Light‐triggered stabilization of microgel aggregates

Supramolecular assembly holds great potential in many technological applications. Such structures, however, tend to destabilize in dynamic environments due to weak interactions between their constituent entities. We report on a highly modular and biofriendly chemistry for the stabilization of supramolecular microgel aggregates. Upon irradiation, these structures undergo intermolecular cross‐linking, providing an efficient mechanism for stabilization.     

2-Nitrobenzaldehyde as a chemical actinometer for solution and ice photochemistry

2-Nitrobenzaldehyde (2NB) is a convenient, photochemically sensitive, and thermally robust actinometer. Although 2NB has been used in a number of solution and ice experiments in the laboratory, the quantum efficiencies and molar absorptivities of 2NB have not been critically evaluated, especially on ice. Using a series of laboratory and field measurements we have measured the light absorbance and photochemical properties of 2-nitrobenzaldehyde in solution (water and/or acetonitrile) and in/on water ice. Our results show that the molar absorptivities of 2NB are only weakly dependent upon temperature and that the quantum yield is independent of temperature in water; the quantum yield is also independent of wavelength, as shown by past reports. Furthermore, we find that the photochemistry of 2NB in/on water ice is the same as in liquid water. While most studies employing 2NB cite and use a quantum yield of 0.50, based on a review of the literature, and on our new experimental data, we recommend a quantum yield of 0.41 for 2NB photolysis for both solution and water ice.     

Spin labeling of Natronomonas pharaonis halorhodopsin: probing the cysteine residues environment

Halorhodopsin from Natronomonas pharaonis (pHR) is a light-driven chloride pump that transports a chloride anion across the plasma membrane following light absorption by a retinal chromophore which initiates a photocycle. Analysis of the amino acid sequence of pHR reveals three cysteine residues (Cys160, Cys184, and Cys186) in helices D and E. Here we have labeled the cysteine residues with nitroxide spin labels and studied using electron paramagnetic resonance (EPR) spectroscopy their mobility, accessibility to various reagents, and the distance between the labels. It was revealed by following the d(1)/d parameter that the distance between the spin labels is ca. 13-15 Angstrom. The EPR spectrum suggests that one label has a restricted mobility while the other two are more mobile. Only one label is accessible to hydrophilic paramagnetic broadening reagents leading to the conclusion that this label is exposed to the water phase. All three labels are reduced by ascorbic acid and reoxidized by molecular oxygen. The rate of the oxidation is accelerated following retinal irradiation indicating that the protein experiences conformation alterations in the vicinity of the labels during the pigment photocycle. It is suggested that Cys186 is exposed to the bulk medium while Cys184, located close to the retinal ionone ring, exhibits an immobilized EPR signal and is characterized by a hydrophobic environment.     

Three-dimensional optical metrology with color-coded extended depth of focus

A novel method of rapid three-dimensional optical metrology that is based on triangulation of a configuration of color-coded light stripes is presented. The method exploits polychromatic illumination and a combined diffractive-refractive element, so the incident light is focused upon a stripe that is axially dispersed, greatly increasing the depth-measuring range without any decrease in the axial or the lateral resolution. The discrimination of each color stripe is further improved by spectral coding and decoding techniques. An 18-fold increase in the depth of focus was experimentally obtained while diffraction-limited light stripes were completely maintained.     

Muon spin relaxation studies in frustrated and/or low-dimensional spin systems

An overview is given on muon spin relaxation (SR) measurements in frustrated and/or low dimensional spin systems. In the frustrated Kagomé lattice system SrCr₈Ga₄O₁₉, we observed dynamic spin fluctuations of 30 GHz, without any static frozen component even atT=0.1 K, much below the susceptibility-cusp temperatureT _g=3.5 K. This is in clear contrast with the case in dilute-alloy spin glassesCuMn andAuFe, where static order develops belowT _g. We also present the dimensionality dependence of the sub-lattice magnetization curves in 2-d Heisenberg systems, the remarkable suppression of the ordering temperature in a 1-d system Sr₂CuO₃, the observation of activation type spin dynamics in a 1-d Ising ferromagnet (DMeFc)(TCNE) aboveT _c, slow spin fluctuations ( 60 MHz) in Haldane-gap systems at low temperatures, and some results from organic 1-d and 2-d magnetic systems.     

μSR studies in an I2-doped phenylenediamine polymer

We report SR studies of the recently synthesized I₂-doped phenylenediamine polymer. Longitudinal-field spectra exhibit typical behavior of a spin-glass with a freezing temperatureT _g 100 K and a spontaneous static local field 500 G at low temperatures. Preliminary magnetization measurements hint of antiferromagnetic spin coupling and hysteretic behavior aroundT _g. These features suggest possible spin-glass and/or antiferromagnetic spin freezing with a high transition temperature due to the doped radical spins in this organic polymer.Postdoctoral fellow of the Humboldt Foundation.     

Muon spin relaxation in heavy fermion systems

Heavy fermion systems have received a great deal of study by a wide variety of techniques, includingSR. In a number of systems, coexisting superconducting and magnetic states have been reported, leading to speculation of an intimate connection between magnetism and superconductivity in these compounds. We observe a spontaneous magnetic field in the superconducting phase of UPt₃. In addition, the broadening of the transverse field muon precession signal only onsets approximately 60 mK below the superconductingT _c. Our results provide evidence that the lower superconducting phase in theH-T phase diagram of UPt₃ is characterised by broken time-reversal symmetry. Measurements of URu₂Si₂ and CeCu_2.2Si₂ indicate that the magnetically ordered volume fraction is temperature dependent in both systems.     

Muon spin relaxation measurements in kagomé lattice system SrCr8Ga4O19

Dynamical spin fluctuations in SrCr_8–xGa_4+xO₁₉ a frustrated spin system on a kagomé lattice, is examined by the longitudinal field muon spin relaxation technique. This system shows a spin-glass (SG)-like cusp in the susceptibility atT _g=3.5(2) K. The slowing down of Cr spin fluctuations is found to occur over a very wide temperature rangeT _g<T<30T _g. AsT/T _g 0 these fluctuations remain without static polarization (order parameter). Such strong fluctuations belowT _g have not been observed before in a conventional SG system.     

三元络合物的动力学研究和机理探讨——钪-铬天青S-溴化十六烷基三甲铵体系

本文测定了CAS,Sc-CAS和Sc-CAS-CTMAB体系的吸收光谱,三元络合物组成比为Sc:CAS∶CTMAB=1∶2∶2,用动力学方法获得经验速率方程R=k[Sc(h)][CAS][CTMAB]^-2,参照Eigen-Tamm机理提出了一种“胶束-溶剂笼”机理,此机理用平衡浓度法处理后,其速率方程与实验结果一致,对三元络合物的几何构型和反应模式也进行了讨论。