Enhanced drug delivery can improve the therapeutic efficacy of drugs and help overcome side effects. However, many reported drug‐delivery systems are too complex and irreproducible for practical use. ...In this work, the design of a hypoxia‐responsive molecular container based on calixarene, called CAC4A, which presents a significant advance in practical, hypoxia‐targeted drug‐delivery, is reported. CAC4A enables a wide variety of clinical drugs to be quantitatively loaded to improve their solubility and stability, as well as enable the administration of reduced doses. Furthermore, as a result of its azo functional groups, which are sensitive to reduction within a hypoxic environment, it is possible to achieve tumor‐targeted drug‐release with reduced side effects. CAC4A fulfils all essential requirements for a drug‐delivery system in addition to multiple advantages, including facile preparation, well‐defined molecular weight, and structure, and universal applicability. Such features collectively enable supramolecular prodrugs to be formulated simply and reproducibly, with potential for bench‐to‐bedside translation. Moreover, CAC4A is amenable to other therapy modalities and can be facilely decorated with functional groups and hybridized with nanomaterials, providing ample possibilities for its role in future drug‐delivery systems.
Carboxylated azocalix4arene is designed as a hypoxia‐responsive molecular container, which affords strong binding toward a series of chemotherapeutic drugs, and improves the drugs’ solubility and stability, demonstrating its universality as a supramolecular drug carrier. Taking one supramolecular prodrug as an example, the efficacy of this hypoxia‐targeted therapy is validated in vitro and in vivo.
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The first example of highly enantioselective intramolecular hydroarylation of allyl aryl ethers was realized by palladium‐catalyzed reductive heck reactions utilizing a new chiral sulfinamide ...phosphine ligand (N‐Me‐XuPhos). N‐Me‐XuPhos can be easily prepared on gram scale from readily available starting materials in a one‐pot synthesis approach. A series of optically active 2,3‐dihydrobenzofurans bearing a quaternary stereocenter were obtained in good yields and with excellent enantioselectivities. The practicality of this reaction was validated in the straightforward synthesis of CB2 receptor agonists. Moreover, deuterium was efficiently incorporated into the products.
A highly chemo‐ and enantioselective intramolecular hydroarylation of allyl aryl ethers remains a long‐standing challenge. Reported herein is the first example of a highly enantioselective intramolecular hydroarylation of allyl aryl ethers by palladium‐catalyzed reductive Heck reactions utilizing a new chiral sulfinamide phosphine ligand (N‐Me‐XuPhos).
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A magnetic CdS quantum dot (Fe3O4/polydopamine (PDA)/CdS) was synthesized through a facile and convenient method from inexpensive starting materials. Characterization of the prepared catalyst was ...performed by means of FTIR spectroscopy, XRD, SEM, TEM, energy‐dispersive X‐ray spectroscopy, and vibrating‐sample magnetometer techniques. Fe3O4/PDA/CdS was found to be a highly active photocatalyst for the amidation of aromatic aldehydes by using air as a clean oxidant under mild conditions. The photocatalyst can be recovered by magnetic separation and successfully reused for five cycles without considerable loss of its catalytic activity.
Going greener: Magnetic CdS quantum dots are designed for application as an efficient photocatalyst for the oxidative amidation of aldehydes by using air as the oxidant under mild conditions. The photocatalyst can be recovered by magnetic separation and successfully reused in five cycles without considerable loss of catalytic activity.
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A highly enantioselective dicarbofunctionalization of unactivated alkenes was implemented by a Pd‐catalyzed asymmetric tandem Heck/Suzuki coupling reaction. This reaction represents the first example ...of a highly enantioselective intramolecular cyclization/cross‐coupling of olefin‐tethered aryl halides with alkyl‐, alkenyl‐ or arylboronic acids, and provides rapid access to a number of chiral compounds, such as dihydrobenzofurans, indolines, chromanes, and indanes bearing a quaternary stereocenter, in good yields with excellent enantioselectivities. The practicality of this reaction was validated in the modification of biologically complex molecules such as peptides, piperitol, CB2 receptor agonists, etc. Moreover, the synthesis of two enantiomers can be easily realized by simple change in the order of the steps in the coupling sequence.
The first example of highly enantioselective intramolecular dicarbofunctionalization of unactivated alkenes with alkyl, aryl, or alkenylboronic acids is reported. It provides an efficient synthesis for various chiral benzene‐fused cyclic compounds bearing an all‐carbon quaternary stereocenter, and demonstrates high functional‐group tolerance. The synthesis of a pair of enantiomers was achieved by a change in the order of the steps in the reaction sequence.
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Highly enantioselective gold‐catalyzed intramolecular cyclization of N‐allenamides was implemented by utilizing a designed chiral sulfinamide phosphine ligand (PC‐Phos). This represents the first ...example of highly enantioselective intramolecular cyclization of N‐allenamides. The practicality of this reaction was validated in the total synthesis of (R)‐desbromoarborescidine A and formal synthesis of (R)‐desbromoarborescidine C and (R)‐deplancheine. Moreover, the catalyst system PC‐Phos/AuNTf2 proved to be specifically efficient to promote the desymmetrization of N‐allenamides in excellent yields with satisfactory ee values.
Ringing the changes: The first example of highly enantioselective gold‐catalyzed intramolecular cyclization of N‐allenamides was implemented by utilizing PC‐Phos ligands. The utility of this reaction was validated by the total synthesis of (R)‐desbromoarborescidine A.
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Sonogashira‐type cross‐couplings are one of the most significant alkynylations in organic chemistry. One of the first palladium‐catalyzed intramolecular Heck/Sonogashira reactions of alkenes with ...terminal alkynes is now reported. With this method, a variety of uniquely substituted chiral benzene‐fused heterocycles bearing a propargyl‐substituted all‐carbon quaternary stereocenter were obtained in a straightforward, high‐yielding, and highly stereoselective manner under mild conditions. Salient features of this process include the use of readily available substrates, high selectivities, a broad substrate scope as well as versatile product functionalizations.
Dual functionalization: An enantioselective palladium‐catalyzed aryl‐alkynylation of alkenes by a Heck/Sonogashira sequence enables the efficient synthesis of various chiral benzene‐fused heterocycles bearing a propargylic all‐carbon quaternary stereocenter. Salient features of this process include the use of readily available substrates, high selectivities, and a broad substrate scope.
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A polyimide covalent organic framework (PI-COF) with high thermal and chemical stabilities has been readily prepared from commercially available and inexpensive reagents and was employed as an ...effective support for heterogeneous copper. It was demonstrated that the obtained Cu@PI-COF is a highly active heterogeneous catalyst which can effectively promote the Chan–Lam coupling reaction of aryl boronic acids and amines in an open flask without the aid of any base or additive. In addition, the catalyst could be readily recovered from the reaction mixture by simple filtration and reused for at least eight cycles without any observable change in structure and catalytic activity.
A simple, new type of chiral sulfinamide monophosphines, the so‐called Ming‐Phos ligands, is reported; these ligands could be easily prepared from inexpensive and commercially available starting ...materials. The Ming‐Phos ligands performed well in the enantioselective gold‐catalyzed cycloaddition reaction of 2‐(1‐alkynyl)‐alk‐2‐en‐1‐ones with nitrones. Both enantiomers of the products could be obtained in good yields and with excellent diastereo‐ and enantioselectivity through transformations that were catalyzed by gold complexes derived from two diastereomers of Ming‐Phos ligand M5 (Ar=1‐naphthyl).
Ming‐Phos: A new type of simple chiral sulfinamide monophosphine ligands, the so‐called Ming‐Phos ligands, can be easily prepared from inexpensive and commercially available starting materials. The enantioselectivity of the reaction of yne–enones 1 with nitrones could be controlled by the diastereomeric ligands (R,RS)‐M5 and (S,RS)‐M5.
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The asymmetric catalytic addition of linear Grignard reagents to ketones has been a long‐standing challenge in organic synthesis. Herein, a novel family of PNP ligands (W‐Phos) was designed and ...applied in copper‐catalyzed asymmetric addition of linear Grignard reagents to aryl alkyl ketones, allowing facile access to versatile chiral tertiary alcohols in good to high yields with excellent enantioselectivities (up to 94 % yield, 96 % ee). The process can also be used to synthesize chiral allylic tertiary alcohols from more challenging α,β‐unsaturated ketones. Notably, the potential utility of this method is demonstrated in the gram‐scale synthesis and modification of various densely functionalized medicinally relevant molecules.
A novel family of PNP ligands (W‐Phos) was designed and applied in the copper‐catalyzed asymmetric addition of linear Grignard reagents to ketones, allowing ready access to versatile chiral tertiary alcohols in high yields and with excellent enantioselectivities.
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In recent years, conventional treatments including surgery, chemotherapy and radiotherapy have been the main approaches in tumour therapy. Cancer immunotherapy is a new therapeutic modality to fight ...cancer by harnessing the power of patients' own immune system. Ongoing research related to these therapies has demonstrated their advantages and intrinsic limitations. Nanomaterial-based platforms are utilized in these emerging fields. In particular, a combination of other treatment methods with cancer immunotherapy to achieve precision medicine and prevent recurrence and metastasis, could improve patients' outcome. The combined multiple treatments have superior efficacy to any monotherapy alone in producing improved anti-cancer activity. Therefore, it's necessary to summarise research advances in nanomaterial-based combination cancer immunotherapy contributing to clinical transformation. This review is based on the principles of cancer immunotherapy and the combined treatment design reflected by advances in materials science, including the structures of nanoplatforms and their underlying mechanisms towards cancer. The ultimate goals are to stimulate the design of better strategies for versatile use in the future based on biomaterial engineering methods to enhance the efficacy of combined cancer treatments, and to provide new ideas for the prospects of a synergistic cancer combination immunotherapy for clinical application transformation.
This review aims to summarize various synergistic combination cancer immunotherapy strategies based on nanomaterials.
