Base-Pairing Properties of Double-Headed Nucleotides

Nucleotides that contain two nucleobases (double-headed nucleotides) have the potential to condense the information of two separate nucleotides into one. This presupposes that both bases must successfully pair with a cognate strand. Here, double-headed nucleotides that feature cytosine, guanine, thymine, adenine, hypoxanthine, and diaminopurine linked to the C2′-position of an arabinose scaffold were developed and examined in full detail. These monomeric units were efficiently prepared by convergent synthesis and incorporated into DNA oligonucleotides by means of the automated phosphoramidite method. Their pairing efficiency was assessed by UV-based melting-temperature analysis in several contexts and extensive molecular dynamics studies. Altogether, the results show that these double-headed nucleotides have a well-defined structure and invariably behave as functional dinucleotide mimics in DNA duplexes.     

Solar Thermal Energy Storage in a Photochromic Macrocycle

The conversion and efficient storage of solar energy is recognized to hold significant potential with regard to future energy solutions. Molecular solar thermal batteries based on photochromic systems exemplify one possible technology able to harness and apply this potential. Herein is described the synthesis of a macrocycle based on a dimer of the dihydroazulene/vinylheptafulvene (DHA/VHF) photo/thermal couple. By taking advantage of conformational strain, this DHA–DHA macrocycle presents an improved ability to absorb and store incident light energy in chemical bonds (VHF–VHF). A stepwise energy release over two sequential ring‐closing reactions (VHF→DHA) combines the advantages of an initially fast discharge, hypothetically addressing immediate energy consumption needs, followed by a slow process for consistent, long‐term use. This exemplifies another step forward in the molecular engineering and design of functional organic materials towards solar thermal energy storage and release.     

Substrates and Cyclic Peptide Inhibitors of the Oligonucleotide-Activated Sirtuin 7**

The sirtuins are NAD⁺-dependent lysine deacylases, comprising seven isoforms (SIRT1–7) in humans, which are involved in the regulation of a plethora of biological processes, including gene expression and metabolism. The sirtuins share a common hydrolytic mechanism but display preferences for different ϵ-N-acyllysine substrates. SIRT7 deacetylates targets in nuclei and nucleoli but remains one of the lesser studied of the seven isoforms, in part due to a lack of chemical tools to specifically probe SIRT7 activity. Here we expressed SIRT7 and, using small-angle X-ray scattering, reveal SIRT7 to be a monomeric enzyme with a low degree of globular flexibility in solution. We developed a fluorogenic assay for investigation of the substrate preferences of SIRT7 and to evaluate compounds that modulate its activity. We report several mechanism-based SIRT7 inhibitors as well as de novo cyclic peptide inhibitors selected from mRNA-display library screening that exhibit selectivity for SIRT7 over other sirtuin isoforms, stabilize SIRT7 in cells, and cause an increase in the acetylation of H3 K18.     

Towards a Comprehensive Stability Theory for Feynman’s Operational Calculus: The Time-Dependent Setting

We obtain lower bounds on blow-up of solutions for the 3D magneto-micropolar equations. More precisely, we establish some estimates for the solution \((\mathbf{u},\mathbf{w},\mathbf{b}) (t)\) in its maximal interval \([0,T^{*})\) provided that \(T^{*}<\infty\), which show for \(\delta\in(0,1)\) that \(\|(\mathbf{u},\mathbf{w},\mathbf{b})(t)\|_{\dot{H}^{s}}\) is at least of the order \((T^{*}-t)^{-(\delta s)/(1+2\delta)}\) for \(s\geq1/2+\delta\). In particular, by choosing a suitable \(\delta\), one concludes that \(\|(\mathbf{u},\mathbf{w},\mathbf{b})(t)\|_{\dot{H}^{s}}\) is at least of the order \((T^{*}-t)^{-s/4}\), and \((T^{*}-t)^{1/4-s/2}\) for \(s\geq1\), and \(1/2< s<3/2\), respectively. We also show that \((T^{*}-t)^{-s/3}\) is a lower rate for \(\|(\mathbf{u},\mathbf{w},\mathbf{b})(t)\|_{\dot{H}^{s}}\) if \(s>3/2\).     

Anisotropic Mixed-Norm Hardy Spaces

We introduce and explore Hardy spaces defined by mixed Lebesgue norms and anisotropic dilations. We prove that the definitions of these spaces in terms of smooth, non-tangential, auxiliary, grand, and Poisson maximal operators coincide. We also study the relation between anisotropic mixed-norm Hardy spaces and mixed-norm Lebesgue spaces.     

Non-linear stochastic response of a shallow cable

The paper considers the stochastic response of geometrical non-linear shallow cables. Large rain-wind induced cable oscillations with non-linear interactions have been observed in many large cable stayed bridges during the last decades. The response of the cable is investigated for a reduced two-degrees-of-freedom system with one modal coordinate for the in-plane displacement and one for the out-of-plane displacement. At first harmonic varying chord elongation at excitation frequencies close to the corresponding eigenfrequencies of the cable is considered in order to identify stable modes of vibration. Depending on the initial conditions the system may enter one of two states of vibration in the static equilibrium plane with the out-of-plane displacement equal to zero, or a whirling state with the out-of-plane displacement different from zero. Possible solutions are found both analytically and numerically. Next, the chord elongation is modelled as a narrow-banded Gaussian stochastic process, and it is shown that all the indicated harmonic solutions now become instable with probability one. Instead, the cable jumps randomly back and forth between the two in-plane and the whirling mode of vibration. A theory for determining the probability of occupying either of these modes at a certain time is derived based on a homogeneous, continuous time three states Markov chain model. It is shown that the transitional probability rates can be determined by first-passage crossing rates of the envelope process of the chord wise component of the support point motion relative to a safe domain determined from the harmonic analysis of the problem.     

Rate coefficients for reactions of OH radicals with CH3D,CH2D2, CHD3, and CD4

Fourier transform infrared (FTIR) smog chamber techniques were used to investigate the atmospheric chemistry of the isotopologues of methane. Relative rate measurements were performed to determine the kinetics of the reaction of the isotopologues of methane with OH radicals in cm³ molecule⁻¹ s⁻¹ units: k(CH₃D + OH) = (5.19 ± 0.90) × 10⁻¹⁵, k(CH₂D₂ + OH) = (4.11 ± 0.74) × 10⁻¹⁵, k(CHD₃ + OH) = (2.14 ± 0.43) × 10⁻¹⁵, and k(CD₄ + OH) = (1.17 ± 0.19) × 10⁻¹⁵ in 700 Torr of air diluent at 296 ± 2 K. Using the determined OH rate coefficients, the atmospheric lifetimes for CH_4–xD_x (x = 1–4) were estimated to be 6.1, 7.7, 14.8, and 27.0 years, respectively. The results are discussed in relation to previous measurements of these rate coefficients.