Robust ring-opening reaction via asymmetrically coordinated Fe single atoms scaffolded by spoke-like mesoporous carbon nanospheres.

The ability to construct metal single-atom catalysts (SACs) asymmetrically coordinated with organic heteroatoms represents an important endeavor toward developing high-performance catalysts over symmetrically coordinated counterparts. Moreover, it is of key importance in creating supporting matrix with porous architecture for situating SACs as it greatly impacts the mass diffusion and transport of electrolyte. Herein, we report the crafting of Fe single atoms with asymmetrically coordinated nitrogen (N) and phosphorus (P) atoms scaffolded by rationally designed mesoporous carbon nanospheres (MCNs) with spoke-like nanochannels for boosting ring-opening reaction of epoxide to produce an array of pharmacologically important ß-amino alcohols. Notably, interfacial defects in MCN derived from the use of sacrificial template create abundant unpaired electrons, thereby stably anchoring N and P atoms and in turn Fe atoms on MCN. Importantly, the introduction of P atom promotes the symmetry-breaking of common four N-coordinated Fe sites, resulting in the Fe-N3P sites on MCN (denoted Fe-N3P-MCN) with an asymmetric electronic configuration and thus superior catalytic capability. As such, the Fe-N3P-MCN catalysts manifest a high catalytic activity for ring-opening reaction of epoxide (97% yield) over the Fe-N3P docked on nonporous carbon surface (91%) as well as the sole Fe-N4 SACs grounded on the same MCN support (89%). Density functional theory calculations reveal that Fe-N3P SAC lowers the activation barrier for the C-O bond cleavage and the C-N bond formation, thus accelerating the ring-opening of epoxide. Our study provides fundamental and practical insights into developing advanced catalysts in a simple and controllable manner for multistep organic reactions.

Understanding zwitterionic ring-expansion polymerization through mass spectrometry.

Zwitterionic ring-expansion polymerization (ZREP) is a polymerization method in which a cyclic monomer is converted into a cyclic polymer through a zwitterionic intermediate. In this review, we explored the ZREP of various cyclic polymers and how mass spectrometry assists in identifying the product architectures and understanding their intricate reaction mechanism. For the majority of polymers (from a few thousand to a few million Da) matrix-assisted laser desorption/ionization time-of-flight mass spectrometry is the most effective mass spectrometry technique to determine the true molecular weight (MW) of the resultant product, but only when the dispersity is low (approximately below 1.2). The key topics covered in this study were the ZREP of cyclic polyesters, cyclic polyamides, and cyclic ethers. In addition, this study also addresses a number of other preliminary topics, including the ZREP of cyclic polycarbonates, cyclic polysiloxanes, and cyclic poly(alkylene phosphates). The purity and efficiency of those syntheses largely depend on the catalyst. Among several catalysts, N-heterocyclic carbenes have exhibited high efficiency in the synthesis of cyclic polyesters and polyamides, whereas tris(pentafluorophenyl)borane [B(C6F5)3] is the most optimal catalyst for cyclic polyether synthesis.

Bimetallic Manganese Catalysts: A Route to Controlled and Switchable Polymerization of Lactones.

The sustainable solution to the environmental problem of polymeric materials calls for efficient and well-controlled ring-opening polymerization catalytic systems. Inspired by the highly reactive and stereospecific bimetallic catalysts, three kinds of bimetallic Salen-Mn catalysts supported by biaryl linking moieties are synthesized and applied to polymerization catalysis of lactide (LA) and ϵ-caprolactone (ϵ-CL) in this work. The polymerization is initiated in situ by the ring-opening of epoxide compounds, in which the ionic cocatalyst could accelerate the reaction process. The Mn-Mn coordination effect contributes to the higher activity and iso-selectivity towards LA compared to the mononuclear Salen-Mn catalyst. The reactivity and stereoselectivity are determined by the conformation of catalysts, specifically the Mn-Mn separation and dihedral angle. Finally, the CO2 -controlled switchable polymerizations are carried out with LA and ϵ-CL. The reversibility of the on-off switching operation is influenced by the combination between CO2 molecules and active species. The success in binuclear Salen-Mn catalysts not only expands the range of bimetallic catalyst analogues but also claims the promising potential of Mn-based catalysts in practical and theoretical research.

Ring-Opening of 1,3-Imidazole Based Mesoionic Carbenes (iMICs) and Ring-Closing Clicks: Facile Access to iMIC-Compounds.

Herein, ring-opening of mesoionic carbenes (iMICs) (iMIC=[ArC{N(Dipp)}2 C(SiMe3 )C:) (Dipp=2,6-iPr2 C6 H3 , Ar=Ph, 4-Me2 NC6 H4 or 4-PhC6 H4 ) based on an 1,3-imidazole scaffold to yield N-ethynylformimidamide (eFIM) derivatives as crystalline solids (eFIM={(Dipp)N=C(Ar)N(Dipp)}C≡CSiMe3 ) is reported. eFIMs are thermally stable under inert gas atmosphere and show moderate air stability (t1/2= 3 h for Ar=Ph). eFIMs are excellent surrogates of iMICs, which generally have a limited shelf-life, and readily undergo ring-closing click reactions with a variety of main-group as well as transition metal Lewis acids to form hitherto challenging iMIC-compounds in good to excellent yields. In addition to the relevance of eFIMs in the synthesis of iMIC-compounds, quantification of the stereoelectronic properties of a representative iMIC (Ar=Ph) by experimental and theoretical methods suggests remarkably σ-donor property and steric profile of these new ligand sets.

Synthesis, Structures, and Properties for PIII-Doped Hetero-Buckybowls and Their Phosphonium Salts.

Doping polycyclic aromatic hydrocarbons with heteroatoms enables manipulation of their electronic structures. Herein, the structures and properties of phosphorus (P) doped heterosumanenes (HSEs) are regulated by varying the valence states of P-dopant. The phosphine sulfide (PV) and chalcogens (S, Se, Te) co-doped HSEs (1-3) are reduced to trivalent phosphorus (PIII) doped analogues 4-6. Then, the PIII-dopants on 4-6 are converted to phosphonium salts (R4P+), giving 7-9. The valence states of P-dopant show great influence on molecular geometries and electronic structures. Taking P and S co-doped HSEs as example, bowl-depths increase in the order of 1 (PV) < 7 (R4P+) < 4 (PIII), and the HOMO energy levels and HOMO-LUMO gaps increase to be 7 < 1 < 4. Consistent with the theoretical calculation, the first oxidation potentials decrease and the absorption/emission bands show blue shift from 7 to 1 to 4. The transformation of PV to PIII leads to large variations on the coordination with Ag+, owing to the alteration of coordination site from P=S to PIII. The phosphonium salts show ring-opening of phosphole rings under electrochemical reduction. It is found that chalcogen atoms play pivotal roles on coordination patterns of coordination complexes and the conversion rates of ring-opening reactions.

Organophotocatalytic Remote Thiocyanation Reaction via Ring-Opening Functionalization of Cycloalkanols.

The remote C(sp3)-SCN bond formation via ring-opening functionalization of cycloalkanols with N-thiocyanatosaccharin as the precursor of SCN radicals and pyrylium salt as the organic photocatalyst under visible light has been developed. Thus, various terminal keto thiocyanates were prepared without transition metals and oxidants in moderate to good yields. The simplicity, wide substrate scope and mild conditions feature its synthetic application capability.

A Facile Approach to Construct Novel Polyesters as Soft Midblock for Thermoplastic Elastomers.

The development of innovative synthetic strategies to create functional polycaprolactones is highly demanded for advanced material applications. In this contribution, we reported a facile synthetic strategy to prepare a class of CL-based monomers (R-TO) derived from epoxides. They readily polymerize via well-controlled ring-opening polymerization (ROP) to afford a series of polyesters P(R-TO) with high molecular weight (Mn up to 350 kDa). Sequential addition copolymerization of MTO and L-lactide (L-LA) allowed to access of a series of ABA triblock copolymers with composition-dependent mechanical properties. Notably, P(L-LA)100-b-P(MTO)500-b-P(L-LA)100 containing the amorphous P(MTO) segment as a soft midblock and crystalline P(L-LA) domain as hard end block behaved as an excellent thermoplastic elastomer (TPE) with high elongation at break (1438±204 %), tensile strength (23.5±1.7 MPa), and outstanding elastic recovery (>88 %).

Plenty of Space in the Backbone: Radical Ring-Opening Polymerization.

Radical polymerization is the most widely applied technique in both industry and fundamental science. However, its major drawback is that it typically yields polymers with non-functional, non-degradable all-carbon backbones-a limitation that radical ring-opening polymerization (rROP) allows to overcome. The last decade has seen a surge in rROP, primarily focused on creating degradable polymers. This pursuit has resulted in the creation of the first readily degradable materials through radical polymerization. Recent years have witnessed innovations in new monomers that address previous design limitations, such as ring strain and reactivity ratios. Furthermore, advances in integrating rROP with reversible deactivation radical polymerization (RDRP) have facilitated the incorporation of complex, customizable chemical payloads into the main polymer chain. This short review discusses the latest developments in monomer design with a focused analysis of their limitations in a broader historical context. Recently evolving strategies for compatibility of rROP monomers with RDRP are discussed, which are key to precision polymer synthesis. The latest chemistry surveyed expands the horizon beyond mere hydrolytic degradation. Now is the time to explore the chemical potential residing in the previously inaccessible polymer backbone.

Skeletal Editing through Molecular Recombination of 2H-Indazoles to Azo-Linked-Quinazolinones.

A new protocol by the combinatory use of two equivalent of indazoles starting material with one being the carbon source via its C3-reactivity and the other, the coupling partner has been developed for the selectfluor-mediated single atom skeletal editing of 2H-indazoles. The azo-linked-2,3-disubstituted quinazolin-4-one derivatives were obtained through a carbon atom insertion between the two nitrogens of the indazole ring and simultaneous oxidation at C3 position of both indazole moieties. Mechanistic investigations reveal that the amidic carbonyl oxygen of the product is derived from water and the reaction proceeds through in-situ generated N-centred indazolone radical intermediate.

Gold-catalyzed endo-selective Ring-opening of Epoxides and its Application in Construction of Poly-ethers.

Tetrahydropyran and tetrahydropyran-fused poly-ethers scaffolds are found in many classes of natural products and medicinally relevant small molecules. Here we describe a catalytic system for 6-endo selective ring-opening of epoxides by Au(I) or Au(III) catalyst that provides rapid access to various tetrahydropyran-derived motifs. It also could efficiently construct the subunits of marine ladder-like poly-ethers through emulating the Nakanishi's hypothesis on the biosynthesis of these toxins. The synthetic utility of this method is also demonstrated in the preparation of the tricyclic core of tetrahydropyran-containing macrolide natural products lituarines A-C.

Skeletal Editing of Isatins for Heterocycle Molecular Diversity.

Isatins have been widely used in the preparation of a variety of heterocyclic compounds, where the skeletal editing of isatins has shown significant advantages for the construction of diverse heterocycles. This review highlights the progress made in the last decade (2013-2023) in the skeletal editing of the isatin scaffold. A series of ring expansion reactions for the construction of quinoline skeleton, quinolone skeleton, polycyclic quinazoline skeleton, medium-sized ring skeleton, as well as a series of ring opening reactions for the generation of 2-(azoly)aniline skeleton by the cleavage of C-C bond and C-N bond are highlighted. It is hoped that this review will provide some understanding of the chemical transformations of isatins and contribute to the further realization of its molecular diversity.

Ring-opening polymerization of lactide catalyzed using metal-coordinated enzyme-like amino acid assemblies.

Polylactide (PLA), a biocompatible and biodegradable polymer, is widely used in diverse biomedical applications. However, the industry standard for converting lactide into PLA involves toxic tin (Sn)-based catalysts. To mitigate the use of these harmful catalysts, other environmentally benign metal-containing agents for efficient lactide polymerization have been studied, but these alternatives are hindered by complex synthesis processes, reactivity issues, and selectivity limitations. To overcome these shortcomings, we explored the catalytic activity of Cu-(Phe)2 and Zn-(Phe)2 metal-amino acid co-assemblies as potential catalysts of the ring-opening polymerization (ROP) of lactide into PLA. Catalytic activity of the assemblies was monitored at different temperatures and solvents using 1H-NMR spectroscopy to determine the catalytic parameters. Notably, Zn-(Phe)2 achieved >99% conversion of lactide to PLA within 12 h in toluene under reflux conditions and was found to have first-order kinetics, whereas Cu-(Phe)2 exhibited significantly lower catalytic activity. Following Zn-(Phe)2-mediated catalysis, the resulting PLA had an average molecular weight of 128 kDa and a dispersity index of 1.25 as determined by gel permeation chromatography. Taken together, our minimalistic approach expands the realm of metal-amino acid-based supramolecular catalytic nanomaterials useful in the ROP of lactide. This advancement shows promise for the future design of simplified biocatalysts in both industrial and biomedical applications.

A Study of Small Molecule-Based Rhodamine-Derived Chemosensors and their Implications in Environmental and Biological Systems from 2012 to 2021: Latest Advancement and Future Prospects.

Rhodamine-based chemosensors have sparked considerable interest in recent years due to their remarkable photophysical properties, which include high absorption coefficients, exceptional quantum yields, improved photostability, and significant red shifts. This article presents an overview of the diverse fluorometric, and colorimetric sensors produced from rhodamine, as well as their applications in a wide range of fields. The ability of rhodamine-based chemosensors to detect a wide range of metal ions, including Hg+2, Al3+, Cr3+, Cu2+, Fe3+, Fe2+, Cd2+, Sn4+, Zn2+, and Pb2+, is one of their major advantages. Other applications of these sensors include dual analytes, multianalytes, and relay recognition of dual analytes. Rhodamine-based probes can also detect noble metal ions such as Au3+, Ag+, and Pt2+. They have been used to detect pH, biological species, reactive oxygen and nitrogen species, anions, and nerve agents in addition to metal ions. The probes have been engineered to undergo colorimetric or fluorometric changes upon binding to specific analytes, rendering them highly selective and sensitive by ring-opening via different mechanisms such as Photoinduced Electron Transfer (PET), Chelation Enhanced Fluorescence (CHEF), Intramolecular Charge Transfer (ICT), and Fluorescence Resonance Energy Transfer (FRET). For improved sensing performance, light-harvesting dendritic systems based on rhodamine conjugates has also been explored for enhanced sensing performance. These dendritic arrangements permit the incorporation of numerous rhodamine units, resulting in an improvement in signal amplification and sensitivity. The probes have been utilised extensively for imaging biological samples, including imaging of living cells, and for environmental research. Moreover, they have been combined into logic gates for the construction of molecular computing systems. The usage of rhodamine-based chemosensors has created significant potential in a range of disciplines, including biological and environmental sensing as well as logic gate applications. This study focuses on the work published between 2012 and 2021 and emphasises the enormous research and development potential of these probes.

Unlocking the Potential of Polythioesters.

As the demand for sustainable polymers increases, most research efforts have focused on polyesters, which can be bioderived and biodegradable. Yet analogous polythioesters, where one of the oxygen atoms has been replaced by a sulfur atom, remain a relatively untapped source of potential. The incorporation of sulfur allows the polymer to exhibit a wide range of favorable properties, such as thermal resistance, degradability, and high refractive index. Polythioester synthesis represents a frontier in research, holding the promise of paving the way for eco-friendly alternatives to conventional polyesters. Moreover, polythioester research can also open avenues to the development of sustainable and recyclable materials. In the last 25 years, many methods to synthesize polythioesters have been developed. However, to date no industrial synthesis of polythioesters has been developed due to challenges of costs, yields, and the toxicity of the by-products. This review will summarize the recent advances in polythioester synthesis, covering step-growth polymerization, ring-opening polymerization (ROP), and biosynthesis. Crucially, the benefits and challenges of the processes will be highlighted, paying particular attention to their sustainability, with the aim of encouraging further exploration and research into the fast-growing field of polythioesters.

Visible Light-Regulated Ring-Opening Polymerization of Lactones by Employing Indigo as a Photoacid Catalyst.

The development of visible light-regulated polymerizations for precision synthesis of polymers has drawn considerable attention in the past years. In this study, an ancient dye, indigo, is successfully identified as a new and efficient photoacid catalyst, which can readily promote the ring-opening polymerization of lactones under visible light irradiation in a well-controlled manner, affording the desired polyester products with predictable molecular weights and narrow dispersity. The enhanced acidity of indigos by excitation is crucial to the H-bonding activation of the lactone monomers. Chain extension and block copolymer synthesis are also demonstrated with this method.

Microstructural Analysis of Benzoxazine Cationic Ring-Opening Polymerization Pathways.

Herein, an evaluation of the initial step of benzoxazine polymerization is presented by mass spectrometry, with a focus on differentiating the phenoxy and phenolic products formed by distinct pathways of the cationic ring opening polymerization (ROP) mechanism of polybenzoxazine formation. The use of infrared multiple photon dissociation (IRMPD) and ion mobility spectrometry (IMS) techniques allows for differentiation of the two pathways and provides valuable insights into the ROP mechanism. The results suggest that type I pathway is favored in the initial stages of the reaction yielding the phenoxy product, while type II product should be observed at later stages when the phenoxy product would interconvert to the most stable type II phenolic product. Overall, the findings presented here provide important information on the initial step of the benzoxazine polymerization, allowing the development of optimal polymerization conditions and represents a way to evaluate other multifunctional polymerization processes.

From Forest to Future: Synthesis of Sustainable High Molecular Weight Polyamides Using and Investigating the AROP of ß-Pinene Lactam.

Polyamides (PA) are among the most essential and versatile polymers due to their outstanding characteristics, for example, high chemical resistance and temperature stability. Furthermore, nature-derived monomers can introduce hard-to-synthesize structures into the PAs for unique polymer properties. Pinene, as one of the most abundant terpenes in nature and its presumable stability-giving bicyclic structure, is therefore highly promising. This work presents simple anionic ring-opening polymerizations of ß-pinene lactam (AROP) in-bulk and in solution. PAs with high molecular weights, suitable for further processing, are produced. Their good mechanical, thermal (Td s up to 440 °C), and transparent appearance render them promising high-performance biomaterials. In the following, the suitability of different initiators is discussed. Thereby, it is found that NaH is the most successful for in-bulk polymerization, with a degree of polymerization (DP) of about 322. For solution-AROP, iPrMgCl·LiCl is successfully used for the first time, achieving DPs up to about 163. The obtained PAs are also hot-pressed, and the dynamic mechanical properties are analyzed.

Hybrid Photoiniferter and Ring-Opening Polymerization Yields One-Pot Anisotropic Nanorods.

Polymerization-induced self-assembly (PISA) has emerged as a scalable one-pot technique to prepare block copolymer (BCP) nanoparticles. Recently, a PISA process, that results in poly(l-lactide)-b-poly(ethylene glycol) BCP nanoparticles coined ring-opening polymerization (ROP)-induced crystallization-driven self-assembly (ROPI-CDSA), was developed. The resulting nanorods demonstrate a strong propensity for aggregation, resulting in the formation of 2D sheets and 3D networks. This article reports the synthesis of poly(N,N-dimethyl acrylamide)-b-poly(l)-lactide BCP nanoparticles by ROPI-CDSA, utilizing a two-step, one-pot approach. A dual-functionalized photoiniferter is first used for controlled radical polymerization of the acrylamido-based monomer, and the resulting polymer serves as a macroinitiator for organocatalyzed ROP to form the solvophobic polyester block. The resulting nanorods are highly stable and display anisotropy at higher molecular weights (>12k Da) and concentrations (>20% solids) than the previous report. This development expands the chemical scope of ROPI-CDSA BCPs and provides readily accessible nanorods made with biocompatible materials.

Chemical Recycling and Physical Tuning of Necklace-Shaped Polydimethylsiloxanes Bearing Anthracene Dimer Units.

The problem of plastic waste in the environment calls for the development of new polymeric materials designed specifically for easy recycling at the end of their life cycle. Herein, a green polymer system comprising a series of necklace-shaped polydimethylsiloxanes bearing anthracene dimer units is developed. The polymers have low environmental impact and are easily recycled. Further, their flexibility and glass transition temperatures are easy to control. These necklace-shaped inorganic polymers are synthesized by photopolymerizing (dimerizing) anthracene-terminated oligo-dimethylsiloxane monomers. A key achievement of the present work is the successful chemical recovery of the monomers from the polymers through thermal depolymerization, enabling monomer-polymer recycling. By applying equilibrium polymerization with base catalysts, monomers with a controlled distributed chain length are synthesized from monomers with a constant chain length. The necklace-shaped polymers synthesized from these randomized monomers have amorphous structures and readily form transparent films. It is possible to modulate the thermal and mechanical properties of the polymers by controlling the average chain length of the polydimethylsiloxane between the anthracene dimers. This investigation presents a method for the synthesis and cyclic utilization of polymer materials with a wide range of applications, including plastics and elastomers.

Polypeptide- and Protein-Based Conjugate Nanoparticles via Aqueous Ring-Opening Polymerization-Induced Self-Assembly (ROPISA).

Protein-polymer conjugates and polymeric nanomaterials hold great promise in many applications including biomaterials, medicine, or nanoelectronics. In this work, the first polymerization-induced self-assembly (PISA) approach performed in aqueous medium enabling protein-polymer conjugates and nanoparticles entirely composed of amino acids is presented by using ring-opening polymerization (ROP). It is indeed shown that aqueous ring-opening polymerization-induced self-assembly (ROPISA) can be used with protein or peptidic macroinitiators without prior chemical modification and afford the simple preparation of nanomaterials with protein-like property, for example, to implement biomimetic thermoresponsivity in drug delivery.