Turn-on fluorometric NADPH assay using orange emitting graphene oxide quantum dots

The authors describe a method for synthesizing graphene oxide quantum dots (GOQDs) possessing orange fluorescence with emission wavelength that can be tuned over the range from 537 to 593 nm by variation of the excitation wavelength. The GOQD display peroxidase-mimicking catalytic activity. Specifically, they catalyze the oxidation of dopamine to produce 4-(2-aminoethyl)benzene-1,2-quinone (AQ) which is colored and can quench the fluorescence of GOQDs. However, quenching is reversed by addition of NADP⁺, but not by its reduced form (NADPH). Based on these findings, an assay was worked out to monitor enzymatic reactions involving NADP⁺. The method allows NADPH to be detected in the 2–175 μM concentration range, with a 0.6 μM detection limit.

Open image in new window

Graphical abstract Schematic of a top-down method for synthesizing fluorescent graphene oxide quantum dots (GOQD) by chemical degrading, exfoliation and self-assembly of graphene oxide (GO). The GOQDs display peroxidase-like activity and can oxidize dopamine to form a colored quinone that quenches the fluorescence of the GOQDs. The quenching efficiency is reduced, however, in the presence of NADP⁺.

     

Hierarchical self-assembly of bolaamphiphiles with a hybrid spacer and L-glutamic acid headgroup: pH- and surface-triggered hydrogels, vesicles, nanofibers, and nanotubes

Bolaamphiphiles with L-glutamic acid headgroups and hybrid linkers, each composed of two rigid benzene rings and different polymethylene units, were designed, and morphological controls of the hierarchical self-assemblies were realized via changing solution pH and application to solid surfaces. At a low pH of 3, bolaamphiphiles formed hydrogels with water and molecules with short and long spacers formed nanofibers and helical nanoribbon-nanotubes, respectively. In a pH 12 aqueous solution, vesicles were observed from cryo-TEM measurements for amphiphiles with short spacers that could transfer to huge vesicles when cast onto a mica surface. Amphiphiles with longer spacers self-assembled into nanoparticles in a pH 12 aqueous solution while micellar fibers were formed on a mica surface. Those assemblies were characterized with UV-vis, CD, and FT-IR spectroscopy and AFM and TEM observations. With molecular structure modification and the fine tuning of conditions, morphology transitions between various nanostructures were obtained from the self-assembled bolaamphiphiles. The environmental pH can induce different interaction modes between the headgroups, and at high pH, there are strong interactions between molecular assemblies and the mica surface. It is suggested that the active headgroups, rigid necks, and flexible linkers with different lengths render molecules with diverse aggregation morphologies.     

大气声传播通道的声源当量估计方法

提出了一种基于大气声传播通道的爆炸声源能量估计方法,通过将计算大气声学的传播能量分布结果与大气中传播的声压幅度衰减模型相结合,使用平流层通道与热层通道传播损失能量比例作为修正量,提高了对爆炸声源能量的估计精度。在多次地面爆炸实验得到的数据中,使用观测距离800 km以上且同时存在平流层通道与热层通道的次声接收信号,对比了平流层顶风速修正的能量估计方法与该文提出的基于大气声传播通道的能量估计方法。实验结果验证了相对于传统风速修正的能量估计方法,该方法可显著降低估计误差。     

Tetramic acid derivatives and polyphenols from sponge-derived fungus and their biological evaluation

Fifteen compounds, including two tetramic acid derivatives, penicillenol A₁ (1) and penicillenol A₂ (2), six polyphenols containing both phenolic bisabolane sesquiterpenoid and diphenyl ether units, expansols A–F (3–8), together with six phenolic bisabolane sesquiterpenoids (9–14) and diorcinol (15), were isolated from the fermentation broth of the marine-derived fungus ZSDS1-F11 isolated from the sponge Phakellia fusca Thiele collected in the Yongxing island of Xisha. Their structures were elucidated mainly by using extensive NMR spectroscopic and mass spectrometric analyses. Compounds 3–5, 7 and 8 showed potent COX-1 inhibitory activity with IC₅₀ values of 5.3, 16.2, 30.2, 41.0 and 56.8 μM, respectively. Meanwhile, compounds 3–8 showed potent COX-2 inhibitory activity with IC₅₀ values of 3.1, 5.6, 3.0, 5.1, 3.2 and 3.7 μM, respectively. In addition, compound 1 exhibited antituberculosis activity with 96.1% inhibition at concentration of 10 μM.     

Supramolecular Fluorescent Nanoparticles Constructed via Multiple Non‐Covalent Interactions for the Detection of Hydrogen Peroxide in Cancer Cells

Overabundance of hydrogen peroxide originating from environmental stress and/or genetic mutation can lead to pathological conditions. Thus, the highly sensitive detection of H₂O₂ is important. Herein, supramolecular fluorescent nanoparticles self‐assembled from fluorescein isothiocyanate modified β‐cyclodextrin (FITC‐β‐CD)/rhodamine B modified ferrocene (Fc‐RB) amphiphile were prepared through host–guest interaction between FITC‐β‐CD host and Fc‐RB guest for H₂O₂ detection in cancer cells. The self‐assembled nanoparticles based on a combination of multiple non‐covalent interactions in aqueous medium showed high sensitivity to H₂O₂ while maintaining stability under physiological condition. Owing to the fluorescence resonance energy transfer (FRET) effect, addition of H₂O₂ led to obvious fluorescence change of nanoparticles from red (RB) to green (FITC) in fluorescent experiments. In vitro study showed the fluorescent nanoparticles could be efficiently internalized by cancer cells and then disrupted by endogenous H₂O₂, accompanying with FRET from “on” to “off”. These supramolecular fluorescent nanoparticles constructed via multiple non‐covalent interactions are expected to have potential applications in diagnosis and imaging of diseases caused by oxidative stresses.     

Self-assembly of copper(II) ion-mediated nanotube and its supramolecular chiral catalytic behavior

Self-assembly of several low-molecular-weight L-glutamic acid-based gelators, which individually formed helical nanotube or nanofiber structures, was investigated in the presence of Cu(2+) ion. It was found that, when Cu(2+) was added into the system, the self-assembly manner changed significantly. Only in the case of bolaamphiphilic glutamic acid, N,N'-hexadecanedioyl-di-L-glutamic acid (L-HDGA), were the hydrogel formation as well as the nanotube structures maintained. The addition of Cu(2+) ion caused a transition from monolayer nanotube of L-HDGA to a multilayer nanotube with the thickness of the tubular wall about 10 nm. For the other amphiphiles, the gel was destroyed and nanofiber structures were mainly formed. The formed Cu(2+)-containing nanostructures can function as an asymmetric catalyst for Diels-Alder cycloaddition between cyclopentadiene and aza-chalcone. In comparison with the other Cu(2+)-containing nanostructures, the Cu(2+)-mediated nanotube structure showed not only accelerated reaction rate, but enhanced enantiomeric selectivity. It was suggested that, through the Cu(2+) mediated nanotube formation, the substrate molecules could be anchored on the nanotube surfaces and produced a stereochemically favored alignment. When adducts reacted with the substrate, both the enantiomeric selectivity and the reaction rate were increased. Since the Cu(2+)-mediated nanotube can be fabricated easily and in large amount, the work opened a new way to perform efficient chiral catalysis through the supramolecular gel.     

Piecewise affine parameterized value-function based bilevel non-cooperative games

Mathematical Programming - Generalizing certain network interdiction games communicated to us by Andrew Liu and his collaborators, this paper studies a bilevel, non-cooperative game wherein the...     

3kA冷绝缘高温超导电缆的设计和短路冲击试验

为验证接入系统的高温超导电缆的暂态特性,研制了220kV/3kA 1.5米冷绝缘高温超导模型电缆,并成功进行了短路电流为40.4kArms、持续时间为2s的短路冲击试验。文中详细阐述了起到支撑、液氮流通通道和保护作用的铜骨架的设计,超导电缆本体均流设计,并对该模型电缆进行了接入系统的短路冲击试验,试验表明,该超导电缆可满足220kV电网暂态冲击要求,验证了超导电缆本体和铜骨架设计的正确和合理性。     

DBU-promoted tandem Michael-addition/cyclization for the synthesis of polysubstituted pyrroles

An efficient and transition-metal-free method for the synthesis of the structurally diversified pyrroles is described. Various α,β-unsaturated ynones reacted with N-substituted ethyl glycine ethyl ester hydrochlorides in the presence of DBU to form the corresponding products in good yields. This protocol has the advantages of readily available starting materials, mild reaction conditions and a wide scope of substrates, which provides a practical route for the synthesis of polysubstituted pyrroles.