The Expanded Genetic Alphabet

All biological information, since the last common ancestor of all life on Earth, has been encoded by a genetic alphabet consisting of only four nucleotides that form two base pairs. Long‐standing efforts to develop two synthetic nucleotides that form a third, unnatural base pair (UBP) have recently yielded three promising candidates, one based on alternative hydrogen bonding, and two based on hydrophobic and packing forces. All three of these UBPs are replicated and transcribed with remarkable efficiency and fidelity, and the latter two thus demonstrate that hydrogen bonding is not unique in its ability to underlie the storage and retrieval of genetic information. This Review highlights these recent developments as well as the applications enabled by the UBPs, including the expansion of the evolution process to include new functionality and the creation of semi‐synthetic life that stores increased information.     

Chemical investigation of three plutonium–beryllium neutron sources

Thorough physical and chemical characterization of plutonium–beryllium (PuBe) neutron sources is an important capability with applications ranging from material accountancy to nuclear forensics. Characterization of PuBe sources is not trivial owing to range of existing source designs and the need for adequate infrastructure to deal with radiation and protect the analyst. This study demonstrates a method for characterization of three PuBe sources that includes physical inspection and imaging followed by controlled disassembly and destructive analysis.     

The Direct Conversion of Carboxylic Acids to Carboxamides via Reaction with Unsolvated Bis(Diorganoamino) Magnesium Reagents

It has been found that unsolvated bis (diorganoamino) magnesium compounds react smoothly with carboxylic acids to give the corresponding carboxamides directly in good to excellent yields.     

cis,trans-1,5-Cyclodecadiene—Sulfur Dioxide Copolymer

An alternating linear copolymer of cis,trans-1,5-cyclodecadiene and sulfur dioxide has been prepared in quantitative yield. Transannular carbon-carbon bond formation gives four saturated carbon atoms between the sulfone groups. The polymer is resistant to alkali but degrades thermally above 150°C with random chain cleavage.     

Hamiltonian traffic dynamics in microfluidic-loop networks

Recent microfluidic experiments revealed that large particles advected in a fluidic loop display long-range hydrodynamic interactions. However, the consequences of such couplings on the traffic dynamics in more complex networks remain poorly understood. In this Letter, we focus on the transport of a finite number of particles in one-dimensional loop networks. By combining numerical, theoretical, and experimental efforts, we evidence that this collective process offers a unique example of Hamiltonian dynamics for hydrodynamically interacting particles. In addition, we show that the asymptotic trajectories are necessarily reciprocal despite the microscopic traffic rules explicitly break the time-reversal symmetry. We exploit these two remarkable properties to account for the salient features of the effective three-particle interaction induced by the exploration of fluidic loops.     

Oxygen-sensitive 19F NMR imaging of the vascular system in vivo

The fluorine nuclear magnetic resonance spin-lattice relaxation rate (1/T1) of the perfluorochemical blood substitute perfluorotripropylamine (FTPA) is very sensitive to oxygen tension. This presents the possibility of measuring blood oxygen tension by 19F MR imaging. We obtained oxygen-sensitive 19F NMR images of the circulatory system of rats infused with emulsified FTPA. Blood oxygenation was assessed under conditions of both air- and 100% O2-breathing. T1 relaxation times were derived from MR images using a partial saturation pulse sequence. The T1 times were compared with a phantom calibration curve to calculate average blood pO2 values in the lung, liver, and spleen. The results showed marked, organ-specific increases in blood oxygen tension when the rat breathed 100% O2 instead of air.     

Solventextraktion von Platinmetallen mit N-mono-und N,N-di-substituierten Benzoylthioharnstoffen

Summary Benzoylthioureas are excellent reagents for solvent extraction and have a high selectivity for platinum-group metals. Very effective separations of platinum-group metals are possible due to control of the extraction parameters and variation of the ligand structure. An easy synthesis and a high chemical resistence allow technical applications.

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Herrn Prof. Dr. G. Tölg zum 60. Geburtstag gewidmet     

Dynamic fragmentation of powders in spherical geometry

Experimental evidence from a wide range of sources shows that the expanding cloud of explosively disseminated material comprises of “particles” or fragments which have different dimensions from those associated with the original material. Photographic evidence shows jets or fingers behind these expanding fragments. Powders and liquids have often been used to surround explosives to act as blast mitigants; this is the main driver for our research. Other examples of areas where these features are observed include fuel air explosives and enhanced blast explosives as well as quasi-static pressure mitigation systems. In this paper, we consider the processes occurring when an explosive interacts with a surrounding layer of powder in spherical geometry. Results from explosive experiments designed to investigate the effects of powder grain size and powder fill-to-burster charge mass ratio ( \(F\) / \(B\) ) are presented and compared with results from numerical modelling to explore what determines the primary fragment size distribution resulting from explosive dissemination of a layer of material and when this process begins. The evidence clearly shows that the process starts during the first wave transit period of the powder material and, despite the surrounding material initially being a loose powder, shows the characteristics of a brittle fracture mechanism. Later time video evidence shows the same number of jets or fingers as are identified by X-rays of the early, primary fragmentation process. The number of fragments is only a very weak function of the initial grain size of the powder.     

Water-Soluble Organometallic Compounds. 8[1]. Synthesis, Spectral Properties, and Crystal Structures of 1,3,5-Triaza-7-phosphaadamantane (PTA) Derivatives of Metal Carbonyl Clusters: Ru3(CO)9(PTA)3 and Ir4(CO)7(PTA)5

The syntheses of Ru₃(CO)₉(PTA)₃ and Ir₄(CO)₇(PTA)₅ were accomplished through the thermal reactions of Ru₃(CO)₁₂ or Ir₄(CO)₁₂ with the water-soluble phosphine, PTA(1,3,5-triaza-7-phosphaadamantane). The ruthenium derivative was shown by X-ray crystallography to consist of a triangular Ru₃ core with three nearly equal Ru–Ru bonds, with each ruthenium atom bearing an equatorially positioned PTA ligand. In Ir₄(CO)₇(PTA)₅ the iridium atoms define a tetrahedron which is bridged on three edges by CO ligands. One basal iridium atom contains two PTA ligands, while the other two basal and the apical iridium atoms each possess one PTA ligand in their coordination spheres. Although, Ru₃(CO)₉(PTA)₃ is only sparingly soluble in pure water, it is very soluble in aqueous solution of pH<4. Indeed the triruthenium cluster can be extracted reversibly between an aqueous and an organic phase (e.g., CH₂Cl₂) by changing the pH of the aqueous phase. On the other hand the more highly PTA substituted cluster, Ir₄(CO)₇(PTA)₅, exhibits good solubility in aqueous solution (pH 7 and below) and a variety of organic solvents. Both cluster derivatives are stable in deoxygenated, aqueous solutions for extended period of time (>24 h).