Na’il Saleh

Model for Photoinduced Bending of Slender Molecular Crystals

The growing realization that photoinduced bending of slender photoreactive single crystals is surprisingly common has inspired researchers to control crystal motility for actuation. However, new mechanically responsive crystals are reported at a greater rate than their quantitative photophysical characterization; a quantitative identification of measurable parameters and molecular-scale factors that determine the mechanical response has yet to be established. Herein, a simple mathematical description of the quasi-static and time-dependent photoinduced bending of macroscopic single crystals is provided. This kinetic model goes beyond the approximate treatment of a bending crystal as a simple composite bilayer. It includes alternative pathways for excited-state decay and provides a more accurate description of the bending by accounting for the spatial gradient in the product/reactant ratio. A new crystal form (space group P21/n) of the photoresponsive azo-dye Disperse Red 1 (DR1) is analyzed within the constraints of the aforementioned model. The crystal bending kinetics depends on intrinsic factors (crystal size) and external factors (excitation time, direction, and intensity).

Redox-Responsive Viologen-Mediated Self-Assembly of CB[7]-Modified Patchy Particles

Sulfonated surface patches of poly(styrene)-based colloidal particles (CPs) were functionalized with cucurbit[7]uril (CB[7]). The macrocycles served as recognition units for diphenyl viologen (DPV(2+)), a rigid bridging ligand. The addition of DPV(2+) to aqueous suspensions of the particles triggered the self-assembly of short linear and branched chainlike structures. The self-assembly mechanism is based on hydrophobic/ion-charge interactions that are established between DPV(2+) and surface-adsorbed CB[7]. DPV(2+) guides the self-assembly of the CPs by forming a ternary DPV(2+)⊂(CB[7])2 complex in which the two CB[7] macrocycles are attached to two different particles. Viologen-driven particle assembly was found to be both directional and reversible. Whereas sodium chloride triggers irreversible particle disassembly, the one-electron reduction of DPV(2+) with sodium dithionite causes disassembly that can be reversed via air oxidation. Thus, this bottom-up synthetic supramolecular approach allowed for the reversible formation and directional alignment of a 2D colloidal material.

Viologen-Templated Arrays of Cucurbit[7]uril-Modified Iron Oxide Nanoparticles

Magnetic and fluorescent assemblies of iron-oxide nanoparticles (NPs) were constructed by threading a viologen-based ditopic ligand, DPV(2+), into the cavity of cucurbituril (CB[7]) macrocycles adsorbed on the surface of the NPs. Evidence for the formation of 1:2 inclusion complexes that involve DPV(2+) and two CB[7] macrocycles was first obtained in solution by (1)H NMR and emission spectroscopy. DPV(2+) was found to induce self-assembly of nanoparticle arrays (DPV(2+)⊂CB[7]NPs) by bridging CB[7] molecules on different NPs. The resulting viologen-crosslinked iron-oxide nanoparticles exhibited increased saturation magnetization and emission properties. This facile supramolecular approach to NP self-assembly provides a platform for the synthesis of smart and innovative materials that can achieve a high degree of functionality and complexity and that are needed for a wide range of applications.

In vivo cytogenetic studies on rat’s bone-marrow cells of structurally related Schiff base complexes

The in vivo interactions of structurally-related Ni(II) and Fe(III) Schiff base complexes based on N-(8-quinolyl)salicylaldimine (HL1) and N-(8-quinolyl)napthaldimine (HL2) ligands with DNA molecules in the bone-marrow cells of rats were demonstrated using chromosomal aberrations (CAs) assay. The complexes differ by one aromatic group on the aldehyde site of the Schiff base (basicity or lipophilicity), or by the type of the central metal ions (Ni(II) or Fe(III)). Animals were injected intraperitoneally (i.p) with different concentrations of each drug, and CAs were examined in bone-marrow cells, 15 hours later. A significant increase in the frequency of CAs was induced upon treatment with 15 mg / kg weight of L1 complexes (P < 0.001), and not with L2 complexes (P > 0.05). Also, the magnitude of aberrations induced by L1-Ni(II) was higher than that induced by L1-Fe(III) (P < 0.01). The binding data, estimated using UV-Visible absorption technique, showed that the metal binding of HL1 was much greater than that of HL2 and that the affinity of HL1 towards Ni(II) is higher than that for Fe(III) ions. Thus, the trends in the presented in vivo results signify the important role of complex stability in predicting the clastogenicity of metal-ion-chelating Schiff base drugs.

Intermolecular interactions between cucurbit[7]uril and pilocarpine.

The interactions between cucurbit[7]uril (CB7) macrocycles and pilocarpine (PIL) were investigated in aqueous solution by using (1)H NMR and circular dichroism (CD) spectroscopic techniques. The characterizations of the freeze-drying solid complex were conducted by electrospray ionization mass spectroscopy (ESI-MS), Fourier transform-infrared spectroscopy (FT-IR), thermogravimetry, and differential scanning calorimetry (DSC) techniques. The DSC and thermogravimetry confirmed the production of a thermally stable solid complex. The NMR, CD and ESI-MS measurements confirmed asymmetric induction during the complexation reaction, in which the γ-lactone ring of PIL (not the imidazole nucleus) has been fully encapsulated within the cavity of CB7. The stability of the drug has significantly enhanced as evidenced by the high-performance liquid chromatographic (HPLC) method. The results are discussed in the context of utilizing non-conventional supramolecular host-guest approaches to enhance the chemical stability in aqueous media of hydrophilic PIL drugs as model compounds. The non-classical stereospecific interactions between CB7 and PIL drugs are also highlighted.

Genotoxicity of structurally related copper and zinc containing Schiff base complexes.

Abstract The utilization of Schiff bases in the industrial and pharmaceutical fields has led to an increase in their syntheses and evaluation of their biological activities. In this study, we described the synthesis and genotoxicity of two Schiff bases that share common platform in their construction, namely, naphthalene, and are complexed to either Cu(II) or Zn(II). The genotoxicity of these complexes was evaluated in cultured lymphocytes using sister chromatid exchanges (SCEs) and chromosomal aberrations (CAs), and in rats using the urine 8-OH-2-deoxyguanosine (8-OH-dG) assay. The results showed that the examined complexes are genotoxic, but with different degrees. The order of genotoxicity of the complexes at 10 µg/mL was: Cu(L3)(NCS)(H2O) > Zn(L3)(NCS)(H2O) > Cu(L2)(NCS) > Zn(L2)(NCS), where L2 and L3 are the conjugate bases of N-(8-quinolyl)napthaldimine and N-(anilinyl)napthaldimine, respectively. However, at the 1-µg/mL concentration, only the Cu(L3)(NCS)(H2O) complex induced significant CAs, whereas at the 0.1-µg/mL concentration, only Cu(L3)(NCS)(H2O) and Zn(L2)(NCS) complexes induced significant SCEs, compared to controls. In the urine 8-OH-dG assay, all complexes at 10 mg/100 g body weight (b.w.) were found to cause DNA damage with the following order: Cu(L3)(NCS)(H2O) > Zn(L2)(NCS) > Zn(L3)(NCS)(H2O) > Cu(L2)(NCS), whereas no significant DNA damage was observed in animals exposed to 1 and 0.1 mg/100 g b.w. (p > 0.05). In conclusion, the two examined Schiff base complexes are found to induce DNA damage, but with different degrees.

Bioinspired Molecular Lantern: Tuning the Firefly Oxyluciferin Emission with Host–Guest Chemistry

Fireflies generate flashes of visible light via luciferase-catalyzed chemiexcitation of the substrate (luciferin) to the first excited state of the emitter (oxyluciferin). Microenvironment effects are often invoked to explain the effects of the luciferase active pocket on the emission; however, the exceedingly complex spectrochemistry and synthetic burdens have precluded elucidation of the nature of these interactions. To decipher the effects of microenvironment on the light emission, here the hydrophobic interior of cucurbit[7]uril (CB7) is used to mimic the nonpolar active pocket of luciferase. The hydrophobic interior of CB7 induces shifts of the ground-state pKas by 1.9-2.5 units to higher values. Upon sequestration, the emission maxima of neutral firefly oxyluciferin and its conjugate monodeprotonated base are blue-shifted by 40 and 39 nm, respectively, resulting in visual color changes of the emitted light.