<Emphasis Type="Italic">Tetra</Emphasis>-armed conjugated microporous polymers for gas adsorption and photocatalytic hydrogen evolution

Two novel tetra-armed conjugated microporous polymers with different geometries have been designed and synthesized via Suzuki-Miyaura cross coupling polycondensation. Both polymers are stable in various organic solvents tested and are thermally stable. The pyrene-containing polymer of PrPy with the rigid pyrene unit shows a higher Brunauer-Emmet-Teller specific surface area of 1219 m² g^?1 than the tetraphenylethylene-containing polymer of PrTPE (770 m² g^?1), which leads to a high CO₂ uptake ability of 3.89 mmol g^?1 at 1.13 bar/273 K and a H₂ uptake ability of 1.69 wt% at 1.13 bar/77 K. The photocatalytic hydrogen production experiments revealed that PrPy also shows a better photocatalytic performance than PrTPE due to the higher conjugation degree and planar structure, the broader UV-visible (UV-Vis) absorption, the lower photoluminescence lifetime, and the higher specific surface area.     

Structural insight into the inactivation of <Emphasis Type="Italic">Mycobacterium tuberculosis</Emphasis> non-classical transpeptidase Ldt<Subscript>Mt2</Subscript> by biapenem and tebipenem

Background

The carbapenem subclass of β-lactams is among the most potent antibiotics available today. Emerging evidence shows that, unlike other subclasses of β-lactams, carbapenems bind to and inhibit non-classical transpeptidases (L,D-transpeptidases) that generate 3 → 3 linkages in bacterial peptidoglycan. The carbapenems biapenem and tebipenem exhibit therapeutically valuable potencies against Mycobacterium tuberculosis (Mtb).

Results

Here, we report the X-ray crystal structures of Mtb L,D-transpeptidase-2 (Ldt_Mt2) complexed with biapenem or tebipenem. Despite significant variations in carbapenem sulfur side chains, biapenem and tebipenem ultimately form an identical adduct that docks to the outer cavity of Ldt_Mt2. We propose that this common adduct is an enzyme catalyzed decomposition of the carbapenem adduct by a mechanism similar to S-conjugate elimination by β-lyases.

Conclusion

The results presented here demonstrate biapenem and tebipenem bind to the outer cavity of Ldt_Mt2, covalently inactivate the enzyme, and subsequently degrade via an S-conjugate elimination mechanism. We discuss structure based drug design based on the findings and propose that the S-conjugate elimination can be leveraged to design novel agents to deliver and locally release antimicrobial factors to act synergistically with the carbapenem carrier.

     

An alternating direction and projection algorithm for structure-enforced matrix factorization

Structure-enforced matrix factorization (SeMF) represents a large class of mathematical models appearing in various forms of principal component analysis, sparse coding, dictionary learning and other machine learning techniques useful in many applications including neuroscience and signal processing. In this paper, we present a unified algorithm framework, based on the classic alternating direction method of multipliers (ADMM), for solving a wide range of SeMF problems whose constraint sets permit low-complexity projections. We propose a strategy to adaptively adjust the penalty parameters which is the key to achieving good performance for ADMM. We conduct extensive numerical experiments to compare the proposed algorithm with a number of state-of-the-art special-purpose algorithms on test problems including dictionary learning for sparse representation and sparse nonnegative matrix factorization. Results show that our unified SeMF algorithm can solve different types of factorization problems as reliably and as efficiently as special-purpose algorithms. In particular, our SeMF algorithm provides the ability to explicitly enforce various combinatorial sparsity patterns that, to our knowledge, has not been considered in existing approaches.     

A new construction of the Clifford-Fourier kernel

In this paper, we develop a new method based on the Laplace transform to study the Clifford-Fourier transform. First, the kernel of the Clifford-Fourier transform in the Laplace domain is obtained. When the dimension is even, the inverse Laplace transform may be computed and we obtain the explicit expression for the kernel as a finite sum of Bessel functions. We equally obtain the plane wave decomposition and find new integral representations for the kernel in all dimensions. Finally we define and compute the formal generating function for the even dimensional kernels.     

Optimal mean–variance asset-liability management with stochastic interest rates and inflation risks

This paper considers an optimal asset-liability management problem with stochastic interest rates and inflation risks under the mean–variance framework. It is assumed that there are \(n+1\) assets available in the financial market, including a risk-free asset, a default-free zero-coupon bond, an inflation-indexed bond and \(n-2\) risky assets (stocks). Moreover, the liability of the investor is assumed to follow a geometric Brownian motion process. By using the stochastic dynamic programming principle and Hamilton–Jacobi–Bellman equation approach, we derive the efficient investment strategy and efficient frontier explicitly. Finally, we provide numerical examples to illustrate the effects of model parameters on the efficient investment strategy and efficient frontier.     

Selective CO2-to-C2H4 Photoconversion Enabled by Oxygen-Mediated Triatomic Sites in Partially Oxidized Bimetallic Sulfide

Selective CO₂ photoreduction into C₂ fuels under mild conditions suffers from low product yield and poor selectivity owing to the kinetic challenge of C−C coupling. Here, triatomic sites are introduced into bimetallic sulfide to promote C−C coupling for selectively forming C₂ products. As an example, FeCoS₂ atomic layers with different oxidation degrees are first synthesized, demonstrated by X-ray photoelectron spectroscopy and X-ray absorption near edge spectroscopy spectra. Both experiment and theoretical calculation verify more charges aggregate around the introduced oxygen atom, which enables the original Co−Fe dual sites to turn into Co−O−Fe triatomic sites, thus promoting C−C coupling of double *COOH intermediates. Accordingly, the mildly oxidized FeCoS₂ atomic layers exhibit C₂H₄ formation rate of 20.1 μmol g⁻¹ h⁻¹, with the product selectivity and electron selectivity of 82.9 % and 96.7 %, outperforming most previously reported photocatalysts under similar conditions.     

Synthesis of Multifluoromethylated γ-Sultines by a Photoinduced Radical Addition–Polar Cyclization

Despite the significance of sultines in synthesis, medicine, and materials science, the chemistry of sultines has remained unexplored due to their inaccessibility. Herein, we demonstrate the development of a photoredox-catalyzed multifluoromethyl radical addition/SO₂ incorporation/polar cyclization cascade approach to multifluoromethylated γ-sultines. The reactions proceed by single electron transfer induced multifluoromethyl radical addition to an alkene followed by SO₂ incorporation, and single-electron reduction for polar 5-exo-tet cyclization. Key to the success of the protocol is the use of easily oxidizable multifluoroalkanesulfinates as bifunctional reagents. The reactions proceed with excellent functional-group tolerance to deliver γ-sultines in moderate to excellent yields.     

A Spiro Phosphamide Catalyzed Enantioselective Proton Transfer of Ylides in a Free Carbene Insertion into N−H Bonds

Free carbene readily causes multiple side reactions due to its high energy, thus its asymmetric transformation is very difficult. We present here our findings of high-pK_a Brønsted acid catalysts that enable free carbene insertion into N−H bonds of amines to prepare chiral α-amino acid derivatives with high enantioselectivity. Under irradiation with visible light, diazo compounds produce high-energy free carbenes that are captured by amines to form free ylide intermediates, and then the newly designed high-pK_a Brønsted acids, chiral spiro phosphamides, promote the proton transfer of ylides to afford the products. Computational and kinetic studies uncover the principle for the rational design of proton-transfer catalysts and explain how the catalysts accelerate this transformation and provide stereocontrol.     

Low Bandgap 2D Perovskite Single Crystal with Anomalous-large Charges/ions Collection Ratio for Ultra-sensitive and Stable X-ray Detectors

The low-dimensional halide perovskites have attracted increasing attention due to their improved moisture stability, reduced defects, and suppressed ions migration in many optoelectronic devices such as solar cells, light-emitting diodes, X-ray detectors, and so on. However, they are still limited by their large band gap and short charge carriers’ diffusion length. Here, we demonstrate that the introduction of metal ions into organic interlayers of two-dimensional (2D) perovskite by cross-linking the copper paddle-wheel cluster-based lead bromide ([Cu(O₂C−(CH₂)₃−NH₃)₂]PbBr₄) perovskite single crystals with coordination bonds can not only significantly reduce the perovskite band gap to 0.96 eV to boost the X-ray induced charge carriers, but can also selectively improve the charge carriers’ transport along the out-of-plane direction and blocking the ions motion paths. The [Cu(O₂C−(CH₂)₃−NH₃)₂]PbBr₄ single-crystal device can reach a record charges/ions collection ratio of 1.69×10¹⁸±4.7 % μGy_air⁻¹ s, and exhibit a large sensitivity of 1.14×10⁵±7% μC Gy_air⁻¹ cm⁻² with the lowest detectable dose rate of 56 nGy_air s⁻¹ under 120 keV X-rays irradiation. In addition, [Cu(O₂C−(CH₂)₃−NH₃)₂]PbBr₄ single-crystal detector exposed to the air without any encapsulation shows excellent X-ray imaging capability with long-term operational stability without any attenuation of 120 days.     

Nickel-Catalyzed Markovnikov-Selective Hydrodifluoromethylation of Alkynes Using BrCF2H

A Markovnikov-selective hydrodifluoromethylation of alkynes with BrCF₂H via nickel catalysis is described. This protocol proceeds via a migratory insertion of nickel hydride to alkyne followed by a CF₂H-coupling, enabling straightforward access to diverse branched CF₂H-alkenes with high efficiency and exclusive regioselectivity. The mild condition applies to a wide array of aliphatic and aryl alkynes with good functional group compatibility. Mechanistic studies are presented to support the proposed pathway.