Light-Responsive Hexagonal Assemblies of Triangular Azo Dyes

The rational design of small building block molecules and understanding their molecular assemblies are of fundamental importance in creating new stimuli-responsive organic architectures with desired shapes and functions. Based on the experimental results of light-induced conformational changes of four types of triangular azo dyes with different terminal functional groups, as well as absorption and fluorescence characteristics associated with their molecular assemblies, we report that aggregation-active emission enhancement (AIEE)-active compound (1) substituted with sterically crowded tert-butyl (t-Bu) groups showed approximately 35% light-induced molecular switching and had a strong tendency to assemble into highly stable hexagonal structures with AIEE characteristics. Their sizes were regulated from nanometer-scale hexagonal rods to micrometer-scale sticks depending on the concentration. This is in contrast to other triangular compounds with bromo (Br) and triphenylamine (TPA) substituents, which exhibited no photoisomerization and tended to form flexible fibrous structures. Moreover, non-contact exposure of the fluorescent hexagonal nanorods to ultraviolet (UV) light led to a dramatic hexagonal-to-amorphous structure transition. The resulting remarkable variations, such as in the contrast of microscopic images and fluorescence characteristics, were confirmed by various microscopic and spectroscopic measurements.     

Review of Fluorescence Spectroscopy in Environmental Quality Applications

Fluorescence spectroscopy is an optical spectroscopic method that has been applied for the assessment of environmental quality extensively during the last 20 years. Most of the earlier works have used conventional light sources in spectrofluorometers to assess quality. Many recent works have used laser sources of light for the same purpose. The improvement of the energy sources and of the higher resolution spectrometers has led to a tremendous increase in applications. The motivation for the present review study is the increasing use of laser sources in environmental applications. The review is divided in two parts. The fundamental principles of fluorescence spectroscopy are described in the first part. The environmental applications are described in the second part.     

The First Online Capillary Electrophoresis-Microscale Thermophoresis (CE-MST) Method for the Analysis of Dynamic Equilibria—The Determination of the Acidity Constant of Fluorescein Isothiocyanate

This article presents the first successful application of a capillary electrophoresis-microscale thermophoresis tandem technique (CE-MST) for determining the values of equilibrium constant, realized by connecting online the CE and MST instruments using a fused-silica capillary. The acid-base dissociation of fluorescein isothiocyanate, expressed by the acidity constant value (pK_a), was used as a model. The measurement procedure consisted of introducing a mixture containing the analyte and a deliberately added interferent into the CE capillary, electrophoretic separation of the analyte from the interferent, the detection of the analyte with a CE-integrated detector, detection with a MST detector, and then stopping the flow temporarily by turning off the voltage source to conduct the thermophoretic measurement. The analysis of migration times, peak areas and MST responses obtained concurrently for the same sample allowed us to determine the pK_a value using three independent methods integrated within one instrumentation. The analyte was effectively separated from the interferent, and the acidity values turned out to be consistent with each other. An attempt was also made to replace the standard commercial CE instrument with a home-made portable CE setup. As a result, the similar pK_a value was obtained, at the same time proving the possibility of increasing cost efficiency and reducing energy consumption. Overall, the CE-MST technique has a number of limitations, but its unique analytical capabilities may be beneficial for some applications, especially when sample separation is needed prior to the thermophoretic measurement.     

Precise Quantification of Molybdate In Vitro by the FRET-Based Nanosensor ‘MolyProbe’

Molybdenum (Mo) is an essential trace element in all kingdoms of life. Mo is bioavailable as the oxyanion molybdate and gains biological activity in eukaryotes when bound to molybdopterin, forming the molybdenum cofactor. The imbalance of molybdate homeostasis results in growth deficiencies or toxic symptoms within plants, fungi and animals. Recently, fluorescence resonance energy transfer (FRET) methods have emerged, monitoring cellular and subcellular molybdate distribution dynamics using a genetically encoded molybdate-specific FRET nanosensor, named MolyProbe. Here, we show that the MolyProbe system is a fast and reliable in vitro assay for quantitative molybdate determination. We added a Strep-TagII affinity tag to the MolyProbe protein for quick and easy purification. This MolyProbe is highly stable, resistant to freezing and can be stored for several weeks at 4 °C. Furthermore, the molybdate sensitivity of the assay peaked at low nM levels. Additionally, The MolyProbe was applied in vitro for quantitative molybdate determination in cell extracts of the plant Arabidopsis thaliana, the fungus Neurospora crassa and the yeast Saccharomyces cerevisiae. Our results show the functionality of the Arabidopsis thaliana molybdate transporter MOT1.1 and indicate that FRET-based molybdate detection is an excellent tool for measuring bioavailable Mo.     

Increase in the Intracellular Bulk Water Content in the Early Phase of Cell Death of Keratinocytes,Corneoptosis, as Revealed by 65 GHz Near-Field CMOS Dielectric Sensor

While bulk water and hydration water coexist in cells to support the expression of biological macromolecules, how the dynamics of water molecules, which have long been only a minor role in molecular biology research, relate to changes in cellular states such as cell death has hardly been explored so far due to the lack of evaluation techniques. In this study, we developed a high-precision measurement system that can discriminate bulk water content changes of ±0.02% (0.2 mg/cm³) with single-cell-level spatial resolution based on a near-field CMOS dielectric sensor operating at 65 GHz. We applied this system to evaluate the temporal changes in the bulk water content during the cell death process of keratinocytes, called corneoptosis, using isolated SG1 (first layer of stratum granulosum) cells in vitro. A significant irreversible increase in the bulk water content was observed approximately 1 h before membrane disruption during corneoptosis, which starts with cytoplasmic high Ca²⁺ signal. These findings suggest that the calcium flux may have a role in triggering the increase in the bulk water content in SG1 cells. Thus, our near-field CMOS dielectric sensor provides a valuable tool to dissect the involvement of water molecules in the various events that occur in the cell.     

Evolution of Artificial Arginine Analogues—Fluorescent Guanidiniocarbonyl-Indoles as Efficient Oxo-Anion Binders

In this article, we present fluorescent guanidiniocarbonyl-indoles as versatile oxo-anion binders. Herein, the guanidiniocarbonyl-indole (GCI) and methoxy-guanidiniocarbonyl-indole (MGCI) were investigated as ethylamides and compared with the well-known guanidiniocarbonyl-pyrrole (GCP) concerning their photophysical properties as well as their binding behavior towards oxo-anions. Hence, a variety of anionic species, such as carboxylates, phosphonates and sulfonates, have been studied regarding their binding properties with GCP, GCI and MGCI using UV-Vis titrations, in combination with the determination of the complex stoichiometry using the Job method. The emission properties were studied in relation to the pH value using fluorescence spectroscopy as well as the determination of the photoluminescence quantum yields (PLQY). Density functional theory (DFT) calculations were undertaken to obtain a better understanding of the ground-lying electronic properties of the investigated oxo-anion binders. Additionally, X-ray diffraction of GCP and GCI was conducted. We found that GCI and MGCI efficiently bind carboxylates, phosphonates and sulfonates in buffered aqueous solution and in a similar range as GCP (K_ass ≈ 1000–18,000 M⁻¹, in bis-tris buffer, pH = 6); thus, they could be regarded as promising emissive oxo-anion binders. They also exhibit a visible fluorescence with a sufficient PLQY. Additionally, the excitation and emission wavelength of MGCI was successfully shifted closer to the visible region of the electromagnetic spectrum by introducing a methoxy-group into the core structure, which makes them interesting for biological applications.     

Nanostructured Polyelectrolyte-based System as a Toolbox for Metal Ions Detection

The capability of certain heavy metal ions to induce fluorescence decrease by a quenching mechanism suggested us to design and build a sensor potentially tunable for different ions at different concentrations. We propose a quenching-based sensor exploiting a nanostructured architecture in which fluorescent molecules (the sensing probe) are entrapped to recognize a specific analyte (heavy metal ions) through an optical transduction. The polyelectrolyte nanostructured system, named nanocapsule, improves the fluorophore-ion quenching sensitivity allowing a micromolar detection. Furthermore we couple our sensor with an electrical device in order to refine the sensing procedure: the electric field created allows a metal ions spatial gradient, necessary to detect a specific element on a single sample solution, avoiding a comparative analysis with an intensity reference value. Results obtained will show the advantages and the potentialities of our system as a smart toolbox for metal ions detection.     

Interaction of molecules of the neonicotinoid imidacloprid and its structural analogs with human serum albumin

We have used fluorescence spectroscopy methods to show that imidacloprid and its structural analogs form complexes with human serum albumin (HSA). The nature of the spectral changes in the ligand×protein systems and the calculated complexation parameters suggest that these low molecular weight compounds mainly bind to a specific section of the protein molecule, near the tryptophan residue in the 214 position of the polypeptide chain. We have found that the association constants are on the order of 10⁴ M⁻¹, and the affinity of the ligands for HSA varies in the series 6-chloronicotinic acid > 6-methoxynicotinic acid = imidacloprid > the keto analog of imidacloprid. The major contribution to the complexation energy probably comes from hydrophobic interaction forces with participation of the aromatic pyridine ring of the ligands, while additional enhancement of ligand-protein affinity can be provided by the nitroimine group of imidacloprid. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 6, pp. 859–866, November–December, 2008.     

Excitation of the Characteristic K Series Radiation,Coherent and Incoherent Scatter of Low Energy Gamma Rays

On the basis of a simplified mathematical model there is calculated the probability of a photon of characteristic K series radiation excited by a photon of low energy gamma radiation hitting the detector. There are also included the probabilities for coherently and incoherently scattered primary radiation considering electron binding energies.     

一种锌配合物用于炭疽生物标志物的检测

采用溶剂热合成方法,合成了一种新型金属配位聚合物{[Zn₂(L)(H₂O)(DMA)]·DMA·2.3H₂O}_n (1),其中L^4-为完全脱去质子的N,N''-二(4-羧基苄基)-5-氨基间苯二甲酸,DMA为N,N-二甲基乙酰胺。单晶X射线衍射结果显示,该配合物属于三斜晶系,空间群为P$overline{1}$,a=0.989 6(5) nm,b=1.370 5(5) nm,c=1.382 1(5) nm,α=80.067(5)°,β=76.729(5)°,γ=76.611(5)°,结构是由二维金属有机层通过π…π相互作用而扩展成的三维超分子骨架。红外光谱验证了锌离子与L^4-配体成功配位。粉末X射线衍射(PXRD)实验证实了配合物1具有较高的纯度。热重分析结果显示配合物1在室温至416.9 ℃区间内具有较好的热稳定性。在273 nm的激发光下,配合物1在437 nm处有较强的荧光发射,可以在30 s内快速检测乙醇溶液中的炭疽生物标志物——吡啶-2,6-二甲酸,具有选择性高、抗干扰能力强、检测限低(约为15 μmol·L^-1)等特点。结合PXRD图和紫外可见吸收光谱揭示了其检测机理为晶体骨架坍塌而诱导的荧光猝灭。