Contribution of Cytosine‐Containing Cyclobutane Dimers to DNA Damage Produced by Photosensitized Triplet–Triplet Energy Transfer

Mutagenic cyclobutane pyrimidine dimers (CPDs) can be induced in DNA through either direct excitation or photosensitized triplet–triplet energy transfer (TTET). In the latter pathway, thymines are expected to receive the excitation energy from the photosensitizer and react with adjacent pyrimidines. By using state‐of‐the art analytical tools, we provide herein additional information on the formation of cytosine‐containing CPDs. We thus determined the yield of all possible CPDs upon TTET in a series of natural DNAs with various base compositions. We show that the distribution of CPDs cannot be explained only by excitation of individual thymines. We propose that the mechanism for TTET involves at least dinucleotides as the minimal targets. The observation of the formation of cytosine–cytosine CPDs also suggests that additional pathways are involved in this photosensitized reaction.     

Induced Chiroptical Changes of a Water‐Soluble Cryptophane by Encapsulation of Guest Molecules and Counterion Effects

We report the synthesis of the water‐soluble cryptophanol derivative 1 and the study of the chiroptical properties of its two enantiomers (>99 % ee) by polarimetry, electronic circular dichroism (ECD), and vibrational circular dichroism (VCD). We show that cryptophanol 1 exhibits unusual chiroptical properties in water under basic conditions (pH>12). For instance, the shapes of the ECD and VCD spectra of 1 in water were strongly dependent on the nature of the alkali metal ions (Li⁺, Na⁺, K⁺, Cs⁺) surrounding the cryptophane and whether or not a guest molecule is present inside the cavity of the host. To the best of our knowledge, this is the first example in which the nature of these counterions governs the chiroptical properties of a host molecule. Moreover, specific ECD spectra were obtained depending on the size of the guest molecules. This makes 1 a good sensor for small neutral molecules in aqueous solvent. Finally, VCD experiments associated with DFT calculations show that the chiroptical changes can be directly correlated to the presence of charges close to the aromatic rings and with a conformational change of the alkyl chains upon encapsulation.     

Microwave control electrodes for scalable,parallel, single-qubit operations in a surface-electrode ion trap

We propose a surface ion trap design incorporating microwave control electrodes for near-field single-qubit control. The electrodes are arranged so as to provide arbitrary frequency, amplitude and polarization control of the microwave field in one trap zone, whilst a similar set of electrodes is used to null the residual microwave field in a neighbouring zone. The geometry is chosen to reduce the residual field to the 0.5 % level without nulling fields; with nulling, the crosstalk may be kept close to the 0.01 % level for realistic microwave amplitude and phase drift. Using standard photolithography and electroplating techniques, we have fabricated a proof-of-principle electrode array with two trapping zones. We discuss requirements for the microwave drive system and prospects for scalability to a large 2-D trap array.     

Of Dogs and Fleas: The Dynamics of N Uncoupled Two-State Systems

The historical Ehrenfest model dating back to 1907 describes the process of equilibration together with fluctuations around the thermal equilibrium. This approach represents a special case in the dynamics of N uncoupled two-state systems. In this article we present a generalization of the original model by introducing an additional parameter p which denotes the probability of a single state change. Analytical solutions for the probability distribution of the system's state as well as the fluctuation distribution are derived. Interestingly, close inspection of the fluctuation distribution reveals an intrinsic time scale. Sampling the system's state at much slower rates yields the familiar macroscopic exponential distribution for equilibrium processes. For faster measurements a power law extends roughly over log₁₀ N orders of magnitude followed by an exponential tail. At some point, further increases of the sampling rate merely result in a shift of the fluctuation distribution towards higher values leaving plateau at small fluctuation sizes behind. Since the generic solution is rather unwieldy, we derive and discuss simple and intuitive analytical solutions in the limit of small p and large N. Furthermore, we relax the quantization of time by considering a complementary approach in continuous time. Finally we demonstrate that the fluctuation distributions resulting from the two different approaches bear identical characteristic features.     

Q-switched Yb-doped nonlinear microstructured fiber laser for the emission of broadband spectrum

We report on an innovative configuration of a supercontinuum laser based on an Yb-doped nonlinear microstructured fiber. Due to this particular fiber design combining amplification and nonlinear properties, a wideband output spectrum is generated in the fiber under the Q-switched regime. By exploiting stimulated Brillouin scattering, high peak power pulses are achieved and contribute to a spectral broadening due to a nonlinear wavelength conversion process. Both infrared (1000-1200 nm) and visible (650-750 nm) spectra are generated with an average power of 200 mW.     

High affinity of water-soluble cryptophanes for cesium cations

Exceptionally high affinity for cesium cations was achieved in aqueous solution using two enantiopure cryptophanes. Complexation of cesium was evidenced by (133)Cs NMR spectroscopy and by electronic circular dichroism (ECD). Binding constants as high as 6 × 10(9) M(-1) have been measured by isothermal titration calorimetry (ITC). Very strong complexation of rubidium cations (K ~10(6) M(-1)) has also been measured. Chiral hosts allowed the detection of the two cations at low concentrations (μM) using ECD.     

Surface chemistry and optimization of focused ion beam iodine-enhanced etching of indium phosphide

Focused ion beam physical sputtering and iodine-enhanced etching of indium phosphide (InP) were performed. Up to 15× enhanced etching rates over sputtering were measured at room temperature, due to the addition of iodine to the sputter-process. Reaction mechanisms and products are discussed and characterized. The reaction is limited by the desorption of indium triiodide (InI₃) at room temperature. InI₃ has to be removed by sputtering, which simultaneously amorphizes the underlying substrate. Surface roughness and stoichiometry of InP are compared for sputtering and etching. Gallium-contamination and the damaged zone in InP are significantly reduced by iodine-enhanced etching. Based on the reaction mechanisms, an optimum beam scanning strategy is proposed which allows precise microfabrication in reduced time and minimizes damage to the substrate. The method is also applicable for other halide gas etching processes of III-V semiconductors.     

Simultaneous determination of allantoin, hypoxanthine, xanthine, and uric acid in serum/plasma by CE

Allantoin (All) is an oxidative end product of purines in mammals. The small amount of All present in human plasma or serum results from free radical action on urate and may provide a stable marker of in vivo free radical activity. Because free radicals have been implicated in the development and progression of atherosclerosis, this study focused on the metabolic compounds of the All pathway. We propose a new fast CE (CE/UV) method for the simultaneous determination of All, uric acid (UA), hypoxanthine (HX), and xanthine (X) in human plasma. These products were quantified in the plasma of patients with chronic renal failure before hemodialysis (n = 6), patients with chronic heart failure (n = 6) and controls (n = 6). The filtered plasma were diluted ten-fold before the direct injection in CE/UV (195 nm), which allows separating the four compounds in less than 13 min. The metabolites were detectable at concentrations of 0.3-0.6 micromol/L. The method was linear over the range 0.5-150 micromol/L for All, HX, and X and 10-1500 micromol/L for UA (r > 0.99). The analytical performance of this method is satisfactory with intra-assay CV < 3.4%, inter-assay CV < 5% (HX and X < 7%), and recovery (93-101%). The proposed CE-UV method appears to be a useful tool for studying physiological and pathological changes of HX, UA, and All levels in plasma samples, the latter being a possible indicator of free radical damage in vivo.