Dynamic Behavior of Supramolecular Comb Polymers Consisting of Poly(2‐Vinyl Pyridine) and Palladium‐Pincer Surfactants in the Solid State

When poly(2‐vinyl pyridine) is combined with Pd‐pincer‐based organometallic surfactants, a mesomorphic structure forms due to weak stacking interactions between the pyridine units and the Pd‐pincer headgroups. The weak binding between the surfactant and the polymer competes with the tendency of the aliphatic tails of the surfactant to crystallize. Here, we demonstrate that over extended periods of incubation, the crystallization tendency of the surfactant tails causes the surfactant molecules to detach from the polymer and gives rise to additional packing modes of the alkyl tails featuring higher crystalline order. The dynamic behavior of these aged structures was investigated by variable‐temperature small‐angle X‐ray scattering (SAXS) and solid‐state ¹³C NMR, and revealed the influence of thermal changes on the molecular level, and how these changes propagate to the mesoscale structure.     

Rhenium(VII) oxide catalyzed heteroacylative ring-opening dimerization of tetrahydrofuran

Re(2)O(7), which is known primarily as a strong oxidant, was found to be a highly selective Lewis acid catalyst that affects the heteroacylative dimerization of THF at room temperature. This multicomponent reaction, which involves THF, trifluoroacetic anhydride (TFAA), and a carboxylic acid, produces a nonsymmetrical diester, RCO(2)(CH(2))(4)O(CH(2))(4)OCOCF(3), in high yields. The reaction is quite general with respect to the carboxylic acid but is highly selective for unsubstituted THF in preference to other cyclic ethers. It is also highly selective for TFAA in preference to other anhydrides. Isotope labeling experiments indicate that two of the five oxygen atoms in the product originate from THF; one comes from rhenium oxide, and the two carbonyl oxygens originate from the carboxylic acid and from TFAA. The catalytic cycle, which is proposed on the basis of these experiments, involves a multistep sequence of nucleophilic attacks, starting with an attack of a rhenium oxo ligand on a coordinated THF, then attack of the resultant alkoxide ligand on a second coordinated THF, nucleophilic addition of the resultant alkoxide ligand to the coordinated carboxylic acid (an intramolecular metal-oxygen bond metathesis), and, finally, electrophilic cleavage of the other coordinated alkoxide by TFAA to produce the nonsymmetrical diester. This synthetically useful reaction highlights the unique, frequently avoided Lewis acidity of transition-metal oxides.     

Parallel biomolecular computation on surfaces with advanced finite automata

A biomolecular, programmable 3-symbol-3-state finite automaton is reported. This automaton computes autonomously with all of its components, including hardware, software, input, and output being biomolecules mixed together in solution. The hardware consisted of two enzymes: an endonuclease, BbvI, and T4 DNA ligase. The software (transition rules represented by transition molecules) and the input were double-stranded (ds) DNA oligomers. Computation was carried out by autonomous processing of the input molecules via repetitive cycles of restriction, hybridization, and ligation reactions to produce a final-state output in the form of a dsDNA molecule. The 3-symbol-3-state deterministic automaton is an extension of the 2-symbol-2-state automaton previously reported, and theoretically it can be further expanded to a 37-symbol-3-state automaton. The applicability of this design was further amplified by employing surface-anchored input molecules, using the surface plasmon resonance technology to monitor the computation steps in real time. Computation was performed by alternating the feed solutions between endonuclease and a solution containing the ligase, ATP, and appropriate transition molecules. The output detection involved final ligation with one of three soluble detection molecules. Parallel computation and stepwise detection were carried out automatically with a Biacore chip that was loaded with four different inputs.     

Chemical Synthesis of Proteins with Non‐Strategically Placed Cysteines Using Selenazolidine and Selective Deselenization

Although native chemical ligation has enabled the synthesis of hundreds of proteins, not all proteins are accessible through typical ligation conditions. The challenging protein, 125‐residue human phosphohistidine phosphatase 1 (PHPT1), has three cysteines near the C‐terminus, which are not strategically placed for ligation. Herein, we report the first sequential native chemical ligation/deselenization reaction. PHPT1 was prepared from three unprotected peptide segments using two ligation reactions at cysteine and alanine junctions. Selenazolidine was utilized as a masked precursor for N‐terminal selenocysteine in the middle segment, and, following ligation, deselenization provided the native alanine residue. This approach was used to synthesize both the wild‐type PHPT1 and an analogue in which the active‐site histidine was substituted with the unnatural and isosteric amino acid β‐thienyl‐l ‐alanine. The activity of both proteins was studied and compared, providing insights into the enzyme active site.     

The Inner Structure of Black Holes

We study the gravitational collapse of a self-gravitating charged scalar-field. Starting with a regular spacetime, we follow the evolution through the formation of an apparent horizon, a Cauchy horizon and a final central singularity. We find a null, weak, mass-inflation singularity along the Cauchy horizon, which is a precursor of a strong, spacelike singularity along the r = 0 hypersurface. The inner black hole region is bounded (in the future) by singularities. This resembles the classical inner structure of a Schwarzschild black hole and it is remarkably different from the inner structure of a charged static Reissner-Nordström or a stationary rotating Kerr black holes.     

Conjugated polymer with rigid donor poly(para‐divinylphenylamino) backbone and pendant cyanoacetic acid acceptor for dye sensitized solar cells

A donor backbone [poly(para‐divinylphenylamino)]‐acceptor (cyanoacetic acid side group) type conjugated polymer ( P2 ) has been synthesized and used as the active material for dye‐sensitized solar cells. DFT calculation shows that the insertion of vinyl link in the polymer backbone leads to a planar structure in P2 and changes the excited state significantly. Photoelectrochemical cells based on the DSSC format were fabricated using the polymers as sensitizers. The cell constructed using P2 exhibits a considerably high peak IPCE and J‐V response, with an overall power conversion efficiency of 3.67%. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2958–2965     

Realization of a sonic black hole analog in a Bose-Einstein condensate

We have created an analog of a black hole in a Bose-Einstein condensate. In this sonic black hole, sound waves, rather than light waves, cannot escape the event horizon. A steplike potential accelerates the flow of the condensate to velocities which cross and exceed the speed of sound by an order of magnitude. The Landau critical velocity is therefore surpassed. The point where the flow velocity equals the speed of sound is the sonic event horizon. The effective gravity is determined from the profiles of the velocity and speed of sound. A simulation finds negative energy excitations, by means of Bragg spectroscopy.