Biological effects of essential oils - A review

http://pubs.acs.org/doi/pdf/10.1021/cr400546e

Fluorescent Sensors for Measuring Metal Ions in Living Systems

The brain is a singular organ of unique biological complexity that serves as the command center for cognitive and motor function. As such, this specialized system also possesses a unique chemical composition and reactivity at the molecular level. In this regard, two vital distinguishing features of the brain are its requirements for the highest concentrations of metal ions in the body and the highest per-weight consumption of body oxygen. In humans, the brain accounts for only 2% of total body mass but consumes 20% of the oxygen that is taken in through respiration. As a consequence of high oxygen demand and cell complexity, distinctly high metal levels pervade all regions of the brain and central nervous system. Structural roles for metal ions in the brain and the body include the stabilization of biomolecules in static (e.g., Mg2+ for nucleic acid folds, Zn2+ in zinc-finger transcription factors) or dynamic (e.g., Na+ and K+ in ion channels, Ca2+ in neuronal cell signaling) modes, and catalytic roles for brain metal ions are also numerous and often of special demand.

Metals in Neurobiology: Probing Their Chemistry and Biology with Molecular Imaging

Design strategies for water-soluble small molecular chromogenic and fluorogenic probes.

Luminescent sensors and switches in the early 21st century

Copper is an essential micronutrient that plays a central role for a broad range of biological processes. Although there is compelling evidence that the intracellular milieu does not contain any free copper ions, the rapid kinetics of copper uptake and release suggests the presence of a labile intracellular copper pool. To elucidate the subcellular localization of this pool, we have synthesized and characterized a membrane-permeable, copper-selective fluorescent sensor (CTAP-1). Upon addition of Cu(I), the sensor exhibits a 4.6-fold emission enhancement and reaches a quantum yield of 14%. The sensor exhibits excellent selectivity toward Cu(I), and its emission response is not compromised by the presence of millimolar concentrations of Ca(II) or Mg(II) ions. Variable temperature dynamic NMR studies revealed a rapid Cu(I) self-exchange equilibrium with a low activation barrier of deltaG++ = 44 kJ.mol(-1) and k(obs) approximately 10(5) s(-1) at room temperature. Mouse fibroblast cells (3T3) incubated with the sensor produced a copper-dependent perinuclear staining pattern, which colocalizes with the subcellular locations of mitochondria and the Golgi apparatus. To evaluate and confirm the sensor's copper-selectivity, we determined the subcellular topography of copper by synchrotron-based x-ray fluorescence microscopy. Furthermore, microprobe x-ray absorption measurements at various subcellular locations showed a near-edge feature that is characteristic for low-coordinate monovalent copper but does not resemble the published spectra for metallothionein or glutathione. The presented data provide a coherent picture with strong evidence for a kinetically labile copper pool, which is predominantly localized in the mitochondria and the Golgi apparatus.

https://www.pnas.org/content/pnas/102/32/11179.full.pdf

Imaging of the intracellular topography of copper with a fluorescent sensor and by synchrotron x-ray fluorescence microscopy

A series of donor-substituted 1,3,5-triaryl-2-pyrazoline fluorophores were structurally characterized by X-ray analysis, and their photophysical properties studied by steady-state absorption and emission spectroscopy. The photoinduced electron-transfer thermodynamics of the derivatives was estimated on the basis of the spectroscopic data and redox potentials of the fluorophores. The aryl substituents in the 1- and 3-position of the pyrazoline ring influence the photophysical properties of the fluorophores in distinctly different ways. The excited-state equilibrium energy ΔE00 is primarily influenced by changes of the substituent in the 1-position, whereas the reduction potential of the fluorophore is essentially determined by the 3-aryl group. Density functional calculations were used to probe the electronic structure and energy ordering of the emissive and the electron-transfer state. The results from the computational analysis agree qualitatively well with the experimental data. In addition, we have eva...

Tuning the photoinduced electron-transfer thermodynamics in 1,3,5-triaryl-2-pyrazoline fluorophores: X-ray structures, photophysical characterization, computational analysis, and in vivo evaluation.

A large class of cation-responsive fluorescent sensors utilizes a donor-spacer-acceptor (D-A) molecular framework that can modulate the fluorescence emission intensity through a fast photoinduced intramolecular electron transfer (PET) process. The emission enhancement upon binding of the analyte defines the contrast ratio of the probe, a key property that is particularly relevant in fluorescence microscopy imaging applications. Due to their unusual electronic structure, 1,3,5-triarylpyrazoline fluorophores allow for the differential tuning of the excited-state energy DeltaE(00) and the fluorophore acceptor potential E(A/A(-)), both of which are critical parameters that define the electron transfer (ET) thermodynamics and thus the contrast ratio. By systematically varying the number and attachment positions of fluoro substituents on the fluorophore pi-system, DeltaE(00) can be adjusted over a broad range (0.4 eV) without significantly altering the acceptor potential E(A/A(-)). Experimentally measured D-A coupling and reorganization energies were used to draw a potential map for identifying the optimal ET driving force that is expected to give a maximum fluorescence enhancement for a given change in donor potential upon binding of the analyte. The rational design strategy was tested by optimizing the fluorescence response of a pH-sensitive probe, thus yielding a maximum emission enhancement factor of 400 upon acidification. Furthermore, quantum chemical calculations were used to reproduce the experimental trends of reduction potentials, excited-state energies, and ET driving forces within the framework of linear free energy relationships (LFERs). Such LFERs should be suitable to semiempirically predict ET driving forces with an average unsigned error of 0.03 eV, consequently allowing for the computational prescreening of substituent combinations to best match the donor potential of a given cation receptor. Within the scaffold of the triarylpyrazoline platform, the outlined differential tuning of the electron transfer parameters should be applicable to a broad range of cation receptors for designing PET sensors with maximized contrast ratios.

/pdf/differential-tuning-of-the-electron-transfer-parameters-in-1-1clklswgd9.pdf

Differential Tuning of the Electron Transfer Parameters in 1,3,5-Triarylpyrazolines: A Rational Design Approach for Optimizing the Contrast Ratio of Fluorescent Probes

Liuchun Yang

Papers

Imaging of the intracellular topography of copper with a fluorescent sensor and by synchrotron x-ray fluorescence microscopy

Tuning the photoinduced electron-transfer thermodynamics in 1,3,5-triaryl-2-pyrazoline fluorophores: X-ray structures, photophysical characterization, computational analysis, and in vivo evaluation.

Differential Tuning of the Electron Transfer Parameters in 1,3,5-Triarylpyrazolines: A Rational Design Approach for Optimizing the Contrast Ratio of Fluorescent Probes

A novel micro-sphere activated carbon synthesized from waste cigarette butts for ammonia adsorption.