Gold extraction at the molecular level using α- and β-cyclodextrins

• Susana Santos Braga

Beilstein J. Org. Chem. 2025, 21, 1116–1125, doi:10.3762/bjoc.21.89

• the inclusion of complex aurate ions such as tetrabromoaurate, dicyanoaurate and a few other tetrahaloaurates. The review describes the properties of self-assembly of cyclodextrins with these ions, with highlight to α-CD and, more recently, β-CD, requiring the use of a co-former/precipitating agent

• spontaneous complex formation between α-CD and tetrabromoaurate and its current status of use in a few mining sites in the United States. Keywords: bromoaurate; cyanoaurate; cyclodextrin inclusion; self-assembly; supramolecular interactions; Introduction Gold has allured and captivated humankind ever since

• complex matrices such as ores and industrial waste. Review Isolating gold with α-cyclodextrin Process discovery and the role of self-assembly The discovery that α-CD could be used to isolate gold was made serendipitously [37]. A young researcher of the Stoddart group, Zhichang Liu, was trying to prepare

Recent advances in controllable/divergent synthesis

• Jilei Cao,
• Leiyang Bai and
• Xuefeng Jiang

Beilstein J. Org. Chem. 2025, 21, 890–914, doi:10.3762/bjoc.21.73

• structurally diverse macrocycles through the dynamic self-assembly of α,α’-linked oligopyrrolic dialdehydes and alkyldiamines (Scheme 10) [39]. Their investigation revealed distinct solvent-mediated selectivity in product formation. Condensation of the pyridine-bridged oligopyrrolic dialdehyde 37 with simple

Acyclic cucurbit[n]uril bearing alkyl sulfate ionic groups

• Christian Akakpo,
• Peter Y. Zavalij and
• Lyle Isaacs

Beilstein J. Org. Chem. 2025, 21, 717–726, doi:10.3762/bjoc.21.55

• [n])), and those prepared by metal ligands and H-bonding self-assembly processes [1][2][10][11][12][13][14][15][16][17][18][19][20]. Macrocycles have played key roles in important real-world products including the household deodorizer FebreezeTM, glucose monitors, and as solubilizing excipients [21

Origami with small molecules: exploiting the C–F bond as a conformational tool

• Patrick Ryan,
• Ramsha Iftikhar and
• Luke Hunter

Beilstein J. Org. Chem. 2025, 21, 680–716, doi:10.3762/bjoc.21.54

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

• symmetry to enable promising catalytic modes. Keywords: cavity confinement catalysis; enzyme mimicry; robust organic cages; self-assembly; supramolecular catalysis; Introduction I frequently introduce my research on organic cage enzyme mimics with the following observation. For hundreds of years

• precision. In this perspective, I identify three clear areas for increased focus to achieve this ambition: (1) the development of modular cavities featuring sub-Ångstrom-confined bifunctionality (including frustrated charges); (2) improved access to stable cavities with reduced symmetry via self-assembly by

• trying to squash a rock with soft tweezers – the tweezers will preferentially bend before breaking the rock). The trade-off of rapid synthesis of MOCs by self-assembly is that they can lack robustness, and so catalysis conditions have to be mild enough to avoid cage disassembly [22], although

Hydrogen-bonded macrocycle-mediated dimerization for orthogonal supramolecular polymerization

• Wentao Yu,
• Zhiyao Yang,
• Chengkan Yu,
• Xiaowei Li and
• Lihua Yuan

Beilstein J. Org. Chem. 2025, 21, 179–188, doi:10.3762/bjoc.21.10

• Wentao Yu Zhiyao Yang Chengkan Yu Xiaowei Li Lihua Yuan College of Chemistry, Sichuan University, Chengdu 610064, China 10.3762/bjoc.21.10 Abstract Orthogonal self-assembly represents a useful methodology to construct supramolecular polymers with AA- and AB-type monomers, as commonly used for

• materials. Keywords: hydrogen-bonded macrocycle; orthogonal self-assembly; shape-persistent; supramolecular polymer; Introduction Host–guest interactions, particularly those involving macrocycles as hosts [1], have found a myriad of applications in supramolecular chemistry [2][3][4] owing to their ability

• to create noncovalent, dynamic, yet in some cases strong forces between molecules. Adding an additional element of interactions to supramolecular systems endows them with a feature of “orthogonal self-assembly”, a process in which molecular species are assembled into aggregates by two or more types

Hot shape transformation: the role of PSar dehydration in stomatocyte morphogenesis

• Remi Peters,
• Levy A. Charleston,
• Karinan van Eck,
• Teun van Berlo and
• Daniela A. Wilson

Beilstein J. Org. Chem. 2025, 21, 47–54, doi:10.3762/bjoc.21.5

• ) in biomedical applications, boasting advantages in biocompatibility and degradability. While the self-assembly behavior of block copolymers containing polysarcosine-containing polymers has been reported, their potential for shape transformation remains largely untapped, limiting their versatility

• -polystyrene block copolymers (PEG-PS) stand out for their versatility and adaptability. These copolymers exhibit a remarkable propensity for self-assembly, allowing the formation of vesicles capable of undergoing diverse shape transformations. Notably, they can adopt the distinctive stomatocyte morphology

• glutamate) (PBLG) as the hydrophobic block, which was done to prevent ending on a primary amine in the final product which could disrupt self-assembly due to its ionizable nature. Subsequently, PBLG served as a macroinitiator for the polymerization of sarcosine NCA, yielding the final polymer with high

Efficient synthesis of fluorinated triphenylenes with enhanced arene–perfluoroarene interactions in columnar mesophases

• Yang Chen,
• Jiao He,
• Hang Lin,
• Hai-Feng Wang,
• Ping Hu,
• Bi-Qin Wang,
• Ke-Qing Zhao and
• Bertrand Donnio

Beilstein J. Org. Chem. 2024, 20, 3263–3273, doi:10.3762/bjoc.20.270

• -67034 Strasbourg, France 10.3762/bjoc.20.270 Abstract The high potential of non-covalent arene–fluoroarene intermolecular interactions in the design of liquid crystals lies in their ability to strongly promote self-assembly, improve the order and stability of the supramolecular mesophases, and enable

Tailored charge-neutral self-assembled L₂Zn₂ container for taming oxalate

• David Ocklenburg and
• David Van Craen

Beilstein J. Org. Chem. 2024, 20, 3007–3015, doi:10.3762/bjoc.20.250

• metallocontainers which are formed by metal-driven self-assembly have become especially popular to bind various kinds of anions since such systems offer easy to tune confinements. Usually, the utilized complexes are net positive which makes them ideal hosts for anions [56][57][58][59][60][61][62][63]. However, the

• positively charged or charge-neutral, is their metal-driven self-assembly. Unfortunately, this can also be their Achilles' heel, as the underlying coordination bonds are fragile compared to covalent bonds. For example, metallocages can easily break apart by the addition of competitive anions which are highly

• troubles with the formed complexes in this respect. The final step of the ligand preparation is the CuAAC click reaction. The protecting Boc group of the 8-hydroxyquinoline units was cleaved during the workup right away resulting in ligand L-H2 with 44% yield. Self-assembly in DMSO with zinc(II) via its

Applications of microscopy and small angle scattering techniques for the characterisation of supramolecular gels

• Connor R. M. MacDonald and
• Emily R. Draper

Beilstein J. Org. Chem. 2024, 20, 2608–2634, doi:10.3762/bjoc.20.220

• that the hierarchal molecular self-assembly of these materials into larger structures directly influences behaviours such as performance and stability. It is therefore imperative that these materials are characterised effectively over multiple length scales. Two effective methods of achieving this are

• utilise the self-assembly of small molecules into a network of long anisotropic structures which can entangle or cross-link. This network can immobilise the solvent, resulting in a material with both solid-like and liquid-like characteristics. The versatility of these compounds arises from their self

• change in the self-assembly, meaning a true representation of the supramolecular material may not be investigated which is rarely confirmed when applied to the characterisation of such systems. To identify such changes in structure, other characterisation techniques that probe the structures without the

A review of recent advances in electrochemical and photoelectrochemical late-stage functionalization classified by anodic oxidation, cathodic reduction, and paired electrolysis

• Nian Li,
• Ruzal Sitdikov,
• Ajit Prabhakar Kale,
• Joost Steverlynck,
• Bo Li and
• Magnus Rueping

Beilstein J. Org. Chem. 2024, 20, 2500–2566, doi:10.3762/bjoc.20.214

• alternative to the harsh Pummerer rearrangement. Methanol played a crucial role in achieving the desired transformation and it was suggested to promote the self-assembly of reagents 24 and 25 for the formation of 27, which allows the selective abstraction of H+ from the less sterically hindered side

HFIP as a versatile solvent in resorcin[n]arene synthesis

• Hormoz Khosravi,
• Valeria Stevens and
• Raúl Hernández Sánchez

Beilstein J. Org. Chem. 2024, 20, 2469–2475, doi:10.3762/bjoc.20.211

• unique bowl-shape structures and self-assembly in solution have facilitated their widespread use as building blocks in nanomaterials [61][62]. Nevertheless, precisely due to their vast number of applications, functionalized resorcin[n]arenes are needed that meet the needs of the desired function. For

Novel truxene-based dipyrromethanes (DPMs): synthesis, spectroscopic characterization and photophysical properties

• Shakeel Alvi and
• Rashid Ali

Beilstein J. Org. Chem. 2024, 20, 2163–2170, doi:10.3762/bjoc.20.186

• ), organogels, molecular wires, self-assembly and so forth [14][15][16][17][18][19][20][21][22][23][24][25]. Moreover, nowadays these invaluable compounds have also received great attention of supramolecular chemists, and finds applications in sensing, catalysis, donor–acceptor systems, energy transfer and

• in addition to the stimulating photophysical properties and distinct architectures emerging from the self-assembly processes [42]. Noticeably, most extensively used DPMs belong to the 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY), owing to their high propensity toward chemical manipulations and

• potential applications in the arena of supramolecular chemistry in general, sensing, molecular recognition and self-assembly in particular in has yet to be explored. Moreover, applications of the truxene derivatives in catalysis are also scared, and needs to be advanced in future research. Experimental

Cage-like microstructures via sequential Ugi reactions in aqueous emulsions

• Rita S. Alqubelat,
• Yaroslava A. Menzorova and
• Maxim A. Mironov

Beilstein J. Org. Chem. 2024, 20, 2078–2083, doi:10.3762/bjoc.20.179

• obtain colloidosomes covered with fissures of a controlled size [10]. A simpler method recently proposed involves the self-assembly of starch granules on the surface of emulsion droplets. However, this approach did not allow the pore size to be controlled [14]. Thus, the currently available methods for

Understanding X-ray-induced isomerisation in photoswitchable surfactant assemblies

• Beatrice E. Jones,
• Camille Blayo,
• Jake L. Greenfield,
• Matthew J. Fuchter,
• Nathan Cowieson and
• Rachel C. Evans

Beilstein J. Org. Chem. 2024, 20, 2005–2015, doi:10.3762/bjoc.20.176

• hydrophilicity [6]. This, in turn, affects the interfacial and self-assembly properties of the PS [4][5][6]. The uniquely tuneable properties of these photoswitchable molecules have led to their successful application in areas such as DNA compaction [8], photorheological fluids [9][10] and micellar catalysis [11

• phototuneable interfacial [16][17][18] and self-assembly properties [19][20]. However, further understanding of factors which affect the isomerisation of these new surfactants, and the effect this has on their self-assembled structures, is still needed to tailor them towards application. Small-angle scattering

• acidification effect from radiolytic D+ formation [43]. The change from H2O to D2O may also affect the surfactant self-assembly due to the change in hydrogen-bond strength [44]. Fitting to the SAXS data shows that AzoTAB and AAPTAB in the E-isomeric forms form elliptical cylindrical and ellipsoidal micelles

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

• by the addition of zinc(II) which opens the tweezers, releasing the guest and leading to the disappearance of the photosensitizing properties of the system. In an extension of this work, discrete tetranuclear Pt complexes with Pt–Pt interaction were obtained by self-assembly between 21 and

Facile access to pyridinium-based bent aromatic amphiphiles: nonionic surface modification of nanocarbons in water

• Lorenzo Catti,
• Shinji Aoyama and
• Michito Yoshizawa

Beilstein J. Org. Chem. 2024, 20, 32–40, doi:10.3762/bjoc.20.5

• similar to AA [12][13], indicating self-assembly via the hydrophobic effect and π-stacking interactions (Figure 3a,b). The self-assembly in water was further supported by UV–visible analysis, displaying slight red-shifts of the anthracene absorption bands relative to the spectrum in methanol (Δλmax = +3

• the self-assembly of in average six PA-CH3 amphiphiles into a small aromatic micelle (Figure 3g). In a similar way, the generation of micelles (PA-OCH3)n, (PA-OH)n, and (PA-Im)n was confirmed via NMR, UV–visible, and DLS analyses upon dissolution of the corresponding amphiphiles in water (Figure 3c,d

Unprecedented synthesis of a 14-membered hexaazamacrocycle

• Anastasia A. Fesenko and
• Anatoly D. Shutalev

Beilstein J. Org. Chem. 2023, 19, 1728–1740, doi:10.3762/bjoc.19.126

• -pyrazolo[3,4-d]pyrimidin-5-amine followed by dimerization to give the final macrocycle. A convenient synthesis of the latter starting from 4-imino-2-methyl-2,4-dihydro-5H-pyrazolo[3,4-d]pyrimidin-5-amine was developed. A plausible pathway for the macrocycle self-assembly is discussed. Some features of the

• structure and reactivity of the obtained macrocycle are outlined. Keywords: amidrazones; hexaazamacrocycles; pyrazolo[3,4-d]pyrimidines; ring contraction; self-assembly; Introduction The chemistry of polyazamacrocycles (PAMs) is currently one of the most rapidly developing areas of heterocyclic chemistry

• obtained instead [40]. Since this type of macrocycle self-assembly seems to be very promising, we decided to reproduce the Dolzhenko’s procedure, then study the macrocyclization in detail, and extend this approach to the synthesis of other polyunsaturated 1,2,4,8,9,11-hexaazamacrocycles. Herein, we report

Tying a knot between crown ethers and porphyrins

• Maksym Matviyishyn and
• Bartosz Szyszko

Beilstein J. Org. Chem. 2023, 19, 1630–1650, doi:10.3762/bjoc.19.120

• synthesising these systems, including cyclisation reactions, self-assembly, and their remarkable reactivity. The potential applications of porphyrin-crown ether hybrids are also highlighted. Moreover, the discussion identifies the challenges associated with synthesising and characterising hybrids, outlining

• the possible future directions. Keywords: crown ethers; porphyrinoids; self-assembly; sensors; supramolecular chemistry; Introduction Many areas of modern supramolecular chemistry, organic, inorganic, materials and coordination chemistry, are based upon macrocyclic compounds of specifically-designed

• ]. The CsF binding led to a supramolecular self-assembly process, inducing a sandwich host–guest complex formation in the solid state (Scheme 2). It was established that fluoride is preferred over any other halide anions. The binding of the ion pairs was observed in highly polar solvent media, but in the

pH-Responsive fluorescent supramolecular nanoparticles based on tetraphenylethylene-labelled chitosan and a six-fold carboxylated tribenzotriquinacene

• Nan Yang,
• Yi-Yan Zhu,
• Wei-Xiu Lin,
• Yi-Long Lu and
• Wen-Rong Xu

Beilstein J. Org. Chem. 2023, 19, 635–645, doi:10.3762/bjoc.19.45

• TPE labelling degree. Self-assembly behavior of CS-TPE in water. To investigate the self-assembly behavior of CS-TPE in water, the critical aggregation concentrations (CACs) of CS-TPE were determined by measuring their optical transmittance at different concentrations (Figure S2, Supporting

• makes it suitable for oral drug delivery. However, the aggregation behavior of CS-TPE under alkaline conditions may influence its drug release efficiency. Thus, the development of modified systems with reduced propensity to accumulate should be of interest. Self-assembly behavior of TBTQ-C6/CS-TPE in

A new oxidatively stable ligand for the chiral functionalization of amino acids in Ni(II)–Schiff base complexes

• Alena V. Dmitrieva,
• Oleg A. Levitskiy,
• Yuri K. Grishin and
• Tatiana V. Magdesieva

Beilstein J. Org. Chem. 2023, 19, 566–574, doi:10.3762/bjoc.19.41

• derived from glycine Schiff bases containing a source of chirality is the most convenient and widely used template for modification of the glycine fragment under mild conditions. The template can be easily obtained via self-assembly of the starting components in the presence of metal ions (commonly Ni(II

• )-benzylproline lead to (S)-N-(2-benzoyl-5-tert-butylphenyl)-1-benzylpyrrolidine-2-carboxamide (L7) in 73% yield with 96% ee (see Supporting Information File 1). The self-assembly of the three components L7, Ni(NO3)2, and glycine gave the corresponding (GlyNi)L7 complex which was isolated in 66% yield and fully

Investigation of cationic ring-opening polymerization of 2-oxazolines in the “green” solvent dihydrolevoglucosenone

• Solomiia Borova and
• Robert Luxenhofer

Beilstein J. Org. Chem. 2023, 19, 217–230, doi:10.3762/bjoc.19.21

• of view [28]. Accordingly, Hoogenboom et al. investigated the CROP of 2-alkyl-2-oxazoline in sulfolane and investigated its effect on monomer distribution and self-assembly of the performed copolymer [30][31][32]. However, the degradability of sulfolane into acidic components, its relatively high

Comparison of crystal structure and DFT calculations of triferrocenyl trithiophosphite’s conformance

• Ruslan P. Shekurov,
• Mikhail N. Khrizanforov,
• Ilya A. Bezkishko,
• Tatiana P. Gerasimova,
• Almaz A. Zagidullin,
• Daut R. Islamov and
• Vasili A. Miluykov

Beilstein J. Org. Chem. 2022, 18, 1499–1504, doi:10.3762/bjoc.18.157

• properties. Such switchable systems with conjugated organic fragments containing an FeII/FeIII system were used in organic electronics as molecular switches, optoelectronic materials and in biochemistry as photonic or redox devices [6]. A promising approach is the coordination self-assembly of multiferrocene

1,4,6,10-Tetraazaadamantanes (TAADs) with N-amino groups: synthesis and formation of boron chelates and host–guest complexes

• Artem N. Semakin,
• Ivan S. Golovanov,
• Yulia V. Nelyubina and
• Alexey Yu. Sukhorukov

Beilstein J. Org. Chem. 2022, 18, 1424–1434, doi:10.3762/bjoc.18.148

• self-assembly reactions from simple precursors and easily functionalized through addition reactions at heteroatoms [15][16][17][18][19][20]. Some time ago, our group introduced 1,4,6,10-tetraazaadamantane (TAAD) as a promising molecular platform for the design of functional tripodal molecules (Figure

Thiophene/selenophene-based S-shaped double helicenes: regioselective synthesis and structures

• Mengjie Wang,
• Lanping Dang,
• Wan Xu,
• Zhiying Ma,
• Liuliu Shao,
• Guangxia Wang,
• Chunli Li and
• Hua Wang

Beilstein J. Org. Chem. 2022, 18, 809–817, doi:10.3762/bjoc.18.81

• channels (Figures S4 and S8 in Supporting Information File 2), which is a suitable characteristic for helicene compounds used as supramolecular self-assembly units [34][35][36][37][38][39][40][41]. Spectroscopic features of DH-1–3 The UV–vis absorption spectra of DH-1–3 in dichloromethane are shown in

• arrangement in the crystal packing structures of DH-1 and DH-2 indicate that these compounds may be used as supramolecular self-assembly units. Changes in molecular structure may substantially modulate the optical band gap of heteroacenes, and the replacement of heteroatoms from S to Se could fine-tune their