Beyond symmetric self-assembly and effective molarity: unlocking functional enzyme mimics with robust organic cages

• Keith G. Andrews

Beilstein J. Org. Chem. 2025, 21, 421–443, doi:10.3762/bjoc.21.30

• compartmentalization of contrasting reactivities is possible to avoid such incompatibilities [189][199][200][201]. Likewise, the lability of metal–ligand dative bonds can make post-assembly modifications of MOCs challenging [202][203] – for instance it is difficult to lock the dative bonds in place, and reactions that

Emerging trends in the optimization of organic synthesis through high-throughput tools and machine learning

• Pablo Quijano Velasco,
• Kedar Hippalgaonkar and
• Balamurugan Ramalingam

Beilstein J. Org. Chem. 2025, 21, 10–38, doi:10.3762/bjoc.21.3

• components consisting of styrene, α,α′-azobisisobutyronitrile (AIBN), and p-xylene were infused using a computer-controlled segmented-flow platform. These approaches allow the compartmentalization of reaction mixtures without cross-contamination and enhance experimental throughput significantly. The concept

Switchable molecular tweezers: design and applications

• Pablo Msellem,
• Maksym Dekthiarenko,
• Nihal Hadj Seyd and
• Guillaume Vives

Beilstein J. Org. Chem. 2024, 20, 504–539, doi:10.3762/bjoc.20.45

• frequently employed in biological systems for communication and actuation (e.g., ATP). They, however, generate waste which is very well managed in biological systems by using compartmentalization strategies. Nonetheless, the challenge of waste management in artificial systems remains significant. On the

Enabling artificial photosynthesis systems with molecular recycling: A review of photo- and electrochemical methods for regenerating organic sacrificial electron donors

• Grace A. Lowe

Beilstein J. Org. Chem. 2023, 19, 1198–1215, doi:10.3762/bjoc.19.88

• microscopy [36][37]. In nature, chemical gradients and phase separation are maintained by compartmentalization in liposomes, micelles, and vesicles rather than at interfaces such as ITIES. Artificial photosynthesis systems are being designed to mimic this behavior and recently the field of artificial

• of artificial photosynthesis research investigating the compartmentalization of different reactions using liposomes and membranes [38]. Another alternative could be to use redox-active polymers as recyclable donors which would allow microporous membrane separation. Redox-active polymers are a very

Chemical approaches to discover the full potential of peptide nucleic acids in biomedical applications

• Nikita Brodyagin,
• Martins Katkevics,
• Venubabu Kotikam,
• Christopher A. Ryan and
• Eriks Rozners

Beilstein J. Org. Chem. 2021, 17, 1641–1688, doi:10.3762/bjoc.17.116

Mechanochemistry of supramolecules

• Anima Bose and
• Prasenjit Mal

Beilstein J. Org. Chem. 2019, 15, 881–900, doi:10.3762/bjoc.15.86

• -assembly with a high degree of compartmentalization [2]. In addition, the same building units are often used across an enormous number of structures in a reversible fashion through thermodynamic control [3]. Conversely, small-molecule synthesis is generally performed under kinetically controlled reaction

Nanoreactors for green catalysis

• M. Teresa De Martino,
• Loai K. E. A. Abdelmohsen,
• Floris P. J. T. Rutjes and
• Jan C. M. van Hest

Beilstein J. Org. Chem. 2018, 14, 716–733, doi:10.3762/bjoc.14.61

• calixarenes [38][39]. Besides these supramolecular cage structures compartmentalization can also be achieved in macromolecular nanoreactors. The advantage of employing these polymeric structures is their improved robustness and loading capacity, which makes recycling and efficient usage of catalytic species

• ]. Compartmentalization enables catalyst segregation and shielding, and ensures its facile removal from the reaction mixture after the reaction has taken place [34]; this facilitates reactions to be performed in water followed by liquid–liquid separation of products and catalyst [22]. Moreover, shielding and segregation

• -assembled nanoreactors are macromolecular architectures that are non-covalently assembled from their constituent building units [58][59]. Such nanoreactors allow for physical confinement of catalysts, shielding them from their surroundings [60]. Compartmentalization of catalysts in supramolecular

Chemical systems, chemical contiguity and the emergence of life

• Terrence P. Kee and
• Pierre-Alain Monnard

Beilstein J. Org. Chem. 2017, 13, 1551–1563, doi:10.3762/bjoc.13.155

• bilayers into which PAHs have been incorporated has been reported [75], their dissipation is rapid. That is, utilization of the energy gradient should be directly linked to its formation. The build-up of the proton gradient underlines the importance of having a compartmentalization system. Indeed, the

• light harvesting apparatus to chemical energy gradient formation. Volume-enclosed catalysis: Compartmentalization of an aqueous volume within defined, preferably semi-permeable boundaries, was recognized very early on as paramount for the emergence of life [76]. Following the elucidation of the cellular

• permeability of simple membranes was sufficient to permit an internalized synthetic or catalytic activity albeit at low yield and rate levels. However, both highlighted a different aspect of the compartmentalization: The use of aqueous metal ions could jeopardize the integrity of the compartment [20], and the

Grip on complexity in chemical reaction networks

• Albert S. Y. Wong and
• Wilhelm T. S. Huck

Beilstein J. Org. Chem. 2017, 13, 1486–1497, doi:10.3762/bjoc.13.147

• ][75][76][77]. The underlying principle of compartmentalization, dynamic combinatorial chemistry, and hydrogelation also appears in different types of networks [78][79][80][81][82][83][84]. Chemical networks can be readily made from tunable organic structures, holding considerable potential in the

Framing major prebiotic transitions as stages of protocell development: three challenges for origins-of-life research

• Ben Shirt-Ediss,
• Sara Murillo-Sánchez and
• Kepa Ruiz-Mirazo

Beilstein J. Org. Chem. 2017, 13, 1388–1395, doi:10.3762/bjoc.13.135

• , the majority of ‘compartment-first’ approaches have focused on a second research objective: capturing cell-like behaviours by means of vesicle model systems. Compartmentalization could initially be tried with a two-phase system (e.g., droplets or micro-emulsions) but liposome research techniques

• longer we postpone the appearance of chemical encapsulated systems, the more intractable the problem of compartmentalization will surely become. Indeed, if reaction networks could develop their catalytic efficiency in compartment-free scenarios, their eventual encapsulation within lipid vesicles would

• evolution (as explained in more detail in [60]). Instead of using compartmentalization simply as a way to segregate populations of nucleic acids (with the aim to avoid problems like parasitism [61]), the idea here is that integrated protocells constitute the actual units of evolutionary change from the very

Strategies in megasynthase engineering – fatty acid synthases (FAS) as model proteins

• Manuel Fischer and
• Martin Grininger

Beilstein J. Org. Chem. 2017, 13, 1204–1211, doi:10.3762/bjoc.13.119

• recent years, a wealth of structural data on FAS multienzyme complexes (type I) has further deepened the insight into the principles of fatty acid (FA) synthesis [13][14][15][16][17][18][19]. Molecular mechanisms of FAS/PKS mode of action Compartmentalization Compartmentalization is a phenomenon seen

• . Compartmentalization of synthesis. a) Surface depiction of fungal FAS (PDB-code: 3hmj) with the upper reaction chamber shown without the front part of the barrel wall. One of overall three sets of catalytic domains within a reaction chamber is indicated. Abbreviations as introduced before; additionally, acetyl

Towards open-ended evolution in self-replicating molecular systems

• Herman Duim and
• Sijbren Otto

Beilstein J. Org. Chem. 2017, 13, 1189–1203, doi:10.3762/bjoc.13.118

• locally, a specialized compartmentalization should act in concert with the cooperative replication system. How such compartmentalization might occur is another topic entirely and beyond the scope of this review, but it is proposed that compartmentalization can actually aid in the evolution of replicating

Opportunities and challenges for the sustainable production of structurally complex diterpenoids in recombinant microbial systems

• Katarina Kemper,
• Max Hirte,
• Markus Reinbold,
• Monika Fuchs and
• Thomas Brück

Beilstein J. Org. Chem. 2017, 13, 845–854, doi:10.3762/bjoc.13.85

• ]. Eponymous intermediate of this pathway is the product of the second enzymatic step where 1-deoxy-D-xylulose-5-phosphate (DXP) is reduced to 2-C-methyl-D-erythritol-4-phosphate (see Scheme 1). Parallel occurrence of both pathways in higher plants is regulated through compartmentalization [30] with

Aqueous reductive amination using a dendritic metal catalyst in a dialysis bag

• Jorgen S. Willemsen,
• Jan C. M. van Hest and
• Floris P. J. T. Rutjes

Beilstein J. Org. Chem. 2013, 9, 960–965, doi:10.3762/bjoc.9.110

• longer reaction times. These results clearly show that the encapsulated catalyst system is suitable to successfully drive a complex reaction mixture with various equilibrium reactions to completion. Keywords: aqueous reductive amination; cascade catalysis; compartmentalization; dendritic catalysts

• to incomplete conversions. Incompatible catalysts can be physically separated in various ways, e.g., by applying biphasic reaction conditions [10], membrane reactors [11] or sol–gels [12]. Another way to circumvent incompatibility problems is to achieve compartmentalization by attaching the actual

• amino acids in water. The G4 catalyst showed the same reaction rate in a second run, which validates the concept of maintaining the macromolecular catalyst in the compartment. The work described here could be more widely applicable for compartmentalization of catalytic systems in aqueous media, where

Synthesis of glycoconjugate fragments of mycobacterial phosphatidylinositol mannosides and lipomannan

• Benjamin Cao,
• Jonathan M. White and
• Spencer J. Williams

Beilstein J. Org. Chem. 2011, 7, 369–377, doi:10.3762/bjoc.7.47

• -mannosyltransferases MptB and MptA [18][19], and to demonstrate functional compartmentalization of PPM synthase activity and MptB/MptA [24]. They have also been used as glycolipid substrates supporting the development of inhibitors of PIM/LM/LAM biosynthesis [25][26][27][28]. Various 1,2-linked aminooctyl