Latest ArticlesMannich-type reactions are a widely used method for the synthesis of amines due to the readily availability of nucleophiles and electrophiles. However, the inclusion of alkylarenes instead of active carbon pronucleophiles such as aldehydes and ketones in these addition reactions has been a challenge due to the inherent difficulty of benzylic deprotonation. In this study, we present a novel approach for the construction of N-sulfonyl amines via rhodium-catalyzed addition of unbiased benzylic CH bonds to cyclic N-sulfonyl ketamines through π-coordination. This strategy enables the synthesis of a diverse range of N-sulfonyl amines, and subsequent diversification of the addition products showcases the synthetic potential of this protocol.
Small-molecule drugs are widely used in daily life. There are still issues with the current industrial synthesis techniques for small-molecule drugs, such as the use of expensive metal catalysts, convoluted reaction processes, and non-recyclable catalysts. The benefits of photocatalytic organic synthesis over conventional techniques are mild conditions, environmental friendliness, and great selectivity. Porous framework materials can precisely modulate catalytic sites’ electronic state and ligand structure to improve photocatalytic performance. In particular, MOFs, COFs and PCCs based photocatalysts have received extensive research interest due to their unique morphology, structural adjustability, high photocatalytic performance, unique recyclability, excellent chemical stability, easy synthesis and low cost. Therefore, a key area for future research is the development of porous framework materials as photocatalysts for the synthesis of small-molecule drugs or drug precursors.
Photothermal therapy (PTT) is a cutting-edge cancer treatment that can kill cancer cells in hypoxic environments without relying on oxygen. Seeking of the ideal photothermal agents with a high absorption coefficient in the near-infrared region, and a high excellent photothermal conversion efficiency is of great significance. Sulfone-Rhodanmine dye has showed an impressive absorption wavelength over 700 nm, but suffered from a stability issue. In this study, we synthesized five sulfone rhodamines and investigated the substitution effects on stability. SO2R2 showed high stability and strong absorbance at 714 nm with an excellent photothermal conversion efficiency of 53.06%, making it suitable for accurate photoacoustic imaging-guided photothermal therapy in vivo.
Molecular sieve catalysts, owing to their unique chemical properties, are widely used as catalysts among various catalytic reactions. Abundant Brønsted acid sites in molecular sieve catalysts usually enable active components to disperse well on the catalyst surface, and help to adsorb a large number of gas molecules to achieve maximum catalytic performance. Therefore, a variety of molecular sieve catalysts have been developed and used in the selective catalytic reduction of NOx by NH3 (NH3-SCR). For example, Cu molecular sieve catalysts such as Cu-SSZ-13 and Cu-SAPO-34 with wide temperature windows and stable structure are considered and applied as commercial catalysts for NOx removal in diesel vehicles for a long time. Although molecular sieve catalysts possess many advantages, they still cannot avoid the serious deactivation caused by various factors in practical applications. In this review, reasons leading to the deactivation of molecular sieve catalysts for NOx reduction in actual working conditions were concluded. The deactivation mechanisms of molecular sieve catalysts for NOx reduction were analyzed and the corresponding anti-deactivation strategies were summarized. Finally, challenges and prospects of molecular sieve catalysts for NOx reduction were also proposed.
The design and synthesis of novel photocatalyst with self-temperature control function is an important topic in the field of advanced environmental functional materials. In this work, submicron-sized magnetic phase change microcapsules composed of paraffin core and Fe3O4-loaded silica shell are prepared, on which the Bi2WO6 crystals is grown in situ through hydrothermal reaction to obtain novel magnetic phase-change-microcapsule-supported Bi2WO6 catalyst (MP@FS/BWO). The MP@FS/BWO has a paraffin encapsulation ratio of 57.1%, and the phase change enthalpy of 105.1 J/g in a temperature range of 50–60 ℃, which endows the MP@FS/BWO with a certain self-temperature regulation ability. MP@FS/BWO shows excellent catalytic performance in the decomposition of rhodamine B under the simulated sunlight irradiation. After the light source is turned off, it still has good catalytic ability by maintaining high temperature due to its temperature control function based on the phase transition process. The MP@FS/BWO can be easily recycled by magnetic separation and shows good structural stability and reusability. This work provides a new idea for the development of long-effect and energy-saving outdoor photocatalysts.
In 2022, The MOE Key Laboratory of Macromolecular Synthesis and Functionalization in Zhejiang University had achieved several important results. First, a series of well-defined dinuclear organoboron catalysts were developed to precisely control the enchainment of ether and carbonate segments during the copolymerization of CO2 and epoxides. Second, polyester had been synthesized through cationic copolymerization of cyclic anhydride. Third, ring-opening polymerization of carbon dioxide based valerolactone had been achieved, revealing the prospect of 3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one (EVL) in utilizing CO2 and synthesizing functional polymers. Fourth, machine learning methods have been applied to biomaterial research, enabling high-throughput screening of functional biomaterial surfaces for implantable devices, and searching for potent antimicrobial peptides in whole combinatorial peptide libraries. Fifth, methods of characterization of biomacromolecule RNA transcription and manipulation of nucleoside modification were developed. Sixth, artificial enzymes-armed Bifidobacterium Longum probiotics were established to tune down gut inflammation. Seventh, three-dimensional (3D) printing technologies were used to engineer tough supramolecular hydrogels. Eighth, hydroplastic foaming graphene frameworks for acoustic and conductive polymer composites were provided for application. Ninth, aggregate photophysics about the nature of through-space interactions (TSIs) and manipulating their strength in small molecules with non-conjugated structure had been elucidated. Tenth, the forming mechanism of a newfound nested texture in poly(l-lactic acid) (PLLA) spherulitic films had been revealed. Finally, the isotropically dyeing mechanism of KDP single crystals grown from hydrogels have been explored. The related works are reviewed in this paper.
Nitroaromatic hydrogenation catalysis without precious metals remains a longstanding challenge. The rate of electron transfer is the crucial factor affecting hydrogenation catalysis. Herein, an ionic Cd-based metal-organic framework (I-Cd-MOF) exhibiting a unique structure with one-dimensional (1D) opening nanochannels and good electron transfer ability was synthesized for catalyzing hydrogenation of 4-nitrophenol (4-NP). The catalytic activity of the unique I-Cd-MOF without noble metals is detected, which is higher than most reported noble metal catalysts. Remarkably, the reaction rate of I-Cd-MOF (4.28 min−1) is about 47.6 times higher than that of the Cd-based neutral MOF (N-Cd-MOF) with the similar crystalline structure. Liquid chromatograph mass spectrometer (LC-MS) and theoretical results demonstrate that 4-NP and five intermediates are stabilized in the channels of I-Cd-MOF, which increases the possibility of contact with H* and H2 generated at the Cd sites. The I-Cd-MOF was extended to other nitroaromatic hydrogenation catalysis, which still displays excellent activity. More importantly, the I-MOF@Filter membrane was successfully constructed for continuous hydrogenation catalytic reactions, which maintains a high catalytic performance after 7 cycles of recycling without washing. This work fills in the application of the I-MOFs in hydrogenation catalytic reactions and provides an effective way for the rapid and green degradation of nitroaromatic compounds.
Matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS) plays an indispensable role in analyzing protein covalent structures. The reliable identification of amino acid residues and modifications relies on the mass accuracy, which is highly dependent on calibration. However, the accuracy provided by the currently available calibrants still needs further improvement in terms of compatibility with multiple tandem MS modes or ion polarity modes, calibratable range, and minimizing suppression of and interference with analyte signals. Here aiming at developing a versatile calibrant to solve these problem, we designed a synthetic peptide format of calibrant R(GDP) (referred to as "Gly-Asp-Pro, GDP") according to the chemical natures of amino acids and polypeptide fragmentation rules in tandem MS. With four types of amino acid residues selected and arranged through rational designs, a GDP peptide produces highly regulated fragments that give rise to evenly spaced signals in each tandem MS mode and is compatible with both positive and negative ion modes. In internal calibration, its regulated fragmentation pattern minimizes interference with analyte signals, and using a single peptide as the input minimizes suppression of the analyte signals. As demonstrated by analyses of proteins including monoclonal antibody and Aβ-42, these features allowed significant increase of the mass accuracy and precision, which improved sequence coverage and sequence resolution in sequence analyses (including de novo sequencing). This rational design strategy may also inspire further development of synthetic calibrants that benefit structural analysis of biomolecules.
N1-methyladenosine (m1A) is an important RNA modification that functions in various biological processes by interacting with cellular proteins. However, the binding proteins of N1-methyldeoxyadenosine (1mdA) in DNA remain largely unknown. Herein, we employed a quantitative proteomics strategy to identify the potential binding proteins of 1mdA in human cells. Our results revealed that serine‑threonine kinase receptor-associated protein (STRAP) can bind to 1mdA-carrying DNA. We further demonstrated that STRAP participates in alkylating agent-induced DNA damage response and can promote the repair of 1mdA embedded in DNA. Moreover, we investigated the effects of STRAP on 1mdA-induced perturbation in transcription using a shuttle vector- and next-generation sequencing-based assay, and found that STRAP is involved in the transcriptional bypass of 1mdA in human cells. Together, our study revealed STRAP as a novel 1mdA-binding protein in human cells and provided new insight into the biological implications of STRAP and 1mdA modification in human diseases.
Macrocyclic materials have attracted much attention due to their particular chemical and physical properties. Herein we report the precise synthesis and characterization of a new bismacrocycle structure base on cycloparaphenylene (CPP) and pillar[5]arene, named cycloparaphenylene-pillar[5]arenes (CPPn[5]). The bismacrocycle was fully characterized by NMR and HR-MS. The photophysical properties of CPPn[5] were investigated by UV–vis, and the maximum absorption peak was located at 331 nm, which was consistent with density functional theory (DFT) calculations. The fluorescence spectrum was further studied and the emission peak was maximized at 458 nm. The computational results indicate the strain energy of CPPn[5] is 27.80 kcal/mol and the HOMO-LUMO gap is 3.39 eV Notably, CPPn[5] showed interesting supramolecular properties.
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