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1.
The ring-opening polymerization (ROP) of cyclic esters/carbonates is a crucial approach for the synthesis of biocompatible and biodegradable polyesters. Even though numerous efficient ROP catalysts have been well established, their toxicity heavily limits the biomedical applications of polyester products. To solve the toxicity issues relating to ROP catalysts, we report herein a biocompatible coordination network, CZU-1, consisting of Zn44-O)(COO)6 secondary building units (SBUs), biomedicine-relevant organic linkers and guest water, which demonstrates high potential for use in the catalytic ROP synthesis of biomedicine-applicable polyesters. Both experimental and computational results reveal that the guest water in CZU-1 plays crucial roles in the activation of the Zn44-O)(COO)6 SBUs by generating μ4-OH Brønsted acid centers and Zn–OH Lewis acid centers, having a synergistic effect on the catalytic ROP of cyclic esters. Different to the mechanism reported in the literature, we propose a new reaction pathway for the catalytic ROP reaction, which has been confirmed using density functional theory (DFT) calculations, in situ diffuse reflectance IR Fourier transform spectroscopy (DRIFTS), and matrix-assisted laser desorption/ionization time-of-flight mass spectroscopy (MALDI-TOF MS). Additionally, the hydroxyl end groups allow the polyester products to be easily post-modified with different functional moieties to tune their properties for practical applications. We particularly expect that the proposed catalytic ROP mechanism and the developed catalyst design principle will be generally applicable for the controlled synthesis of biomedicine-applicable polymeric materials.

A new ring-opening polymerization mechanism is unveiled based on synergistic catalysis involving Brønsted and Lewis acid centers in a coordination framework.  相似文献   

2.
We report the first example of controlled polymerization of poly(disulfide)s with narrow molecular weight distributions. 1,4,5-oxadithiepan-2-one (OTP), a disulfide-containing 7-membered ring lactone, was polymerized by using the diphenylphosphate (DPP) catalyzed lactone ring-opening polymerization method. The polymerization proceeded in a living manner, and the resulting polymers displayed very narrow polydispersity index (PDI) values below 1.1 and excellent backbone degradability responding to reducing conditions and UV irradiation.

We report the first example of controlled polymerization of poly(disulfide)s with narrow molecular weight distributions.  相似文献   

3.
Rapidly self-deoxygenating Cu-RDRP in aqueous media is investigated. The disproportionation of Cu(i)/Me6Tren in water towards Cu(ii) and highly reactive Cu(0) leads to O2-free reaction environments within the first seconds of the reaction, even when the reaction takes place in the open-air. By leveraging this significantly fast O2-reducing activity of the disproportionation reaction, a range of well-defined water-soluble polymers with narrow dispersity are attained in a few minutes or less. This methodology provides the ability to prepare block copolymers via sequential monomer addition with little evidence for chain termination over the lifetime of the polymerization and allows for the synthesis of star-shaped polymers with the use of multi-functional initiators. The mechanism of self-deoxygenation is elucidated with the use of various characterization tools, and the species that participate in the rapid oxygen consumption is identified and discussed in detail.

The rapidly self-deoxygenating Cu-RDRP in aqueous media is investigated.  相似文献   

4.
Polyesters are important plastics, elastomers and fibres; efficient and selective polymerizations making predictable, high molar mass polymers are required. Here, a new type of catalyst for the ring-opening polymerization (ROCOP) of epoxides and anhydrides combines unusually high chain end-group selectivity, fast rates, and good molar mass control. The organometallic heterodinuclear Al(iii)/K(i) complex, applied with a diol, is tolerant to a range of epoxides/phthalic anhydride and produces only α,ω-hydroxyl telechelic polyesters with molar masses from 6–91 kg mol−1, in all cases with monomodal distributions. As proof of its potential, high molar mass poly(vinyl cyclohexene oxide-alt-phthalic anhydride) (91 kg mol−1) shows 5× greater flexural strain at break (εb = 3.7%) and 9× higher maximum flexural stress (σf = 72.3 MPa) than the previously accessed medium molar mass samples (24 kg mol−1). It is also enchains phthalic anhydride, vinyl cyclohexene oxide and ε-decalactone, via switchable catalysis, to make high molar mass triblock polyesters (81 kg mol−1, Đ = 1.04). This selective catalyst should be used in the future to qualify the properties of these ROCOP polyesters and to tune (multi)block polymer structures.

A heterodinuclear Al(iii)/K(i) organometallic ring-opening copolymerization catalyst shows exceptional rates, end-group selectivity and good loading tolerance to deliver monodisperse polyesters with molar masses up to 91 kg mol−1.  相似文献   

5.
This review presents an updated and alternative perspective on enzymatic synthesis to obtain polyesters, with a focus on the precursor materials for absorbable sutures: poly-lactic, poly-glycolic, and poly-lactic-co-glycolic acids. Currently, the profitable path towards the industrial synthesis of polyesters is ring-opening polymerization (ROP) of lactones, which is an experimentally complex process and implies a hazardous environmental impact due to the need for energy consumption, use of large volumes of toxic organic solvents and of non-biocompatible metal-based catalysts. On the contrary, enzymatically driven reactions may be performed under mild conditions in simple reactors. Mechanistic and experimental issues of the two major biocatalyzed strategies -direct condensation and ROP- were analyzed from a green chemistry perspective. These enzyme-catalyzed poly-esterifications often return low yield and/or low final molecular weight (Mw). Considering all the analyzed published data available, possible strategies to overcome these limitations were postulated: implementation of aqueous biphasic reaction systems, use of ultrasound agitation and sequential addition of reactants or co-solvents. To promote Mw increment, post-reaction treatments can be carried out such as thermally induced short-chain polymerization under vacuum and incorporation of glycols as chain extenders.  相似文献   

6.
ATRP (atom transfer radical polymerization) is one of the most robust reversible deactivation radical polymerization (RDRP) systems. However, the limited oxygen tolerance of conventional ATRP impedes its practical use in an ambient atmosphere. In this work, we developed a fully oxygen-tolerant PICAR (photoinduced initiators for continuous activator regeneration) ATRP process occurring in both water and organic solvents in an open reaction vessel. Continuous regeneration of the oxidized form of the copper catalyst with sodium pyruvate through UV excitation allowed the chemical removal of oxygen from the reaction mixture while maintaining a well-controlled polymerization of N-isopropylacrylamide (NIPAM) or methyl acrylate (MA) monomers. The polymerizations of NIPAM were conducted with 250 ppm (with respect to the monomer) or lower concentrations of CuBr2 and a tris[2-(dimethylamino)ethyl]amine ligand. The polymers were synthesized to nearly quantitative monomer conversions (>99%), high molecular weights (Mn > 270 000), and low dispersities (1.16 < Đ < 1.44) in less than 30 min under biologically relevant conditions. The reported method provided a well-controlled ATRP (Đ = 1.16) of MA in dimethyl sulfoxide despite oxygen diffusion from the atmosphere into the reaction system.

A novel photoinduced ATRP system enabling a well-controlled polymerization in both aqueous and organic solvents in an ambient atmosphere.  相似文献   

7.
以三氟甲烷磺酸亚锡为催化剂, 2-巯基乙醇为引发剂, 在温和条件下引发ε-己内酯的开环聚合, 得到端基为巯基的聚己内酯, 其分子量可控且分布较窄. 在此过程中, 巯基不需要保护而不会影响聚酯的结构, 当聚合温度升高时, 聚合物端基结构不发生改变, 但分子量分布变宽. 端基为巯基的聚己内酯能够通过偶合反应生成中间含二硫键的聚己内酯; 同时, 以2-羟乙基二硫化合物为引发剂合成得到分子中间含二硫键的窄分布聚己内酯, 经还原后也可得到端基为巯基的聚己内酯. 这两种方法条件温和, 效率较高, 具有良好的可控性.  相似文献   

8.
Carrying out the in vivo syntheses of drugs toxic to tumors based on the specific features of the tumor microenvironment is critical for ensuring specific antitumor efficacy. However, achieving in situ high-yield synthetic toxic drugs from non-toxic agents and reducing their drug resistance in hypoxic tumors remain challenges. Herein we created a tumor-microenvironment-responsive porous Pt/Pt(iv) methylene blue coordination polymer nanoshuttle (Pt/PtMBCPNS) photosensitizer with spatiotemporally controlled O2 and singlet oxygen (1O2) self-sufficient for the in vivo high-yield synthesis of drugs and efficient hypoxic tumor therapy. After being endocytosed, the nanophotosensitizer as a cascade catalyst was observed to effectively catalyze the conversion of endogenous H2O2 to O2, and was hence found to play a dual role in the enhanced tumor therapy. PtMBCPNSs, upon being irradiated with red light, efficiently converted O2 into 1O2. Subsequently, 1O2 oxidized non-toxic 1,5-dihydroxynaphthalene to form the anticancer agent juglone with a high yield. In addition, O2 was found to be able to improve the hypoxic microenvironment without light irradiation, thus enhancing the antitumor efficacy of the produced drugs and reducing drug resistance. As a result, by enhancing the synergistic effect of the treatment, this nanophotosensitizer significantly inhibited the growth of tumors and avoided damage to normal tissues/organs. Collectively, this work highlights a robust nanoplatform with the spatiotemporally controlled in vivo high-yield synthesis of drugs and generation of O2 to help overcome the current limitations of chemical-based therapies against hypoxic tumors.

A porous photosensitizer displaying catalase-like activity and drug synthesis ability was synthesized for the synergistic chemo-photodynamic therapy, opening new promising ways for carrying out the precise cooperative treatment of hypoxic tumors.  相似文献   

9.
The need for a scalable synthesis of not sequence defined polypeptides as biomaterials is met by the ring-opening polymerization of α-amino acid N-carboxyanhydrides (NCAs). Even though this polymerization technique appears straight forward, it holds pitfalls in terms of reproducibility and overall control over the polymerization conditions, which depends, beside choice of solvent or initiator, significantly on reagent purity. In addition, the synthesis of monomers can lead to the formation of racemic amino acids. Thus, in this work, we describe the benefits of highly pure monomers in order to control nucleophilic ring-opening polymerization NCAs. Hereby, monomer purity is investigated by relating melting points of NCAs with single-crystal and powder X-ray diffraction crystallography data, which further proves retained stereo-information of NCAs.  相似文献   

10.
The rapid development of new applications of photoredox catalysis has so far outpaced the mechanistic studies important for rational design of new classes of catalysts. Here, we report the use of ultrafast transient absorption spectroscopic methods to reveal both mechanistic and kinetic details of multiple sequential steps involved in an organocatalyzed atom transfer radical polymerization reaction. The polymerization system studied involves a N,N-diaryl dihydrophenazine photocatalyst, a radical initiator (methyl 2-bromopropionate) and a monomer (isoprene). Time-resolved spectroscopic measurements spanning sub-picosecond to microseconds (i.e., almost 8 orders of magnitude of time) track the formation and loss of key reactive intermediates. These measurements identify both the excited state of the photocatalyst responsible for electron transfer and the radical intermediates participating in propagation reactions, as well as quantifying their lifetimes. The outcomes connect the properties of N,N-diaryl dihydrophenazine organic photocatalysts with the rates of sequential steps in the catalytic cycle.

Short-lived intermediates are tracked in real-time by transient absorption spectroscopy during a multi-step photoredox catalysed polymerization reaction.  相似文献   

11.
As a natural diterpenoid, crotophorbolone possesses a challenging trans,trans-5/7/6 framework decorated with six contiguous stereogenic centers and is structurally and biogenetically related to tigliane-type diterpenoids with intriguing bioactivities such as phorbol and prostratin. Based on the convergent strategy, we completed an eighteen-step total synthesis of crotophorbolone starting from (−)-carvone and (+)-dimethyl-2,3-O-isopropylidene-l-tartrate. The key elements of the synthesis involve expedient installation of the six-membered ring and the five-membered ring with multiple functional groups at an early stage, cyclization of the seven-membered ring through alkenylation of the ketone between the five-membered ring and the six-membered ring, functional group-sensitive ring-closing metathesis and final selective introduction of hydroxyls at C20 and C4.

Convergent total synthesis of crotophorbolone was accomplished in 18 longest linear steps. Observation of unexpected thermodynamic stability of a cis,trans-5/7/6 tricycle would benefit synthetic design of tigliane- and daphnane-related diterpenoids.  相似文献   

12.
Heterometallic cooperativity is an emerging strategy to elevate polymerisation catalyst performance. Here, we report the first heterotrimetallic Na/Zn2 and K/Zn2 complexes supported by a ProPhenol ligand, which deliver “best of both” in cyclic ester ring-opening polymerisation, combining the outstanding activity (Na/K) and good control (Zn2) of homometallic analogues. Detailed NMR studies and density-functional theory calculations suggest that the Na/Zn2 and K/Zn2 complexes retain their heterometallic structures in the solution-state. To the best of our knowledge, the K/Zn2 analogue is the most active heterometallic catalyst reported for rac-lactide polymerisation (kobs = 1.7 × 10−2 s−1), giving activities five times faster than the Na/Zn2 complex. These versatile catalysts also display outstanding performance in ε-caprolatone and δ-valerolactone ring-opening polymerisation. These studies provide underpinning methodologies for future heterometallic polymerisation catalyst design, both in cyclic ester polymerisation and other ring-opening (co)polymerisation reactions.

Cooperative heterotrimetallic Na/Zn2 and K/Zn2 complexes combine the excellent activities and control of the homometallic analogues, giving “best of both” in cyclic ester ring-opening polymerisation.  相似文献   

13.
Even though the transformation of syngas into aromatics has been realized via a methanol-mediated tandem process, the low product yield is still the bottleneck, limiting the industrial application of this technology. Herein, a tailor-made zeolite capsule catalyst with Ga doping and SiO2 coating was combined with the methanol synthesis catalyst Cr2O3 to boost the synthesis of value-added aromatics, especially para-xylene, from syngas. Multiple characterization studies, control experiments, and density functional theory (DFT) calculation results clarified that Ga doped zeolites with strong CO adsorption capability facilitated the transformation of the reaction intermediate methanol by optimizing the first C–C coupling step under a high-pressure CO atmosphere, thereby driving the reaction forward for aromatics synthesis. This work not only reveals the synergistic catalytic network in the tandem process but also sheds new light on principles for the rational design of a catalyst in terms of oriented conversion of syngas.

The single-pass conversion of syngas into para-xylene was realized using a bifunctional catalyst Cr2O3/Ga-ZSM-5@SiO2. The Ga species facilitates the methanol consumption process by C–C coupling optimization, enhancing the yield of the target aromatics.  相似文献   

14.
We report the alternating copolymerization of caprolactone and epoxide through the in situ formation of pre-sequenced spiroorthoester monomer. The reaction is catalyzed by the temperature triggered, bifunctional cationic indium complex (±)-[(NNiOtBu)In(CH2SiMe3)][B(C6F5)4] (1). 1 can catalyze the coupling of epoxide and lactone to form spiroorthoester at 60 °C and its double ring-opening polymerization at 110 °C to form poly(ether-alt-ester). The post-polymerization modification and degradation of the poly(ether-alt-ester) are further investigated.

We report the alternating copolymerization of caprolactone and epoxide through the in situ formation of pre-sequenced spiroorthoester monomer.  相似文献   

15.
The ring-opening oxidative amination of methylenecyclopropanes (MCPs) with diazenes catalyzed by py3TiCl2(NR) complexes is reported. This reaction selectively generates branched α-methylene imines as opposed to linear α,β-unsaturated imines, which are difficult to access via other methods. Products can be isolated as the imine or hydrolyzed to the corresponding ketone in good yields. Mechanistic investigation via density functional theory suggests that the regioselectivity of these products results from a Curtin–Hammett kinetic scenario, where reversible β-carbon elimination of a spirocyclic [2 + 2] azatitanacyclobutene intermediate is followed by selectivity-determining β-hydrogen elimination of the resulting metallacycle. Further functionalizations of these branched α-methylene imine products are explored, demonstrating their utility as building blocks.

The ring-opening oxidative amination of methylenecyclopropanes (MCPs) with diazenes catalyzed by py3TiCl2(NR) complexes is reported.  相似文献   

16.
Polypeptide/inorganic hybrid copolymers were obtained by a four-step synthetic approach combining (i) atom transfer polymerization of tert-butyl acrylate, (ii) chemical modification of the bromo end groups of ATRP-polymers into primary amino group using Gabriel reaction, (iii) ring opening polymerization of Nε-trifluoroacetyl-l-lysine or γ-benzyl-l-glutamate N-carboxyanhydrides followed by (iv) the transamidification reaction using a large excess of (3-aminopropyl)trimethoxysilane to substitute the tert-butyl groups of the poly(tert-butyl acrylate) block. Products were characterized using 1H NMR, FT-IR, DSC and MALDI-TOF MS. These techniques proved that polymerization of tert-butyl acrylate was controlled whatever the molecular weight targeted and that bromide was quantitatively converted to amino end group by a original method leading to the synthesis of copolymers in the presence of N-carboxyanhydrides as monomers. Amphiphilic polypeptide/inorganic hybrid copolymers were then achieved.  相似文献   

17.
Higher ring-opening metathesis propagation rates of exo-norbornene derivatives over endo derivatives are well established in the literature. Here, we report for the first time that endo-isomers of oxanorbornene derivatives show higher reactivity towards ring-opening metathesis with Grubbs'' 3rd generation catalyst (G3) than the corresponding exo-isomers. A very high selectivity for the reaction of G3 with endo over the exo-isomers could be shown. Furthermore, single molecular addition of the endo-isomers with G3 was observed. On the other hand, pure exo-monomers could successfully be homopolymerized. Mixtures of exo- and endo- monomers, however, prevented the homopolymerization of the exo-monomer. Such mixtures could successfully be copolymerized with cycloalkenes, resulting in alternating copolymers. An oxanorbornadiene derivative could be shown to undergo single addition reactions, exploited in the preparation of mono-end functional ROMP polymers. These could be selectively derivatized via endgroup selective thiol-ene click reactions. A thiol and alcohol end functional ROMP polymer was synthesized, and the efficient end functionalization was confirmed by 1H NMR spectroscopy and MALDI-ToF spectrometry.

Bridgehead revisited: endo-7-oxa norborneneimide derivatives (green) initiate faster but propagate more slowly than the analogous exo-derivatives (red) in ring-opening metathesis allowing the synthesis of alternating and end functional polymers.  相似文献   

18.
Poly(hexamethylene terephthalate) was cyclo-depolymerized in solution by heating to yield a fraction of cyclic oligomers of hexamethylene terephthalate (c(HT)2-5) with a content around to 95% in dimer to pentamer. Ring-opening polymerization in the melt of c(HT)2-5, either neat or in mixtures with ε-caprolactone (CL) covering a range of HT/CL ratios from 9/1 to 1/9 was carried out to produce polyesters with molecular weights above 30,000 in high yields. The copolyesters had a comonomer composition according to the feed and the microstructure evolved from random to blocky as the content in CL increases. The thermal and mechanical properties of the copolyesters were evaluated for a variety of compositions. Results obtained in this work were compared to those previously obtained by us in the ring-opening copolymerization of CL with a cyclic oligomeric fraction enriched in hexamer and heptamer (c(HT)6-7). Although the polyesters resulting from the use of these two fractions were similar, significant differences were found in polymerization rate evidencing a lower reactivity of c(HT)n with decreasing values of n.  相似文献   

19.
The ring-opening polymerization of 1,4,8-trioxaspiro-[4.6]-9-undecanone (TOSUO) initiated by aluminum isopropoxide, Al(OiPr)3, is typically “living” and allows random and block copolyesters of predictable molecular weight and composition to be prepared. Deacetalization of the polyester chains is complete, and reduction of the accordingly formed ketone groups into hydroxyl groups as well. No chain scission is observed when these two derivatization reactions are carried out. The potential of these novel functional aliphatic polyesters has been discussed as drug colloidal vectors and macroinitiators for the synthesis of biodegradable and biocompatible comb, graft and even hyperbranched polymers.  相似文献   

20.
Photoredox catalysts are integral components of artificial photosystems, and have recently emerged as powerful tools for catalysing numerous organic reactions. However, the development of inexpensive and efficient earth-abundant photoredox catalysts remains a challenge. We here present the photochemical and photophysical properties of a Ni–Mabiq catalyst ([NiII(Mabiq)]OTf (1); Mabiq = 2-4:6-8-bis(3,3,4,4-tetramethyldihydropyrrolo)-10-15-(2,2-biquinazolino)-[15]-1,3,5,8,10,14-hexaene1,3,7,9,11,14-N6)—and of a Zn-containing analogue ([ZnII(Mabiq)OTf] (2))—using steady state and time resolved optical spectroscopy, time-dependent density functional theory (TDDFT) calculations, and reactivity studies. The Ni and Zn complexes exhibit similar absorption spectra, but markedly different photochemical properties. These differences arise because the excited states of 2 are ligand-localized, whereas metal-centered states account for the photoactivity of 1. The distinct properties of the Ni and Zn complexes are manifest in their behavior in the photo-driven aza-Henry reaction and oxidative coupling of methoxybenzylamine.

The development of earth-abundant photoredox catalysts remains a challenge. Studies of Ni- and Zn-Mabiq complexes demonstrate how the coordinating metal ion influences the photochemistry, photodynamics and reactivity of photocatalysts.  相似文献   

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