Selective and Wash-Resistant Fluorescent Dihydrocodeinone Derivatives Allow Single-Molecule Imaging of μ-Opioid Receptor Dimerization

μ-Opioid receptors (μ-ORs) play a critical role in the modulation of pain and mediate the effects of the most powerful analgesic drugs. Despite extensive efforts, it remains insufficiently understood how μ-ORs produce specific effects in living cells. We developed new fluorescent ligands based on the μ-OR antagonist E-p-nitrocinnamoylamino-dihydrocodeinone (CACO), that display high affinity, long residence time and pronounced selectivity. Using these ligands, we achieved single-molecule imaging of μ-ORs on the surface of living cells at physiological expression levels. Our results reveal a high heterogeneity in the diffusion of μ-ORs, with a relevant immobile fraction. Using a pair of fluorescent ligands of different color, we provide evidence that μ-ORs interact with each other to form short-lived homodimers on the plasma membrane. This approach provides a new strategy to investigate μ-OR pharmacology at single-molecule level.     

Trifluoromethylation of [AuF3(SIMes)]: Preparation and Characterization of [Au(CF3)xF3−x(SIMes)] (x=1–3) Complexes

Trifluoromethylation of [AuF₃(SIMes)] with the Ruppert–Prakash reagent TMSCF₃ in the presence of CsF yields the product series [Au(CF₃)_xF_3−x(SIMes)] (x=1–3). The degree of trifluoromethylation is solvent dependent and the ratio of the species can be controlled by varying the stoichiometry of the reaction, as evidenced from the ¹⁹F NMR spectra of the corresponding reaction mixtures. The molecular structures in the solid state of trans-[Au(CF₃)F₂(SIMes)] and [Au(CF₃)₃(SIMes)] are presented, together with a selective route for the synthesis of the latter complex. Correlation of the calculated SIMes affinity with the carbene carbon chemical shift in the ¹³C NMR spectrum reveals that trans-[Au(CF₃)F₂(SIMes)] and [Au(CF₃)₃(SIMes)] nicely follow the trend in Lewis acidities of related organo gold(III) complexes. Furthermore, a new correlation between the Au−C_carbene bond length of the molecular structure in the solid state and the chemical shift of the carbene carbon in the ¹³C NMR spectrum is presented.     

The effect of resistant starches on fat oxidation in healthy adults as measured by a 13CO2-breath test

A resistant starch (RS) mixture (MIX) consisting of fibre of potatoes (FP) and wrinkled pea starch (WPS), and high amylose maize starch (HAMS) were supplemented in adults to evaluate their effects on fat oxidation by means of a ¹³CO₂-breath test. Sixteen subjects received a regular diet either without or with the supplementation of MIX and HAMS in randomised order. After administration of a [U-¹³C]algal lipid mixture, exhaled air was collected over 14?h in 0.5- and 1-h intervals. The ¹³C abundances were measured by nondispersive infrared spectroscopy. In comparison to the dry run (DR), supplementation with MIX and with HAMS increased the cumulative percentage dose recovery: (DR: 16.7?%, MIX: 16.9?%, HAMS: 18.0?%), but without statistical significance. The colonic degradation of MIX and HAMS to short-chain fatty acids tends to lower the formation of carbohydrate-derived acetyl-CoA and contributes to a postprandial lipid oxidation increase by using fat-derived acetyl-CoA as a compensatory fuel source.     

The first molybdenum dioxo compounds with eta 2-pyrazolate ligands: crystal structure and oxo transfer properties

Molybdenum dioxo compounds [MoO2Cl(eta 2-pz)] and [MoO2(eta 2-pz)2] with pz = eta (2)-3,5-di-tert-butylpyrazolate have been synthesized; crystallographic data, catalytic activity, and oxo transfer properties are described.     

Self-starting mode locking of a Nd:glass fiber laser by use of the third-order nonlinearity of low-temperature-grown GaAs

We present a diode-pumped Nd:glass fiber laser, emitting at 1060 nm, that is passively mode locked by fast nonlinear loss in low-temperature-grown GaAs (LT-GaAs). This new mode-locking mechanism is based on intensity-dependent defocusing in LT-GaAs that occurs after nonresonant generation of free carriers by two-photon absorption. Mode locking is self-starting and produces pulses as short as 4.1 ps.     

A microfluidic system enabling Raman measurements of the oxygenation cycle in single optically trapped red blood cells

Using a lab-on-a-chip approach we demonstrate the possibility of selecting a single cell with certain properties and following its dynamics after an environmental stimulation in real time using Raman spectroscopy. This is accomplished by combining a micro Raman set-up with optical tweezers and a microfluidic system. The latter gives full control over the media surrounding the cell, and it consists of a pattern of channels and reservoirs defined by electron beam lithography that is moulded into rubber silicon (PDMS). Different buffers can be transported through the channels using electro-osmotic flow, while the resonance Raman response of an optically trapped red blood cell (RBC) is simultaneously registered. This makes it possible to monitor the oxygenation cycle of the cell in real time and to investigate effects like photo-induced chemistry caused by the illumination. The experimental set-up has high potential for in vivo monitoring of cellular drug response using a variety of spectroscopic probes.     

Organic p-i-n solar cells

We introduce a p-i-n-type heterojunction architecture for organic solar cells where the active region is sandwiched between two doped wide-gap layers. The term p-i-n means here a layer sequence in the form p-doped layer, intrinsic layer and n-doped layer. The doping is realized by controlled co-evaporation using organic dopants and leads to conductivities of 10^-4 to 10^-5 S/cm in the p- and n-doped wide-gap layers, respectively. The photoactive layer is formed by a mixture of phthalocyanine zinc (ZnPc) and the fullerene C₆₀ and shows mainly amorphous morphology. As a first step towards p-i-n structures, we show the advantage of using wide-gap layers in M-i-p-type diodes (metal layer–intrinsic layer–p-doped layer). The solar cells exhibit a maximum external quantum efficiency of 40% between 630-nm and 700-nm wavelength. With the help of an optical multilayer model, we optimize the optical properties of the solar cells by placing the active region at the maximum of the optical field distribution. The results of the model are largely confirmed by the experimental findings. For an optically optimized device, we find an internal quantum efficiency of around 82% under short-circuit conditions. Adding a layer of 10-nm thickness of the red material N,N-dimethylperylene-3,4:9,10-dicarboximide (Me-PTCDI) to the active region, a power-conversion efficiency of 1.9% for a single cell is obtained. Such optically thin cells with high internal quantum efficiency are an important step towards high-efficiency tandem cells. First tandem cells which are not yet optimized already show 2.4% power-conversion efficiency under simulated AM 1.5 illumination of 125 mW/cm² . PACS 73.61.Ph; 78.30.Jw; 89.30.Cc