超顺磁纳米颗粒弛豫时间传感技术在生化分析中的研究进展

该文介绍了基于超顺磁纳米颗粒的弛豫时间(T2)传感技术及其在生化分析应用中的研究进展.在均匀磁场中,超顺磁纳米颗粒状态的变化(分散或聚集)会改变磁场的均匀度进而引起周围水分子质子弛豫时间的改变,即磁弛豫时间传感效应.磁颗粒经表面修饰后与给体/受体偶联形成磁传感探针,当与待测物发生特异性反应后,引起介质磁颗粒聚集状态改变...     

Tailoring Valence Tautomerism by Using Redox Potentials: Studies on Ferrocene-Based Triarylmethylium Dyes with Electron-Poor Fluorenylium and Thioxanthylium Acceptors

Three new electrochromic ferrocenyl triarylmethylium dyes with fluorenylium ( 1 a ⁺, 1 b ⁺) or thioxanthylium ( 1 c ⁺) residues were selected in order to keep the intrinsic differences of redox potentials for ferrocene oxidation and triarylmethylium reduction small and to trigger valence tautomerism (VT). UV/Vis/NIR and quantitative EPR spectroscopy identified paramagnetic diradical isomers 1 a ^..+– 1 c ^..+ alongside diamagnetic forms 1 a ⁺– 1 c ⁺, which renders these complexes magnetochemical switches. The diradical forms 1 a ^..+– 1 c ^..+ as well as the one-electron-reduced triarylmethyl forms of the complexes were found to dimerize in solution. For radical 1 a ^., dimerization occurs on the timescale of cyclic voltammetry; this allowed us to determine the kinetics and equilibrium constant for this process by digital simulation. Mößbauer spectroscopy indicated that 1 a ⁺ and 1 b ⁺ retain VT even in the solid state. UV/Vis/NIR spectro-electrochemistry revealed the poly-electrochromic behaviour of these complexes by establishing the distinctly different electronic absorption profiles of the corresponding oxidized and reduced forms.     

The effect of temperature on the photoacidity of merocyanine photoacids in water

Merocyanine photoacids are molecular photoswitches that can be used to regulate acid-base reactions reversibly. Despite their growing impact across multiple research areas including materials science and nanotechnology, the effect of temperature on their functioning in aqueous environments has not yet been explored. Here we employ variable-temperature pH and UV-Vis analyses to rationalize their temperature-dependent (photo)chemical behaviors in water, showing that their photoacidity is inversely proportional to the temperature (by ca. ?0.01 pK/°C).     

Photo-, solvent-, and ion-controlled multichromism of imidazolium-substituted diarylethenes

Cationic diarylethenes with an imidazolium ring are synthesized for the first time. The imidazolium cationic moiety is connected directly to the ethene unit as one of the aryl units that take part in the photoinduced pericyclization reaction. The imidazolium-substituted diarylethenes undergo reversible photochromic reactions in a variety of organic media, including ionic liquids, even though they have a delocalized cationic charge in one of the five-membered aromatic rings. The closed-ring isomer shows solvatochromism depending on the solvent donor numbers. Addition of some tetraalkylammonium salts, such as tetrabutyl ammonium nitrate, into the colored organic solution of diarylethene also causes a color change, indicating its ionochromic property. These solvato- and ionochromic properties are considered in connection with the shift of chemical equilibrium between the closed-ring isomers, one with an extended pi-conjugation system and one with limited pi-conjugation due to the strong interaction with solvent molecules and anions with high donor number.     

Acid–Base Controllable Recognition Properties of a Highly Versatile Calix[6]crypturea

Versatile concave receptors with binding properties that can be controlled by external stimuli are rare. Herein, we report on a calix[6]crypturea ( 1 ) that features two different binding sites in close proximity, that is, a tris(2‐aminoethyl)amine (tren)‐based tris‐ureido cap that provides convergent hydrogen‐bond‐donor sites and a hydrophobic cavity suitable for the inclusion of organic guests. The binding properties of this heteroditopic receptor have been evaluated by NMR spectroscopic studies. Compound 1 behaves as a remarkably versatile host that strongly binds neutral molecules, anions, or contact ion pairs. Within each family of guests, compound 1 is able to discriminate between different guests with a high degree of selectivity. Indeed, neutral molecules that possess hydrogen‐bond donor and acceptor groups, chloride anions, and linear ammonium ions associated to F^? or Cl^? are particularly well recognized. In comparison with all the related receptors, compound 1 displays several unique features: 1) charged or neutral species are also recognized in polar or protic solvents, 2) thanks to the flexibility of the calixarene structure, induced‐fit processes allow the binding of large, biologically relevant ammonium salts such as neurotransmitters, and 3) the protonation of the basic cap leads to a positively charged receptor, 1? H⁺, which is reluctant to host anions and in which host properties are now governed by strong charge–dipole interactions with the guests. In other words, compound 1 presents an acid–base controllable tris‐ureido recognition site protected by a hydrophobic corridor that can select guests through induced‐fit processes. Thus, its versatile host properties can be allosterically controlled by protonation and selective guest‐switching processes are possible. To illustrate all these remarkable features, a sophisticated three‐pole supramolecular switch, based on the interconversion of host–guest systems displaying either charged or neutral guests, is described.     

稳定性切换在一阶时滞微分方程中的应用

介绍了时滞动力系统中的对零解稳定性讨论的稳定性切换法,并应用此方法对时滞动力系统中的三个一阶时滞微分方程基本定理给予证明.同时表明了在局部稳定性分析中,该方法有着更大的优势.     

A Visible‐Light‐Driven Molecular Motor Based on Pyrene

The aromatic core of an overcrowded alkene‐based molecular motor is extended with the goal of inducing isomerization with visible light instead of harmful UV light. In our design, the common naphthalene moiety in the upper half of the motor is changed to pyrene. The photochemical and thermal isomerization processes are studied in detail using DFT calculations as well as NMR and UV/VIS spectroscopy. Our studies confirm that extension of the π‐system of the upper half successfully leads to a shift of the excitation wavelength into the visible region, while retaining proper rotary function.     

Photoswitchable double bonds: Synthetic strategies for tunability and versatility

Isomerizations of azo, imine, and alkene groups using light are highly tunable. As such, photoswitches based on these functional groups have become critical components of many responsive molecules and materials. This mini‐review describes recent work focused on controlling various properties of double bond‐based molecular switches, including speed of switching, thermal stability, and wavelength required to initiate switching. Methods used to control structure and function vary, but commonly involve careful probing of the electronic, photochemical, and steric profiles of the molecular switches. Successes and avenues for further investigation will be discussed.