Supramolecular Tuning Enables Selective Oxygen Reduction Catalyzed by Cobalt Porphyrins for Direct Electrosynthesis of Hydrogen Peroxide

We report a supramolecular strategy for promoting the selective reduction of O₂ for direct electrosynthesis of H₂O₂. We utilized cobalt tetraphenylporphyrin (Co-TPP), an oxygen reduction reaction (ORR) catalyst with highly variable product selectivity, as a building block to assemble the permanently porous supramolecular cage Co-PB-1(6) bearing six Co-TPP subunits connected through twenty-four imine bonds. Reduction of these imine linkers to amines yields the more flexible cage Co-rPB-1(6). Both Co-PB-1(6) and Co-rPB-1(6) cages produce 90–100 % H₂O₂ from electrochemical ORR catalysis in neutral pH water, whereas the Co-TPP monomer gives a 50 % mixture of H₂O₂ and H₂O. Bimolecular pathways have been implicated in facilitating H₂O formation, therefore, we attribute this high H₂O₂ selectivity to site isolation of the discrete molecular units in each supramolecule. The ability to control reaction selectivity in supramolecular structures beyond traditional host–guest interactions offers new opportunities for designing such architectures for a broader range of catalytic applications.     

Synthesis and Optoelectronic Properties of a Quinoxalino-Phenanthrophenazine (QPP) Extended Tribenzotriquinacene (TBTQ)

A six-step synthesis towards a tribenzotriquinacene (TBTQ) bearing three quinoxalinophenanthrophenazine (QPP) units is presented. The optoelectronic properties are investigated and the effect of the three-dimensional arrangement of the individual QPP planes is examined using optical spectroscopy, electrochemical analysis and quantum-chemical calculations.     

Total Syntheses of (−)‐Huperzine Q and (+)‐Lycopladines B and C

Utilizing a late‐stage enamine bromofunctionalization strategy, the twelve‐step total synthesis of (?)‐huperzine Q was accomplished. Furthermore, the first total syntheses of (+)‐lycopladines B and C are described. An unprecedented X‐ray crystal structure of an unusual epoxyamine intermediate is also reported, and the synthetic application of this intermediate in natural product synthesis is demonstrated.     

实际光栅系统分辨本领的实验验证

本文通过光栅衍射实验对钠光双线结构的观测，验证了实际光栅系统的分辨本领。     

Parameter uncertainty, sensitivity analysis and prediction error in a water-balance hydrological model

Analysis of uncertainty is often neglected in the evaluation of complex systems models, such as computational models used in hydrology or ecology. Prediction uncertainty arises from a variety of sources, such as input error, calibration accuracy, parameter sensitivity and parameter uncertainty. In this study, various computational approaches were investigated for analysing the impact of parameter uncertainty on predictions of streamflow for a water-balance hydrological model used in eastern Australia. The parameters and associated equations which had greatest impact on model output were determined by combining differential error analysis and Monte Carlo simulation with stochastic and deterministic sensitivity analysis. This integrated approach aids in the identification of insignificant or redundant parameters and provides support for further simplifications in the mathematical structure underlying the model. Parameter uncertainty was represented by a probability distribution and simulation experiments revealed that the shape (skewness) of the distribution had a significant effect on model output uncertainty. More specifically, increasing negative skewness of the parameter distribution correlated with decreasing width of the model output confidence interval (i.e. resulting in less uncertainty). For skewed distributions, characterisation of uncertainty is more accurate using the confidence interval from the cumulative distribution rather than using variance. The analytic approach also identified the key parameters and the non-linear flux equation most influential in affecting model output uncertainty.     

Smoothness and absolute convergence of Fourier series in compact totally disconnected groups

In this paper we study in the context of compact totally disconnected groups the relationship between the smoothness of a function and its membership in the Fourier algebra $\text{G}$G. Specifically, we define a notion of smoothness which is natural for totally disconnected groups. This in turn leads to the notions of Lipshitz condition and bounded variation. We then give a condition on α which if satisfied implies Lip_α(G) ? $\text{R}$(G). On certain groups this condition becomes: $\text{α >}\text{1}\text{2}$ (Bernstein's theorem). We then give a similar condition on α which if satisfied implies that Lip_α(G) ∈ BV(G) ? $\text{R}$(G). On certain groups this condition becomes: α > 0 (Zygmund's theorem). Moreover we show that $\text{α >}\text{1}\text{2}$ is best possible by showing that $\text{Lip}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{(G)}$ ? $\text{R}$(G).     

Total Synthesis of Diverse Tetramic Acid Bearing cis-Decalin Natural Products

We report herein the first total syntheses of four natural antibiotics, vermisporin, PF1052/AB4015-A, AB4015-L, AB4015-B, and one hydrogenated natural product derivative, AB4015-A2, that all feature a tetramic acid bearing cis-decalin ring. The construction of the functionalized cis-decalin ring was achieved by a diastereoselective intramolecular Diels-Alder (IMDA) reaction, which proceeded via a rare endo-boat transition state. Through an intramolecular neighboring-group-oriented strategy, the sterically hindered epoxy group in vermisporin, PF1052/AB4015-A and AB4015-L was installed efficiently. A one-pot aminolysis/Dieckmann condensation cascade using l -amino acid derivatives afforded the desired tetramic acid structure. The total synthesis led to the unambiguous verification of the absolute configuration of these natural products.     

Total Synthesis and Structural Reassignment of Aspergillomarasmine A

The increase and spread of Gram‐negative bacteria that resistant are to almost all currently available β‐lactam antibiotics is a major global health problem. The primary cause for drug resistance is the acquisition of metallo‐β‐lactamases such as metallo‐β‐lactamase‐1 (NDM‐1). The fungal natural product aspergillomarasmine A (AMA), a fungal natural product, is an inhibitor of NDM‐1 and has shown promising in vivo therapeutic potential in a mouse model infected with NDM‐1‐expressing Gram‐negative bacteria. The first total synthesis and stereochemical configuration reassignment of aspergillomarasmine A is reported. The synthesis highlights a flexible route and an effective strategy to achieve the required oxidation state at a late stage. This modular route is amenable to the efficient preparation of analogues for the development of metallo‐β‐lactamase inhibitors to potentiate β‐lactam antibiotics.     

Selective Transformation of Norbornadiene into Functionalized Azaheterocycles and β-Amino Esters with Stereo- and Regiocontrol

Novel functionalized azaheterocycles with multiple chiral centers have been accessed from readily available norbornene β-amino acids or β-lactams across a stereocontrolled synthetic route, based on ring-opening metathesis (ROM) of the staring unsaturated bicyclic amino esters, followed by selective cyclization through ring-closing metathesis (RCM). The RCM transformations have been studied under various experimental conditions to assess the scope of conversion, catalyst, yield, and substrate influence. The structure of the starting norbornene β-amino acids predetermined the structure of the new azaheterocycles, and the developed synthetic route took place with the conservation of the configuration of the chiral centers.     

Generalized Rudin-Shapiro Systems

The classical Rudin–Shapiro construction produces a sequence of polynomials with ±1 coefficients such that on the unit circle each such polynomial P satisfies the "flatness" property ||P||_∞ ≤ √2||P||₂. It is shown how to construct blocks of such flat polynomials so that the polynomials in each block form an orthogonal system. The construction depends on a fundamental generating matrix and a recursion rule. When the generating matrix is a multiple of a unitary matrix, the flatness, orthogonality, and other symmetries are obtained. Two different recursion rules are examined in detail and are shown to generate the same blocks of polynomials although with permuted orders. When the generating matrix is the Fourier matrix, closed-form formulas for the polynomial coefficients are obtained. The connection with the Hadamard matrix is also discussed.