respectively, are fairly stable. Furthermore, most of the salts exhibit excellent impact sensitivities (>40 J), friction sensitivities (>360 N), and are insensitive to electrostatics. The measured densities of these energetic salts range from 1.64 to 2.01 g cm^?3. The detonation pressure values calculated for these salts range from 14.6 to 29.2 GPa, and the detonation velocities range from 6536 to 8275 m s^?1; these values make the salts potential candidates for thermally stable and insensitive energetic materials.     

A novel two‐dimensional CdII coordination polymer: poly[aqua[μ4‐2‐(4‐carboxylatobenzoyl)benzoato]cadmium(II)]

The title Cd^II coordination framework, [Cd(C₁₅H₈O₅)(H₂O)]_n or [Cd(bpdc)(H₂O)]_n [H₂bpdc is 2‐(4‐carboxybenzoyl)benzoic acid], has been prepared and characterized using IR spectroscopy, elemental analysis, thermal analysis and single‐crystal X‐ray diffraction. Each Cd^II centre is six‐coordinated by two O atoms from one 2‐(4‐carboxylatobenzoyl)benzoate (bpdc²⁻) ligand in chelating mode, three O‐donor atoms from three other bpdc²⁻ anions and one O atom from a coordinated water molecule in an octahedral coordination environment. Two crystallographically equivalent Cd^II cations are bridged by one O atom of the 2‐carboxylate group of one bpdc²⁻ ligand and by both O atoms of the 4‐carboxylate group of a second bpdc²⁻ ligand to form a binuclear [(Cd)₂(O)(OCO)] secondary building unit. Adjacent secondary building units are interlinked to form a one‐dimensional [Cd(OCO)₂]_n chain. The bpdc²⁻ ligands link these rod‐shaped chains to give rise to a complex two‐dimensional [Cd(bpdc)]_n framework with a 4,4‐connected binodal net topology of point symbol {4³.6².8}. The compound exhibits a strong fluorescence emission and typical ferroelectric behaviour in the solid state at room temperature.     

Contact duration aware evaluation for content dissemination delay in mobile social network

Groups of people with mobile phones using short‐range connections such as WiFi and Bluetooth to propagate messages can be modeled as, with regard to regular absence of end‐to‐end connection, mobile social networks (MSNs), which can be exploited to offload a significant amount of mobile content from the overloaded infrastructure networks such as 3G. The study of content transmission delay for the applications of mobile content dissemination in MSNs is an important problem, because to enhance the network capacity, the traffic is offloaded at the cost of inducing longer delay. In contrast to existing works, which ignore the factors of contact duration limits and large content size, we present a contact duration aware framework to model the content dissemination process in MSNs, give an explicit expression for the average content dissemination delay, and reveals its relationship with various system parameters of content size, users’ selfishness, number of involved subscribers, infecting ratio, and so on. We apply our proposed model to real‐life traces to assess its reliability by comparing the theoretical results with measured statistics and present extensive upshots to evaluate the influence of various parameters on system performance. The results demonstrate the accuracy of our proposed framework and reveal that system parameters of content size, system infecting ratio and intragroup transmission are the most important factors to influence the content dissemination delay. Copyright © 2013 John Wiley & Sons, Ltd.     

Theoretical performance analysis of radio frequency fingerprinting under receiver distortions

Radio frequency fingerprinting (RFF) is used to uniquely identify individual emitters by exploiting the radio frequency characteristics, which are originated from transmitter imperfections. The theoretical performance is analyzed to evaluate the feasibility of RFF with channel noise and receiver imperfections. The distortions from oscillators and analog‐to‐digital converter (ADC) are considered, and a RFF signal model describing the discrepancies of transmitter imperfections, channel noise, and receiver distortions are constructed. A likelihood ratio test algorithm for RFF is proposed to analyze the theoretical performance. The upper and lower bound of theoretic performance is derived through the analysis of the likelihood ratio test statistic, which enlightens how to design a “just enough” receiver to meet the demands of RFF. The simulation results are in agreement with the theoretical evaluation. Copyright © 2013 John Wiley & Sons, Ltd.     

国内外近30年“电化学”主题概念测查研究进展*

梳理了国内外1990-2020年核心期刊文献中对学生电化学主题概念测评的实证研究,主要涵盖学生电化学概念理解水平以及影响因素等方面。据此探讨其对化学教师教学实施以及国内外化学教育实证研究的启示,以期为中学化学教学及后续研究提供有益参考。