As an important class of transparent polyolefins, cyclic olefin copolymers (COCs) exhibit a wide range of properties, from soft (low cyclic unit content in a random copolymer) to hard (high cyclic unit content in a random copolymer) thermoplastics. A higher cyclic unit content in a random copolymer results in increased rigidity and heat resistance, but at the expense of material toughness, especially under low temperature. To achieve a trade-off, block-type COCs composed of well-defined hard-soft and hard-soft-hard segments with high molecular weights (M_n > 200 kDa) and relatively narrow molecular weight distributions (M_w/M_n < 1.42) were prepared via quasi-living copolymerization. Compared to random copolymers, di-block COCs retained satisfactory heat resistance and optical transparency and exhibited superior tensile properties (tensile strength: 56.2 MPa, elongation at break: 254.4%), while tri-block COCs with the same hard-soft segments and an additional hard segment exhibited even better tensile properties, achieving a tensile strength of 67.3 MPa, elongation at break of 286.9%, all while maintaining high optical transmittance (> 90%). Even at temperatures below 0 °C, the tri-block copolymers EN₅₂-b-EN₁₉-b-EN₄₆ demonstrated a satisfactory tensile strength (> 64.0 MPa) and elongation at break (> 65.6%), highlighting the advantages of the alternating hard-soft segment structural design in COCs.

Vicinal all-carbon quaternary stereocenters are widely present in natural products and bioactive molecules. However, the construction of such motif in one step from readily available starting materials remains a significant challenge. Herein, we report a phosphine-catalyzed divergent γ,γ- and ε,γ-umpolung domino addition of bisoxindoles with allenoates. This method serves as a practical tool for the concise synthesis of a series of bisoxindole derivatives bearing sterically hindered vicinal all-carbon quaternary stereocenters under mild reaction conditions. The applicability of this novel method was demonstrated with the gram-scale synthesis of three known advanced intermediates for the total syntheses of calycanthine, chimonanthine and folicanthine.

Chiral perovskites provide an ideal platform for the construction of linear and nonlinear optical materials due to their diverse chemical variability, structural tunability, and intrinsic non-centrosymmetricity which have broad application prospects for next-generation optoelectronic devices. In this work, a pair of 1D chiral lead halide perovskites (R/S-4MeOPEA)PbCl₃ (4MeOPEA = (4-methoxyphenyl)ethylamine) were synthesized, and characterized systematically. Crystal structure analysis revealed that the one-dimensional (1D) inorganic chain formed by face-shared lead chloride octahedra was separated by the chiral organic spacers. The distorted octahedra endows them with broadband bluish-white light emission centered covering the range 350—700 nm with a width of 104 nm. In addition, the highly anisotropic second-harmonic generation (SHG) with a near unity polarization ratio was observed. This work presents a fresh example of 1D chiral perovskite with exotic linear and nonlinear optical properties, which could provide a new footstone for further optoelectronic devices.

An atmospheric-oxygen-mediated four-component reaction was developed for the divergent synthesis of pyrazolo[1,5-a]pyrimidine and pyrazolo[3,4-b]pyridine derivatives from readily available alcohols and 3-aminopyrazoles. In this transformation, atmospheric oxygen serves as the green oxidant, promoting alcohols as equivalent aldehydes for the synthesis of four types of N-containing heterocycles (> 40 examples). Remarkably, the transformation features metal-free and molecular diversity.

Binuclear platinum(III) complexes were known for their high index of antitumor activity and a lower associated nephrotoxicity. However, the chemistry and reactivity of binuclear platinum(III) compounds have not yet been explored to the same extent as those of platinum(II) and platinum(IV) species. Here, we reported the first binuclear platinum-catalyzed hydrosilylation, monoborylation and diboration reaction of alkynes with excellent selectivity and yield. Moreover, the mechanistic investigation by control experiments, kinetic isotope effect (KIE) study, Hammett plots, NMR spectra, UV−vis spectra, and X-ray photoelectron spectroscopy (XPS) analysis reveal that the Pt(III)₂-catalyzed reactions pass through a σ-bond metathesis process rather than the two-electron redox processes of the mononuclear platinum catalysis. Moreover, there are two different rate-determining steps, in which the migratory insertion step dominates the rate of electron deficient substates and σ-bond metathesis process dominates electron rich counterparts, respectively.

A series of sulfonatopropoxylated cucurbit[8]uril derivatives (SPECB8s) with water-solubility ranging from 344 mmol/L to 360 mmol/L have been prepared. One of the derivatives SPE_5.5CB8 bearing an average of 5.5 sulfonatopropoxy side chains has been revealed to display high biocompatibility, with maximum tolerated dose being as high as 2500 mg/kg for mice. Phase solubility diagram investigations illustrate that SPE_5.5CB8 can solubilize eighteen poorly soluble drugs and, for fifteen of them including remdesivir, its solubilization efficiency is higher than that of Captisol, the most widely used β-cyclodextrin-derived excipient for drug formulation. Moreover, the improved solubilization for remdesivir, which is formulated by Captisol for clinical use, can lead to important increase of its antiviral activity as compared with Captisol.

Organic-inorganic hybrid perovskites (OIHPs) offer precise control over material properties through the substitution of organic cations and halogens. In this study, two OIHPs, [(C₆H₁₀P)(n-BA)]Sb₂X₉ ([C₆H₁₀P]⁺ = [Me₃PCH₂CH₂CH₃]⁺, [n-BA]⁺ = n-butylamine cation, X = I (1), Br (2)), were synthesized by varying halogens within a mixed-cation system. The halogen substitution induced a shift from compound 1, which remains stable without phase transitions, to compound 2, which undergoes a ferroelastic phase transition (mmmF2/m). Compound 1 crystallizes in the non-centrosymmetric Pca2₁ space group and demonstrates a second harmonic generation (SHG) response, while compound 2 displays elasticity in nanoindentation tests. Halogen substitution alters Sb—X bond lengths, inducing structural distortions in the inorganic framework and influencing the spatial configuration of organic cations and inorganic anions. These changes lead to distinct crystallization behaviors, resulting in different physical properties for compounds 1 and 2. This work contributes to the development of multifunctional materials based on halogen regulation in mixed-cation OIHPs.

Monitoring and analyzing expression levels of multiple biomarkers in biological samples can improve disease risk prediction and guide precision medicine but suffers from high cost and being time-consuming. Here, we construct a fast molecular classifier based on freeze-thaw cycling that implements an in silico support vector machine (SVM) classifier model at the molecular level with a panel of disease-related biomarkers expression patterns for rapid disease diagnosis. The molecular classifier employs DNA reaction networks as the computing module and repeated dehydration and concentration process as the driving force to implement a set of simplified mathematical operations (such as multiplication, summation and subtraction) for efficient classification of complex input patterns. We demonstrate that the fast DNA-based molecular classifier enables precise cancer diagnosis within a short turnaround time in synthetic samples compared to those of free diffusion classifiers. We envision that this all-in-one molecular classifier will create more opportunities for inexpensive, accurate, and rapid disease diagnosis, prognosis and therapy, particularly in emergency departments or the point of care.

This study highlights the innovative use of increased rare earth elements to enhance the dielectric properties of materials and devices. The AlOC-129Ln series, features the highest number of rare earth dopants in aluminum oxo clusters to date. The trivalent ions in AlOC-129Ln impart a high dipole moment, significantly elevating the dielectric constant (k) of the doped polymer films. AlOC-129Ce, in particular, exhibits the largest molecular size, which enhances interfacial effects and achieves a relative dielectric constant four times greater than that of undoped polymers and 1.5 times higher than those with single rare earth dopants. The substantial molecular size (~2.5 nm) and robust charge scattering and trapping capabilities of AlOC-129Ln reduce dielectric loss by up to 50% at high frequencies. Additionally, its excellent solution processability enhances breakdown strength by 147%, ensuring superior electrical stability. This research demonstrates the versatility of the cluster doping strategy in effectively balancing dielectric constant and loss, unveiling the promising potential of solution-processable cluster materials in electronic devices.

Chiral proton conductive single-molecule magnets (SMMs) are multifunctional molecular materials that can combine conductor, magnet, and chirality at the nanoscale, but there are still significant challenges to their synthesis. Herein, the hydrazone Schiff base ligand (E)-N′-(2-hydroxybenzylidene)-3-aminopyrazine-2-carbohydrazide (H₂L_Schiff) and the homochiral ligands (R)-(+)-chlocyphos/ (S)-(−)-chlocyphos (R-HL)/(S-HL) were chosen to assemble a pair of Dy₂ enantiomers [Dy₂(R-L)₂(L_Schiff)₂(DMA)₂]·2.5H₂O (R-1) (DMA = N,N-dimethylacetamide) and [Dy₂(S-L)₂(L_Schiff)₂(DMA)₂]·2.5H₂O (S-1) at room temperature. Magnetic investigation indicated that they are field-induced SMMs, with a U_eff/k value of 42.2 K at 1000 Oe, and there is ferromagnetic coupling within the molecule; these magnetic properties may be explained by the ab initio calculations. The presence of a hydrogen bonding network confers the enantiomers proton conductivities. Moreover, R-1 and S-1 show prominent magnetic circular dichroism (MCD) effects at room temperature.

Allenes, characterized by their cumulated carbon–carbon double bonds, have emerged as indispensable synthons in the construction of complex natural products. Their unique reactivity and stereochemical properties render allenes a powerful tool for the efficient and streamlined total synthesis of structurally intricate natural products. This review comprehensively summarizes the total syntheses of complex natural products involving allene cycloaddition reactions reported over the past decade (2014—2024). Among the nearly 20 total syntheses reviewed, the [2+1], [2+2], [3+2], [4+2], [4+3], [5+1] and [2+2+1] cycloaddition reactions of allenes are the most important transformations to construct the key skeleton. This is because of their ability to form multiple bonds in a single step with high atom economy, stereoselectivity, and regioselectivity, often under mild conditions. The strategic application of these reactions in forming key carbon–carbon bonds and controlling stereochemistry makes them practical for the efficient assembly of complex molecular frameworks. With the ongoing exploration of methods for allene generation, particularly the enantioselective approaches, and the continued discovery of novel cyclization reactions of allenes, allene chemistry will maintain its crucial and indispensable role in the total synthesis of natural products.

The preparation and resolution of chiral molecules hold significant importance in scientific and industrial domains, such as drug development and manufacturing. In recent years, chiral porous frameworks have attracted increasing attention in asymmetric catalysis and enantiomer resolution due to their excellent performance. The metal-organic frameworks (MOFs), covalent organic frameworks (COFs), porous organic cages (POCs), and porous coordination cages (PCCs) are important representative of the porous framework family. Significantly, chirality can be easily introduced into these framework materials through simple bottom-up or post-modification methods, thereby promoting their applications related to chirality. In this review, we systematically summarize the synthesis strategies of four classes of chiral framework materials and their applications in asymmetric catalysis and enantiomeric resolution. Finally, we present some perspectives on the future development in chiral porous frameworks.