Temporal Control of Membrane Fusion through Photolabile PEGylation of Liposome Membranes

Membrane fusion results in the transport and mixing of (bio)molecules across otherwise impermeable barriers. In this communication, we describe the temporal control of targeted liposome–liposome membrane fusion and contents mixing using light as an external trigger. Our method relies on steric shielding and rapid, photoinduced deshielding of complementary fusogenic peptides tethered to opposing liposomal membranes. In an analogous approach, we were also able to demonstrate precise spatiotemporal control of liposome accumulation at cellular membranes in vitro.     

Light-induced geometrical changes in acyclic ruthenium(II) complexes and their ruthena-macrocyclic analogues

The two ligands 1 (4'-(3-anisylphenyl)-2,2';6',2' '-terpyridine) and 2 (2-mesityl-8-anisyl-1,10-phenanthroline) (Scheme 2) were synthesized and coordinated to ruthenium. The corresponding complexes Ru(1)(2)(L)n+, where L = Cl-, CH3CN, or C5H5N, have been fully characterized. Notably, the hindering mesityl group of the phenanthroline ligand was shown to lie opposite to the monodentate ligand L both in solution and in the solid state. Upon irradiation in acetonitrile or pyridine, quantitative isomerization of the complex occurred, which consisted of a 90 degrees rotation of the bidentate chelate. In the new isomers the mesityl group was shown to pi stack to the coordinated monodentate ligand with the anisyl group of the phen (1,10-phenanthroline) lying on the other side of the ruthenium atom. The back reaction was performed by heating the photochemical isomers of the complexes in DMSO and exchanging the DMSO with chloride anion, acetonitrile, or pyridine. The stability of the ruthenium(II)-pyridine bond was used in order to inscribe the Ru(terpy)(phen) motif in a molecular ring. Functionalization of the ligands and subsequent cyclization reaction on the complex were performed on the two isomers of Ru(1)(2)(C5H5N)2+. Four macrocyclic complexes including the Ru(terpy)(phen)(py)n+ moiety were obtained and characterized. A (CH2)18 alkane chain or polyethylene glycol chain formed the flexible part of the ruthena-macrocycles. Upon visible light irradiation a dramatic geometrical changeover of the cyclic complex took place, which could be reversed thermally.     

Unusual transformations of the chrysanthemic nitrile skeleton by sodium hydride in n,n-dimethylformamide

It is shown that the title transformations occurred through basecatalyzed opening of the cyclopropane ring into the dienic nitrile $\text{4}$which then reacted with the in situ formed formaldehyde to yield the bicyclic compound $\text{5}$.     

Slow-light spatial solitons

We numerically and experimentally report the observation of slow-light spatial solitons in a Kerr medium owing to light amplification by stimulated Raman scattering. This was achieved in a CS2 nonlinear planar waveguide that possesses both a strong self-focusing nonlinearity to generate the spatial Raman soliton and a Raman susceptibility sharp enough to induce the slow-light process simultaneously. We show that the Raman Stokes component is optically delayed by more than 120 ps for a 140 ps Raman pulse duration and only 3 cm of propagation length, while propagating as a spatial soliton beam.     

Ruthenium-based light-driven molecular machine prototypes: synthesis and properties

In the past years, many dynamic systems often referred to as "molecular machines" have been elaborated. They are generally set in motion by external stimuli like chemical, electrochemical, or photochemical reactions. Light irradiation seems particularly promising since the input signal can be switched on and off fast and readily on a very small place. In this tutorial review, we will highlight recent advances in the design and synthesis of various ruthenium(II) complexed rotaxanes, catenanes, scorpionates or macrocycles. In these compounds, one part of the system is set in motion by photochemically expelling a given chelate. We will discuss the behaviour of various topologically non-trivial systems like catenanes and rotaxanes as well as acyclic and macrocyclic models.     

Molecular and electronic structures of oxo-bis(benzene-1,2-dithiolato)chromate(V) monoanions. A combined experimental and density functional study

Two oxo-bis(benzene-1,2-dithiolato)chromate(V) complexes, namely, [CrO(L(Bu))2]1- and [CrO(L(Me))2]1-, have been synthesized and studied by UV-vis, EPR, magnetic circular dichroism (MCD), and X-ray absorption spectroscopy and by X-ray crystallography; their electro- and magnetochemistries are reported. H2L(Bu) represents the pro-ligand 3,5-di-tert-butylbenzene-1,2-dithiol, and H2L(Me) is the corresponding 4-methyl-benzene-1,2-dithiol. A structural feature of interest for both the complexes is the folding of the dithiolate ligands about the S-S vector providing Cs symmetry to the complexes. Geometry optimizations using all-electron density functional theory with scalar relativistic corrections at the second-order Douglas-Kroll-Hess (DKH2) and zeroth-order regular approximation (ZORA) levels result in excellent agreement with the experimentally determined structures and electronic and S K-edge X-ray absorption spectra. From DFT calculations, the Cs instead of C2v symmetry for the complexes is attributed to the strong S(3p) --> Cr(3d(x2-y2)) pi-donation in Cs geometry providing additional stability to the complexes.     

Ultrafast laser processing of drug particles in water for pharmaceutical discovery

The laser fragmentation technique has been extensively used to produce inorganic nanoparticles, but its practice on organic materials, especially on drugs, is less common. Here, we briefly review the recent advances in laser micro-/nanonization of organic materials and the rationale of using laser fragmentation for drug discovery. We present our case studies of two drug models: fenofibrate and naproxen. Both drugs were fragmented in water with femtosecond (fs) laser and characterized in terms of particle size distribution and physicochemical properties. Effects of fs laser fragmentation were also compared with nanosecond (ns) laser fragmentation and with conventional media milling technique. Fs laser was more suitable to produce sub-micron size drug particles than ns laser, but degradation of drugs after nanonization was also more pronounced than micronization. Physicochemical transformations such as oxidation, hydration and amorphisation might occur during the laser–material interactions. Laser nanonization showed improved dissolution kinetics, similar to media milling. Unlike the conventional milling techniques, laser fragmentation enabled the treatment of minute amount (as small as several milligrams) of drugs with high efficiency, thus is a useful tool for particle size reduction during the early phases of drug discovery.     

Stereospecific cyclisations of substituted α′-lithiatedα(Z), γ-butadienyl sulfoxides

The title compounds $\text{2}$(b-d) were prepared and converted stereospecifically to the lithiated derivatives of cyclic sulfoxides $\text{3}$(b-d) through a proposed concerted disrotatory electrocyclisation.