Nanoreactors for Chemical Synthesis and Biomedical Applications

Zhou, Hua; Tan, Jiajia; Zhang, Xuanjun

doi:10.1002/asia.201900967

Cited by 12 publications

(5 citation statements)

References 81 publications

(63 reference statements)

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“…According to the different composition and formation mechanisms, the materials used for constructing spatially confined nanoreactors can be mainly classified into three kinds: porous inorganic materials, porous crystalline materials with organic components, and self‐assembly of polymers. [ 6 ] Porous inorganic materials involve porous carbon/graphene, porous silica and other inorganic materials. Porous carbon/graphene has excellent properties of good chemical stability and high porosity.…”

Section: Introductionmentioning

confidence: 99%

Spatially Confined Nanoreactors Designed for Biological Applications

Wang,

Xie,

Zhao

2024

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The applications of nanoreactors in biology are becoming increasingly significant and prominent. Specifically, nanoreactors with spatially confined, due to their exquisite design that effectively limits the spatial range of biomolecules, attracted widespread attention. The main advantage of this structure is designed to improve reaction selectivity and efficiency by accumulating reactants and catalysts within the chambers, thus increasing the frequency of collisions between reactants. Herein, the recent progress in the synthesis of spatially confined nanoreactors and their biological applications is summarized, covering various kinds of nanoreactors, including porous inorganic materials, porous crystalline materials with organic components and self‐assembled polymers to construct nanoreactors. These design principles underscore how precise reaction control could be achieved by adjusting the structure and composition of the nanoreactors to create spatial confined. Furthermore, various applications of spatially confined nanoreactors are demonstrated in the biological fields, such as biocatalysis, molecular detection, drug delivery, and cancer therapy. These applications showcase the potential prospects of spatially confined nanoreactors, offering robust guidance for future research and innovation.

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Section: Introductionmentioning

confidence: 99%

Spatially Confined Nanoreactors Designed for Biological Applications

Wang,

Xie,

Zhao

2024

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“…The application of molecules that provide a confined space as catalysts has been the focus of increasing attention in recent years [1–4] . These systems present a cavity as their main feature, [5] where they can host diverse reactants in a chemical environment that may differ significantly from that provided by the bulk solution.…”

Section: Introductionmentioning

confidence: 99%

“…The application of molecules that provide a confined space as catalysts has been the focus of increasing attention in recent years. [1][2][3][4] These systems present a cavity as their main feature, [5] where they can host diverse reactants in a chemical environment that may differ significantly from that provided by the bulk solution. In this context, the macrocycles known as calix [n]arenes have been used as nanoreactors for a large range of processes, including as stabilizers for supported molecular noble-metal catalysts, [6] organic transformations, [7][8][9][10] small molecule activation, [11][12][13] as well as CÀ C [14,15] and CÀ N [16] crosscoupling reactions.…”

Section: Introductionmentioning

confidence: 99%

Conformational Effects of Regioisomeric Substitution on the Catalytic Activity of Copper/Calix[8]arene C−S Coupling

et al. 2022

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Functionalization of the phenolic rim of p-tert-butylcalix [8]arene with phenanthroline to create a cavity leads to formation of two regioisomers. Substitution of positions 1 and 5 produces the known C 2v -symmetric regioisomer 1,5-(2,9-dimethyl-1,10phenanthroyl)-p-tert-butylcalix[8]arene (L 1,5 ), while substitution of positions 1 and 4 produces the C s -symmetric regioisomer 1,4-(2,9-dimethyl-1,10-phenanthroyl)-p-tert-butylcalix[8]arene (L 1,4 ) described herein. [Cu(L 1,4 )I] was synthesized from L 1,4 and CuI in good yield and characterized spectroscopically. To evaluate the effect of its cavity on catalysis, Ullmann-type CÀ S coupling was chosen as proof-of-concept. Selected aryl halides were used, and the results compared with the previously reported Cu(I)/L 1,5 system. Only highly activated aryl halides generate the CÀ S coupling product in moderate yields with the Cu(I)/L 1,4 system. To shed light on these observations, detailed computational investigations were carried out, revealing the influence of the calix[8]arene macrocyclic morphology on the accessible conformations. The L 1,4 regioisomer undergoes a deformation that does not occur with L 1,5 , resulting in an exposed catalytic center, presumably the cause of the low activity of the former system. The 1,4-connectivity was confirmed in the solid-state structure of the byproduct [Cu(L 1,4 À H)(CH 3 CN) 2 ] that features Cu(I) coordinated inside a cleft defined by the macrocyclic framework.

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“…Amphiphilic (macro)molecules, especially block copolymers, , have been studied extensively in the past three decades due to the possibility of producing different nanostructures in water, such as micelles, cylindrical micelles, or vesicles, often with stimuli-responsive behavior. , They find widespread applications in drug delivery, as nanoreactors, in templating and so on. However, in the immiscibility-driven aggregation of structurally diverse amphiphilic (macro)molecules, the morphology primarily depends on the packing parameter (Scheme ), estimated from the relative volume fraction of the hydrophobic and hydrophilic segments.…”

Section: Introductionmentioning

confidence: 99%

Molecular Recognition Driven Bioinspired Directional Supramolecular Assembly of Amphiphilic (Macro)molecules and Proteins

et al. 2021

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Metrics & MoreArticle Recommendations CONSPECTUS: Bioinspired self-assembly has been explored with diverse synthetic scaffolds, among which amphiphiles are perhaps the most extensively studied systems. Classical surfactants or amphiphilic block copolymers, depending on the hydrophobic− hydrophilic balance, produce distinct nanostructures, which hold promise for applications ranging from biology to materials sciences. Nevertheless, their immiscibility-driven aggregation does not provide the opportunity to precisely regulate the internal order, morphology, or functional group display, which is highly desirable, especially in the context of biological applications.A new class of amphiphiles have emerged in the recent past in which the hydrophilic segment(s) is appended with a hydrophobic supramolecular-structure-directing-unit (SSDU), consisting of a π-conjugated chromophore and a H-bonding group. Selfrecognition of the SSDU by attractive directional interactions governs the supramolecular assembly, which is fundamentally different than the repulsive solvent-immiscibility driven aggregation of traditional amphiphiles. Such SSDU-appended hydrophilic polymers exhibit entropy-driven highly stable self-assembly producing distinct nanostructures depending on the H-bonding functional group. For example, polymers with the hydrazide-functionalized SSDU attached form a polymersome, while in a sharp contrast, the same polymers when connected to an amide containing SSDU produce a cylindrical micelle via a spherical-micelle intermediate. This relationship holds true for a series of SSDU-attached hydrophilic polymers irrespective of the hydrophobic/hydrophilic balance or chemical structure, indicating that the supramolecular-assembly is primarily controlled by the specific molecular-recognition motif of the SSDU, instead of the packing parameter-based norms. Beyond synthetic polymers, SSDU-attached proteins also exhibit similar molecular-recognition driven self-assembly as well as coassembly with SSDU-attached polymers or hydrophilic wedges, producing multi-stimuli-responsive nanostructures in which the protein gains remarkable protection from thermal denaturation or enzymatic hydrolysis and exhibits redox-responsive enzymatic activity. Furthermore, SSDU-derived bola-shape π-amphiphiles have been recognized as a useful scaffold for the synthesis of unsymmetric polymersomes, rarely reported in the literature. The building block consists of a hydrophobic naphthalene-diimide (NDI) π-system attached to a hydrophilic functional group (ionic or nonionic) and a nonionic wedge on its two opposite arms. Extended H-bonding among the hydrazide groups, placed only on one side of the central chromophore by design, ensures stacking of the NDIs with parallel orientation and induces a preferred direction of curvature so that the H-bonded chain and consequently the functional groups attached to the same side remain at the inner-wall of the supramolecular polymersome. Automatically, the functional groups, located on the other side, are displayed ...

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Nanoreactors for Chemical Synthesis and Biomedical Applications

Cited by 12 publications

References 81 publications

Spatially Confined Nanoreactors Designed for Biological Applications

Spatially Confined Nanoreactors Designed for Biological Applications

Conformational Effects of Regioisomeric Substitution on the Catalytic Activity of Copper/Calix[8]arene C−S Coupling

Molecular Recognition Driven Bioinspired Directional Supramolecular Assembly of Amphiphilic (Macro)molecules and Proteins

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