From oxygenated monomers to well-defined low-carbon polymers

The synthesis of degradable polymers with easy-to-break in-chain carbon-oxygen bonds has attracted much attention.This minireview introduces the synthesis of a variety of degradable polymers from the(co)polymerizations of several typical oxygenated monomers such as epoxides,cyclic carbonates,cyclic esters,carbon dioxide(CO_(2)),carbonyl sulfide(COS),and cyclic anhydrides.We highlight the catalysts and mechanisms for these(co)polymerizations.The ring-opening copolymerization of five-membered carbonate with cyclic anhydride or COS has been introduced.We also highlight the synthesis of block copolymers and cyclic copolymers with well-defined sequences by the method of growing center switching.We hope that these new polymerization systems can provide new ideas for the development of degradable low-carbon polymers in the future.

Polymeric aluminum porphyrin:Controllable synthesis of ultra-low molecular weight CO_(2)-based polyols

Carbon dioxide-based polyols with ultra-low molecular weight(ULMW,Mn<1000 g/mol)are emergent polyurethane precursors with economic and environmental benefits.However,the lack of effective proton-tolerant catalytic systems limits the development of this field.In this work,the polymeric aluminum porphyrin catalyst(PAPC)system was applied to the copolymerization of CO_(2)and propylene oxide,where sebacic acid,bisphenol A,poly(ethylene glycol),and water were used as chain transfer agents to achieve the controlled synthesis of CO_(2)-polyols.The molecular weight of the resulting CO_(2)-polyols could be facilely regulated in the range of 400–930 g/mol at low catalyst loadings,fully demonstrating its catalytic advantages of high activity,high product selectivity,and excellent proton tolerance of PAPC.Meanwhile,the catalytic efficiency of PAPC could reach up to 2.1–5.2 kg/g under organic CTA conditions,even reaching 1.9 kg/g using water as the CTA.The cPC content could be controlled within 1.0 wt%under the optimized conditions,indicating the excellent controllability of the PAPC system.ULMW CO_(2)-polyols combines the advantages of low viscosity(∼3000 mPa s at 25°C),low glass transition temperature(∼−73°C),and high carbonate unit content(∼40%),which is important for the development of high-performance polyurethanes.

Polymeric catalyst with polymerization-enhanced Lewis acidity for CO_(2)-based copolymers

Ring-opening copolymerization of CO_(2) and epoxides is a promising way to manufacture high value-added materials.Despite a variety of catalyst systems have been reported,the reaction is still limited by low activity and polymer selectivity.Herein,a strategy of polymerization-enhanced Lewis acidity is reported to construct a series of highly efficient polymeric aluminum porphyrin catalysts(PAPCs).The characterization of the coordination equilibrium constant(K_(eq))showed significantly enhanced Lewis acidity of PAPC(K_(eg)=18.2 L/mol)compared to the monomeric counterpart(K_(eq)=6.4 L/mol),accompanied with increased turnover frequency(TOF)from 136 h^(-1) to 5500 h^(-1).Through detailed regulation of Lewis acidity,the highly Lewis acidic PAPC-OTs displayed a record high TOF of 30,200 h^(-1) with polymer selectivity of up to 99%.

Unity Makes Strength:Constructing Polymeric Catalyst for Selective Synthesis of CO_(2)/Epoxide Copolymer

Catalyst design strategies such as bi-functional and di-nuclear catalysts have been developed based on intramolecular interactions,achieving excellent catalytic performance.However,most of these catalysts work in a state of disunity.To make progress in this direction,we reckoned that enhancing the neglected intermolecular interactions of these catalysts might be a suitable approach.Herein,we report a strategy of constructing homogeneous polymeric catalysts based on the philosophy of“unity makes strength”to convert the intermolecular interactions into stronger intramolecular interactions.We united discrete active centers of aluminum(Al)porphyrin and tertiary amine(methyl methacrylate;MMA)via a random copolymerization process into one polymer chain with the subsequent metallization using low-toxic metal AlEt_(2)Cl,to construct polymeric catalysts for selective copolymerization of CO_(2)/epoxide.The spatial confinement enabled the multiple interactions among the active centers,which was distinct from the“point-to-point”interacting systems such as binary,bi-functional,or di-nuclear complexes.Through detailed tuning of the multiple synergistic effects between porphyrin/porphyrin(metal synergistic effect)and Al porphyrin/tertiary amine(Lewis pair effect),the optimized polymeric catalyst showed significantly boosted catalytic activity of 4300 h^(−1),much higher than their mono-nuclear(∼0 h^(−1))and homo-polymeric(750 h^(−1))counterparts.Our present approach for designing polymeric catalysts based on multiple synergistic effects provides a platform for developing highly active catalysts.

Genetically engineered bacterial-like particles induced specific cellular and humoral immunity as effective tick-borne encephalitis virus vaccine

Tick-borne encephalitis(TBE)is a natural focal disease with fatal encephalitis induced by tick-borne encephalitis virus(TBEV),seriously threatening human and public health.Protection of TBE depends on vaccination with inactivated vaccine,which requires high cost and multiple immunizations.Here,we construct genetically engineered bacterial-like particles(BLPs)as an effective TBEV vaccine with simplified immunizations and improved immune efficacy.The TBEV BLPs involve the combination of the gram-positive enhancer matrix from Lactococcus lactis,and TBEV envelope(E)protein expressed by genetically engineered recombinant baculovirus.The prepared TBEV BLPs can effectively stimulate the activation of dendritic cells to present the TBEV E proteins to T and B cells,leading to strong and durable cellular and humoral immune responses in mice.Surprisingly,the serum levels of specific IgG antibodies in mice remain about 10^(6)at 6 months after the secondary immunization.Overall,the TBEV BLPs can be used as a potent vaccine candidate,laying the foundation for developing novel TBEV genetically engineered vaccines.

Organic near-infrared photodetectors with photoconductivityenhanced performance

Organic near-infrared(NIR)photodetectors with essential applications in medical diagnostics,night vision,remote sensing,and optical communications have attracted intensive research interest.Compared with most conventional inorganic counterparts,organic semiconductors usually have higher absorption coefficients,and their thin active layer could be sufficient to absorb most incident light for effective photogeneration.However,due to the relatively poor charge mobility of organic materials,it remains challenging to inhibit the photogenerated exciton recombination and effectively extract carriers to their respective electrodes.Herein,this challenge was addressed by increasing matrix conductivities of a ternary active layer(D–A–D structure NIR absorber[2TT-oC6B]:poly(N,N′-bis-4-butylphenyl-N,N′-bisphenyl)benzidin[PolyTPD]:[6,6]-phenyl-C61-butyric acid methyl ester[PCBM]=1:1:1)upon in situ incident light illumination,significantly accelerating charge transport through percolated interpenetrating paths.The greatly enhanced photoconductivity under illumination is intrinsically related to the unique donor–acceptor molecular structures of PolyTPD and 2TT-oC6B,whereas stable intermolecular interaction has been verified by systematic molecular dynamics simulation.In addition,an ultrafast charge transfer time of 0.56 ps from the NIR aggregation-induced luminogens of 2TT-oC6B absorber to PolyTPD and PCBM measured by femtosecond transient absorption spectroscopy is beneficial for effective exciton dissociation.The solution-processed organic NIR photodetector exhibits a fast response time of 83μs and a linear dynamic range value of 111 dB under illumination of 830 nm.Therefore,our work has opened up a pioneering window to enhance photoconductivity through in situ photoirradiation and benefit NIR photodetectors as well as other optoelectronic devices.

Rational design of AIE-active biodegradable polycarbonates for high-performance WLED and selective detection of nitroaromatic explosives

Luminescent polymers have garnered considerable research attention for their excellent properties and wide range of applications in multi-responsive materials,bioimaging,and photoelectric devices.Thereout,various modulations of polymer structure are often the main approach to obtaining materials with different luminescent colors and functions.However,polymers with biodegradability,tunable color,and efficient emission simultaneously remain a challenge.Herein,we report a feasible strategy to achieve degradable and highly emissive polymers by exquisite combination and interplay of aggregation-induced emission(AIE)unit and environmental-friendly epoxide/CO_(2)copolymerization.A series of polycarbonates P-TEP_(x)CN_(y)(x=0,1,2,4,30,120;y=0,1)were prepared,with emission color changed from blue to yellow by controlling the proportion of two designed AIE-active monomers.Among them,Using P-TCN as emitting layer,high performance white light-emitting diode(WLED)device with an external quantum efficiency(EQE)of 26.09%and CIE coordinates of(0.32,0.32)was achieved.In addition,the designed polymers can be used as selective sensors for nitroaromatic compounds in their nanoaggregate states.

Emission Properties of Individual AIE-Luminogens in Solution at Room Temperature

Here,we combined the photon antibunching analysis,fluorescence correlation spectroscopy,and time-domain fluorescence lifetime imaging microscopy(TD-FLIM)to study the emission properties of a representative AIE-luminogen—4,4’-(benzo[c][1,2,5]thiadiazole-4,7-diyl)bis(N,N-diphenylaniline)(TPA-BT)at the single emitter level in a tetrahydrofuran(THF)/water solution where water is a non-solvent for TPA-BT.Our findings suggest that,at a constant water fraction in the solution,the size of TPA-BT aggregates increases with the TPA-BT concentration;TPA-BT aggregates are not a quantum emitter at room temperature in the solution.Moreover,utilizing TD-FLIM and a gel trapping technique allowed us to study the fluorescence lifetime of individual TPA-BT aggregates.Adding a polar solvent like water does not result in an overall decrease in fluorescence lifetime.Rather,it causes the fluorescence lifetime distribution to become wider,and only some molecules experience a decrease in their fluorescence lifetime.These results could represent a step forward in further understanding the photophysics of AIE-luminogens.

Photodegradation-Induced Turn-On Luminescence of Tetraphenylethylene-Based Trithiocarbonate Polymers

Main observation and conclusion Fluorescent intelligent materials have attracted wide attention because of their great potential applications.One major hurdle for the development and application of fluorescent intelligent materials is the aggregation-caused quenching effect in the solid state.Herein,tetraphenylethylene-based trithiocarbonate polymers with satisfactory molecular weights(Mw up to 24900)were synthesized through a one-pot polymerization route under mild conditions.The polymers were non-emissive due to the quenching effect of the trithiocarbonate group.However,upon UV irradiation,the polymers degraded and strong emission from the tetraphenylethylene unit was observed.Such a unique property endows them with great potential applications,such as photopatterning,anti-counterfeit labels,and UV detection.

Environmentally benign metal catalyst for the ring-opening copolymerization of epoxide and CO_(2): state-of-the-art, opportunities, and challenges

Carbon dioxide(CO_(2))is the main greenhouse gas,whereas it is also a nontoxic,abundant,cheap carbon and oxygen resource.The copolymerization of CO_(2) with epoxide presents a sustainable approach to the synthesis of biodegradable polymers,which upcycles the waste into wealth.Metal complex catalyst plays the central role in the reaction,since it provides oxophilic and Lewis acidic active center both for monomer activation and chain end stabilization,and nucleophiles as Lewis base for initiation.However,heavy metal catalyst with certain toxicity such as cobalt undisputedly dominates the copolymerization catalysis which comprises the overall sustainability.To circumvent the potential environmental hazard,developing highly active catalyst composed of green metals is of great importance especially when the polymer was utilized for agriculture purpose.This work reviews the development of sustainable metal catalysts for the production of CO_(2) copolymer,centered by Al,Mg,Ti,Fe,generally acknowledged as low toxic,environmentally benign,biocompatible,and also abundant in earth's crust.Emphasis is placed in recent five years where several historic examples are also included to construct a full picture of the sustainable catalysis explored to date.

Construction of Self-Reporting Biodegradable CO_(2)-Based Polycarbonates for the Visualization of Thermoresponsive Behavior with Aggregation-Induced Emission Technology

Thermoresponsive polymers with simultaneous biodegradability and signal“self-reporting”outputs that meet for advanced applications are hard to obtain.To address this issue,we developed fluorescence signal“self-reporting”biodegradable thermoresponsive polycarbonates through the immortal copolymerization of CO_(2)and oligoethylene glycol monomethyl ether-functionalized epoxides in the presence of hydroxyl-modified tetraphenylethylene(TPE-OH).TPE-OH was used as chain transfer agent to afford well-defined polycarbonates with controlled molecular weight(6000—17000 g·mol^(–1))and aggregation-induced emission characteristics.Through temperature-dependent fluorescence intensity study,low critical solution transition of TPE-labeled polycarbonates were determined and the fine details of thermal-induced phase transition process were monitored.Further research indicated that temperature-controlled aggregation and dissociation of TPE moieties are the main reason for fluorescence intensity variations.We anticipate that this work could offer a method to visualize the thermal transition process of thermoresponsive polycarbonates and broaden their application fields as smart materials.

Chain-transfer-catalyst: strategy for construction of site-specific functional CO_(2)-based polycarbonates

Site-specific functional polymers are generally synthesized from functionalized chain transfer agents(CTA)in the presence of catalysts.However,the poor solubility or chemical inertness of CTAs may make polymerizations uncontrollable.Now,this issue is addressed by proposing a strategy of designing chain-transfer-catalyst(CTC)that combines catalyst and CTA into one.The occurrence of catalytic effect naturally triggers the chain transfer process to give catalyst-labeled polymers with well-defined structures.As a proof-of-concept,cobalt(III)porphyrin catalysts with one,two and four hydroxyl groups act as efficient CTCs,giving the corresponding site-specific functional poly(propylene carbonate)s(PPC),diversifying the topology of polymers.Furthermore,porphyrin-capped PPCs with controllable Mn in the range of 1,000–16,800 g mol^(-1)were obtained by using monofunctional CTC(CTCOH).Moreover,different from traditional“catalyst+CTA”systems,a novel dynamic network transfer mechanism of CTCOH was proposed.This study provides a CTC strategy for the synthesis of site-specific functional polymers.

Controlled synthesis of CO_2-diol from renewable starter by reducing acid value through preactivation approach

Synthesis of polyols from carbon dioxide（CO2） is attractive from the viewpoint of sustainable development of polyurethane industry;it is also interesting to adjust the structure of the CO2-polyols for versatile requirement of polyurethane.However,when renewable malonic acid was used as a starter,the copolymerization reaction of CO2 and propylene oxide（PO） was uncontrollable,since it proceeded slowly（13 h） and produced 40.4 wt%of byproduct propylene carbonate（PC） with a low productivity of 0.34kg/g.A careful analysis disclosed that the acid value of the copolymerization medium was the key factor for controlling the copolymerization reaction.Therefore,a preactivation approach was developed to dramatically reduce the acid value to 0.6mg（KOH）/gby homopolymerization of PO into oligo-ether-diol under the initiation of malonic acid,which ensured the controllable copolymerization,where the copolymerization time could be shortened by 77%from 13 to 3 h,the PC content was reduced by 76%from 40.4 wt%to 9.4 wt%,and the productivity increased by 61%from 0.34 to 0.55 kg/g.Moreover,by means of preactivation approach,the molecular weight as well as the carbonate unit content in the CO2-diol was also controllable.