Molecular Weight Mn Research Articles

Biomass-based renewable, eco-friendly nanofiber membrane: Large-scale fabrication and application in PM0.3 capture and oily wastewater purification

Biomass-based poly (trimethylene 2,5-furandicarboxylate) (PTF) was synthesized by the simple and low-cost direct esterification method. The high number-average molecular weight (Mn) of about 39.6 kDa was achieved for PTF with a polydispersity index (PDI) of 2.0, which was suitable for spinning. The electrospun PTF nanofiber membranes were fabricated firstly and displayed adjustable diameters, excellent mechanical properties (lifting 550 g weight, foldability) and large-scale preparation potential (area of 100 cm × 50 cm). More impressively, high initial surface potential (13.5 kV) was found for the electrospun in-suit electret membranes, which facilitated the capture of ultrafine PM particles. Subsequently, the PTF membrane showed exceptional particle capture capability with a filtration performance of 99.96 %, low pressure drops of 78 Pa, and a satisfactory quality factor of 0.1 Pa−1. PTF filters also demonstrated long-term service capability for purifying high PM2.5 concentration smoke (15 cycles, 55 min), and could be flexibly introduced into various practical scenarios. Additionally, based on the selective oil/water wettability of PTF membranes, which showed outstanding separation effects of oily wastewater(＞99.88 %, 15 cycles). Therefore, the development and application of the PTF nanofibers provided a sustainable alternative for separation/purification and various fields in the future.

Random Terpolymer of Carbon Dioxide, Butadiene and Epoxides: Synthesis, Functionalization and Degradability

Comprehensive SummaryThe utilization of carbon dioxide (CO2) as a C1 feedstock is consistently attractive, especially in the preparation of sustainable polymeric materials. In this contribution, a terpolymer of CO2, 1,3‐butadiene (BD) and epoxide is synthesized by scandium triflate catalyzed cationic ring‐opening copolymerization of α‐ethylidene‐δ‐vinyl‐δ‐valerolactone (EVL), an intermediate derived from CO2 and BD, with epoxides. The obtained terpolymer with a CO2 content of 22 mol% has a number‐average molecular weight (Mn) up to 7.8 kg/mol and a dispersity (Đ) of 2.4. The reactivity ratios of EVL and cyclohexene oxide (CHO) are determined as 0.01 and 1.07, respectively, suggesting random characteristic of the terpolymer. The preserved C=C double bonds from BD allow for the further modification of the terpolymer by photoinitiated crosslinking. The yielded networks are fluorescent and degradable. This method offers enhanced versatility to the synthesis and additional functionalization of CO2‐based polymers.

High Molar Mass Polycarbonates as Closed-Loop Recyclable Thermoplastics.

Using carbon dioxide (CO2) to make recyclable thermoplastics could reduce greenhouse gas emissions associated with polymer manufacturing. CO2/cyclic epoxide ring-opening copolymerization (ROCOP) allows for >30 wt % of the polycarbonate to derive from CO2; so far, the field has largely focused on oligocarbonates. In contrast, efficient catalysts for high molar mass polycarbonates are underinvestigated, and the resulting thermoplastic structure-property relationships, processing, and recycling need to be elucidated. This work describes a new organometallic Mg(II)Co(II) catalyst that combines high productivity, low loading tolerance, and the highest polymerization control to yield polycarbonates with number average molecular weight (Mn) values from 4 to 130 kg mol-1, with narrow, monomodal distributions. It is used in the ROCOP of CO2 with bicyclic epoxides to produce a series of samples, each with Mn > 100 kg mol-1, of poly(cyclohexene carbonate) (PCHC), poly(vinyl-cyclohexene carbonate) (PvCHC), poly(ethyl-cyclohexene carbonate) (PeCHC, by hydrogenation of PvCHC), and poly(cyclopentene carbonate) (PCPC). All these materials are amorphous thermoplastics, with high glass transition temperatures (85 < Tg < 126 °C, by differential scanning calorimetry) and high thermal stability (Td > 260 °C). The cyclic ring substituents mediate the materials' chain entanglements, viscosity, and glass transition temperatures. Specifically, PCPC was found to have 10× lower entanglement molecular weight (Me)n and 100× lower zero-shear viscosity compared to those of PCHC, showing potential as a future thermoplastic. All these high molecular weight polymers are fully recyclable, either by reprocessing or by using the Mg(II)Co(II) catalyst for highly selective depolymerizations to epoxides and CO2. PCPC shows the fastest depolymerization rates, achieving an activity of 2500 h-1 and >99% selectivity for cyclopentene oxide and CO2.

Topology Controlled All-(Meth)acrylic Thermoplastic Elastomers by Multi-Functional Lewis Pairs-Mediated Polymerization.

It remains challenging to synthesize all-(meth)acrylic triblock thermoplastic elastomers (TPEs), due to the drastically different reactivities between the acrylates and methacrylates and inevitable occurrence of side reactions during polymerization of acrylates. By taking advantage of the easy structural modulation features of N-heterocyclic olefins (NHOs), we design and synthesize strong nucleophilic tetraphenylethylene-based NHOs varying in the number (i.e. mono-, dual- and tetra-) of initiating functional groups. Its combination with bulky organoaluminum [iBuAl(BHT)2] (BHT=bis(2,6-di-tBu-4-methylphenoxy)) constructs Lewis pair (LP) to realize the living polymerization of both acrylates and methacrylates, furnishing polyacrylates with ultrahigh molecular weight (Mn up to 2174 kg ⋅ mol-1) within 4 min. Moreover, these NHO-based LPs enable us to not only realize the control over the polymers' topology (i.e. linear and star), but also achieve triblock star copolymers in one-step manner. Mechanical studies reveal that the star triblock TPEs exhibit better mechanical properties (elongation at break up to 1863 % and tensile strength up to 19.1 MPa) in comparison with the linear analogs. Moreover, the presence of tetraphenylethylene group in the NHOs entitled the triblock TPEs with excellent AIE properties in both solution and solid state.

Pre-Polymer Chain Length: Influence on Permanent Memory Effect of PDLC Devices

This study delved into the correlation between the chain length of PEG polymerizable oligomers and the electro-optical properties exhibited by the resultant PDLC films. A range of di(meth)acrylate oligomers derived from polyethylene glycol with varying molecular weights (Mn = 1000, 2000, 4000, and 6000 g mol−1) was synthesized for incorporation as the polymer matrix in PDLC devices. Comprehensive analyses employing 1H-NMR, 13C-NMR, and MALDI-TOF mass spectroscopy were conducted to validate the structure and purity of the synthesized products. The investigation revealed a significant influence of pre-polymer molecular chain length on the thermal properties of the polymer, including amorphousness and crystallinity, which in turn impact the permanent memory effect. Specifically, it was observed that amorphous PEG polymers serve as an ideal matrix for fostering the permanent memory effect in PDLCs. Among the polymerizable PEG oligomers examined, those with a molecular weight of 1000 g/mol yielded polymer chains existing in an amorphous state, exhibiting a glass transition temperature lower than room temperature (−50 °C). This characteristic imparts flexibility and mobility to the polymer matrix chains, facilitating a 37% permanent memory effect. Conversely, longer polymer chains lead to the formation of crystal aggregates, resulting in semi-crystalline polymer matrices. This reduces the malleability of the polymer chains, thereby nullifying the permanent memory effect in the corresponding PDLC devices.

Design of an Azopolymer for Photo-Switchable Adhesive Applications

Significant research endeavors have been devoted to developing adhesives with reversible switching capabilities, allowing them to activate adhesion in response to diverse environmental stimuli. Among these, photo-switchable adhesives stand out as particularly promising. The presence of a photo-reversible solid-to-liquid transition, characterized by a transition temperature (TSL), in certain azobenzene-containing polymers offers a compelling avenue for creating such adhesives. The development of a method based on Atomic Force Microscopy to measure both the glass transition temperature (Tg) and TSL provided an opportunity to investigate the impact of various structural parameters on the solid-to-liquid transition of azopolymers. Our findings revealed that increasing the molecular weight (Mn) from 3400 to 8100 g/mol needed to achieve a highly cohesive adhesive resulted in an elevation in TSL (&gt;10 °C), making the solid-to-liquid transition at room temperature more challenging. However, incorporating a highly flexible substituent at the para position of the azobenzene group proved effective in significantly reducing the TSL value (from 42 °C to 0 °C). This approach allows for the creation of photo-switchable adhesives with intriguing properties. We believe that our results establish a pathway toward developing a robust room-temperature photo-switchable adhesive.

Synthesis and characterization of amino-functional polyesters composed of lactic acids and serine amino acids

Functional polyesters with good biocompatibility are always important biomaterials. In this study, poly (latide-co-N-trityl serine ester)s (P (LA-co-TSL)s) were synthesized through the copolymerization of lactide (LA) and N-trityl serine lactone (TSL) in toluene under 90 °C with the catalysis of diethylzinc. The molecular weight (Mn) of P (LA-co-TSL) with different TSL molar ratios (4.5%, 8.8%, 25.2%, 41.7% and 100 mol%) ranged from 3.7 kDa to 7.2 kDa with the polydipersity index (PDI) from 1.40 to 1.57. The chemical structure of poly (LA-co-TSL)s was characterized by FTIR, 1H NMR and 13C NMR spectroscopy. As the proportion of TSL in P (LA-co-TSL) increased, the glass transition temperature (Tg) of P (LA-co-TSL) increased gradually, from 56 °C of PLA to 161 °C of Poly (TSL). The initial weitht loss temperature of P (LA-co-TSL) increased as the ratio of TSL increased, from 172 °C of PLA to 230 °C of Poly (TSL). Upon removal of the N-trityl protecting group, amino functional poly (latide-co-serine ester) (P (LA-co-SL)) was realized and confirmd by FTIR and 1H NMR spectra. GPC displayed approximately 19.5% polyester backbone degradation during deprotection with trifluoroacetic acid. DSC analysis illustrated better crystallization properties of the copolyester after amino group deprotection. Using mPEG as an initiator, a new type of block copolymer, mPEG-b-poly (latide-co-N-trityl serine ester)s (mPEG-b-P (LA-co-TSL)s), was obtained. After N-trityl removal, mPEG-b-P (LA-co-TSL) displayed excellent cytocompatibility in L929 cell culture experiments.

Aminophosphine Based Lewis Pair for the Controlled Polymerization of Methyl Methacrylate

AbstractLewis pair polymerization (LPP) has made significant progress in recent decades as a powerful method to synthesize polymers. The matching of electronic and steric properties of Lewis base/acid plays a decisive role in the activity, controlled behavior, and initiation efficiency (I*) of the polymerization. However, exploration of aminophosphine based Lewis base for polymer synthesis has been limited. Herein, commercially available aminophosphine, namely hexamethylphosphorous triamide (HMPT) in combination with common organoaluminum for the polymerization of methyl methacrylate (MMA), is presented. HMPT/iBu3Al shows controlled behavior in MMA polymerization with polymerization degree from 48 to 800, affording defined polymethyl methacrylate (PMMA) with molecular weight (Mn = 15.1–110.7 kg mol−1) with relatively narrow molecular weight distributions (Ð = 1.11–1.37). Matrix‐assisted laser desorption/ionization time of flight mass spectroscopy (MALDI‐TOF‐MS) affirmed the chain‐end fidelity of PMMA. The interaction mode between Lewis pair affects the in situ generated fraction of active species. The basicity and the cone angle of the aminophosphine determine the activity of the formed active species and I*. The successful application highlights the benefits of introducing P─N bonds into Lewis bases, thereby expanding the variety of Lewis base categories.

Cyclic and Linear Tetrablock Copolymers Synthesized at Speed and Scale by Lewis Pair Polymerization of a One-Pot (Meth)acrylic Mixture and Characterized at Multiple Levels.

Cyclic block copolymers (cBCP) are fundamentally intriguing materials, but their synthetic challenges that demand precision in controlling both the monomer sequence and polymer topology limit access to AB and ABC block architectures. Here, we show that cyclic ABAB tetra-BCPs (cABAB) and their linear counterpart (lABAB) can be readily obtained at a speed and scale from one-pot (meth)acrylic monomer mixtures, through coupling the Lewis pair polymerization's unique compounded-sequence control with its precision in topology control. This approach achieves fast (<15 min) and quantitative (>99%) conversion to tetra-BCPs of predesignated linear or cyclic topology at scale (40 g) in a one-pot procedure, precluding the needs for repeated chain extensions, stoichiometric addition steps, dilute conditions, and postsynthetic modifications, and/or postsynthetic ring-closure steps. The resulting lABAB and cABAB have essentially identical molecular weights (Mn = 165-168 kg mol-1) and block degrees/symmetry, allowing for direct behavioral comparisons in solution (hydrodynamic volume, intrinsic viscosity, elution time, and refractive indices), bulk (thermal transitions), and film (thermomechanical and rheometric properties and X-ray scattering patterns) states. To further the morphological characterizations, allylic side-chain functionality is exploited via the thiol-ene click chemistry to install crystalline octadecane side chains and promote phase separation between the A and B blocks, allowing visualization of microdomain formation.

An integrated mechanical degradation model to explore the mechanical response of a bioresorbable polymeric scaffold

Simulation of bioresorbable medical devices is hindered by the limitations of current material models. Useful simulations require that both the short- and long-term response must be considered; existing models are not physically-based and provide limited insight to guide performance improvements. This study presents an integrated degradation framework which couples a physically-based degradation model, which predicts changes in both crystallinity (Xc) and molecular weight (Mn), with the results of a micromechanical model, which predicts the effective properties of the semicrystalline polymer. This degradation framework is used to simulate the deployment of a bioresorbable PLLA (Poly (L-lactide) stent into a mock vessel and the subsequent mechanical response during degradation under different diffusion boundary conditions representing neointimal growth. A workflow is established in a commercial finite element code that couples both the immediate and long-term responses. Clinically relevant lumen loss is reported and used to compare different responses and the effect of neo-intimal tissue regrowth post-implantation on degradation and on the mechanical response is assessed. In addition, the effects of possible changes in Xc, which could occur during processing and stent deployment, are explored.

Polymer Donor with a Simple Skeleton and Minor Siloxane Decoration Enables 19% Efficiency of Organic Solar Cells.

Development of polymer donors with simple chemical structure and low cost is of great importance for commercial application of organic solar cells (OSCs). Here, side-chain random copolymer PMQ-Si605 with a simply 6,7-difluoro-3-methylquinoxaline-thiophene backbone and 5% siloxane decoration of side chain is synthesized in comparison with its alternating copolymer PTQ11. Relative to molecular weight (Mn) of 28.3kg mol-1 for PTQ11, the random copolymer PMQ-Si605 with minor siloxane decoration is beneficial for achieving higher Mn up to 51.1kg mol-1. In addition, PMQ-Si605 can show stronger aggregation ability and faster charge mobility as well as more efficient exciton dissociation in active layer as revealed by femtosecond transient absorption spectroscopy. With L8-BO-F as acceptor, its PMQ-Si605 based OSCs display power conversion efficiency (PCE) of 18.08%, much higher than 16.21% for PTQ11 based devices. With another acceptor BTP-H2 to optimize the photovoltaic performance of PMQ-Si605, further elevated PCEs of 18.50% and 19.15% can be achieved with the binary and ternary OSCs, respectively. Furthermore, PMQ-Si605 based active layers are suitable for processing in high humidity air, an important factor for massive production of OSCs. Therefore, the siloxane decoration on polymer donors is promising, affording PMQ-Si605 as a high-performing and low cost candidate.

Facile Synthesis of High Molecular Weight Poly(ethylene glycol)-b-poly(amino acid)s by Relay Polymerization.

Poly(amino acid)s (PAAs) are one kind of favorable biopolymer that can be used as a drug or gene carrier. However, conventional ring-opening polymerization of PAAs is slow and needs a strict anhydrous environment with an anhydrous reagent as well as the product without enough high molecular weight (Mn), which limits the expanding of PAAs' application. Herein, we took BLG-NCA as the monomer to quickly synthesize one kind of high Mn amphiphilic copolymer, poly(ethylene glycol)-b-poly(γ-benzyl-l-glutamic acid) (PEG-PBLG), by relay polymerization with a simple one-pot method within 3 h in mild conditions (open air, moisture insensitive). In the polymerization process, ring-opening polymerization-induced self-assembly in sodium bicarbonate aqueous solution first occurred to obtain low Mn PEG-PBLG seeds without purification. Then γ-benzyl-l-glutamate N-carboxyanhydride (BLG-NCA) dichloromethane solution was added into PEG-PBLG seeds directly and stirred vigorously to form am emulsion; during this process, the amphiphilic PEG-PBLG seeds will anchor on the interface of DCM and water to ensure the concentration of α-helix rigid PBLG in DCM to maintain the following relay polymerization. Then, high Mn PEG-PBLG was obtained in mild conditions in one pot. We found that the α-helix rigid structure was essential for relay polymerization by studying the synthetic speed of amphiphilic copolymer with different secondary structures. MOE simulation results showed that PBLG and BLG-NCA tended to form a double hydrogen bond, which was beneficial to relay polymerization because of higher local concentrations that can produce more double hydrogen bonds. Our strategy can quickly obtain high Mn PEG-PBLG (224.9 KDa) within 3 h from PEG-NH2 and BLG-NCA in one pot and did not need an extra initiator. After deprotection, the poly(ethylene glycol)-b-poly(l-glutamate acid) (PEG-PGA) with high Mn as a second product can be used as an excellent antitumor drug carrier. The high Mn PEG-PGA can achieve an encapsulation rate of 86.7% and a drug loading rate of 47.3%, which is twice that of the low Mn PEG-PGA. As a result, the synthesis of PEG-PBLG by relay polymerization simplified the process of PEG-PAA polymerization and increased the Mn. In addition, this method opened a way to obtain other kinds of high Mn PEG-PBLG values in the future.

Low molar mass cyclic poly(L-lactide)s: separate transesterification reactions of cycles and linear chains in the solid state.

L-Lactide (LA) was polymerized with neat tin(II) 2-ethylhexanoate (SnOct2) in toluene at 115 °C at low concentration with variation of the LA/Cat ratio. Cyclic polylactides (cPLAs) with number average molecular weights (Mn) between 7000 and 17 000 were obtained. MALDI-TOF mass spectrometry also revealed the formation of a few percent of linear chains. Crystalline cPLAs with Mn around 9000 and 14 000 were annealed at 140 °C in the presence of ScOct2 or dibutyl-2-stanna-1,3-dithiolane (DSTL). Simultaneously, crystallites of extended linear chains and crystallites of extended cycles were formed regardless of the catalyst, indicating that transesterification reaction proceeded different for linear chains and for cycles, governed by thermodynamic control. The formation of extended chain crystallites with low dispersity indicates the existence of symproportionation of short and long chains. A complementary experiment was carried out with a PLA ethyl ester composed mainly of linear chains with a small fraction of cycles.

Melt memory in random ethylene-1-alkene copolymers.

Chain flexibility or stiffness based polymer conformation plays a crucial role in affecting the dynamics and kinetics of polymers, which is related to the hierarchical architecture of chains. A series of random copolymers of ethylene and 1-alkenes including 1-hexene, 1-octene, and 1-dodecene were synthesized with metallocene catalysts. The crystallization behavior and memory effect in random ethylene-1-alkene copolymers with different side groups were investigated via differential scanning calorimetry (DSC) and wide-angle X-ray scattering (WAXS). Rheological tests were performed for understanding their dynamical behavior. The results show that the melting peak and the viscosity decrease but the orthorhombic crystal dimensions increase with co-unit contents increasing in the copolymers. It was found that the scaling relationship between the zero shear viscosity (η0) and molecular weight (Mn) of the copolymers containing ethylene-1-hexene and ethylene-1-octene is 3.6, which is higher than the classical scaling value of 3.4. The memory of crystals in the melt is enhanced with the increase of 1-alkene contents but is independent of the types of 1-alkenes. The enhanced melt memory effect in the copolymers was proposed due to the effect of the 1-alkene based side groups on the dynamics of polymer chains. The present work would be helpful to understand the chain stiffness based polymer dynamics and processing of polyolefins and copolymers prepared with the metallocene catalyst.

Branched copolymer surfactants impart thermoreversible gelation to LAPONITE® gels.

This investigation seeks to integrate LAPONITE® clay gels with thermoresponsive branched copolymer surfactants (BCSs) to develop advanced functional materials with temperature-induced sol-gel behaviour. It is known that a diverse range of molecules adsorb strongly to clays which may be used to control liberation of the species in healthcare applications, and as such the development of polymer/clay hybrid materials which can add function to the native clay behaviour are of great interest. BCS were synthesised with a structure that encompasses poly(ethylene glycol)methacrylate (PEGMA), ethylene glycol dimethacrylate (EGDMA), and dodecanethiol (DDT), conferring versatile and tuneable thermoresponsive attributes. Systematic modulation of the monomer : DDT/initiator ratio was used to facilitate the synthesis of BCS architectures spanning a range of molecular weights. Through application of small-amplitude oscillatory shear (SAOS) rheology and small-angle neutron scattering (SANS) in conjunction with controlled temperature variations, the sol-gel transition dynamics of these nanocomposite materials were elucidated. Complementary insights into the mechanisms underpinning this transition and temperature-induced alterations in the constituents are gleaned through the utilization of SANS techniques employing contrast-matching methodologies to mitigate clay and polymer scattering interference. It is found that heating systems from room- to body- temperature induces self-assembly of BCS in the bulk aqueous phase with concurrent structuration of clay in gel-forming samples with lower number average molecular weight (Mn). SANS study unpicks this phenomenon to find that gelation occurs with concurrent aggregation of BCS in the bulk, inducing clay-clay interactions only in lower Mn BCS systems with large nanoaggregates.

Highly active aggregate catalysts for the synthesis of high-molecular-weight polyesters via copolymerization of epoxides and cyclic anhydrides

Aggregate catalysts efficiently produce high molecular weight polyesters and exhibit high activity and low concentration tolerance in the copolymerization of epoxides and cyclic anhydrides.

Dimethyl sulfoxide as a gas phase charge-reducing agent for the determination of PEGylated proteins' intact mass.

Determination of PEGylated proteins' intact mass by mass spectrometry is challenging due to the molecules' large size, excessive charges, and instrument limitations. Previous efforts have been reported. However, signal variability, ion coalescence, and a generally low degree of robustness have been observed. In this work, we have explored the capabilities of post-column infusion of dimethyl sulfoxide (DMSO) following reversed-phase liquid chromatography-mass spectrometry (RP-LCMS) to determine PEG-filgrastim' intact mass, and to characterize its PEG moiety. The method was optimized around reproducibility (six preparations, and three injection replicates) with an in-house prepared PEG-filgrastim standard. The method showed a mass accuracy of ≤1.2 Da. The average molecular weight (MWEO=483) was 40 147.9 Da. The number average molecular weight (Mn) and the weight average molecular weight (Mw) were observed to be 40 101.1 and 40 113.9 Da, respectively, both with an RSD of 0.03%. The molecular weight distribution of ethylene oxide (EO), the polydispersity index (PDI), was 1.0003 for all preparations with a minimum and maximum number of EO units of 448 ± 2 and 516 ± 2, respectively. The method was finally applied to commercially available Neulasta® lots where the Mn and Mw were 39 995.8 and 40 008.8 Da, respectively, both with an RSD of 0.1%. The minimum and maximum EO units across the lots were observed to be 444.5 ± 1.5 and 514 ± 3, respectively. The PDI for all Neulasta® lots was 1.0003. This study provides an insightful characterization of Neulasta® and describes a robust LC-MS methodology for the characterization of the PEGylated proteins.

Investigation of the in vitro biological activities of polyethylene glycol-based thermally stable polyurethane elastomers.

The intense urge to replace conventional polymers with ecofriendly monomers is a step towards green products. The novelty of this study is the extraction of starch from the biowaste of wheat bran (WB) and banana peel (BP) for use as a monomer in the form of chain extenders. For the synthesis of polyurethane (PU) elastomers, polyethylene glycol (PEG) bearing an average molecular weight Mn = 1000 g mol-1 was used as a macrodiol, which was reacted with isophorone diisocyanate (IPDI) to develop NCO-terminated prepolymer chains. These prepolymer chains were terminated with chain extenders. Two series of linear PU elastomers were prepared by varying the concentration of chain extenders (0.5-2.5 mol%), inducing a variation of 40 to 70 wt% in the hard segment (HS). Fourier-transform infrared (FTIR) spectroscopy confirmed the formation of urethane linkages. Thermal gravimetric analysis (TGA) showed a thermal stability of up to 250 °C. Dynamic mechanical analysis (DMA) revealed a storage modulus (E') of up to 140 MPa. Furthermore, the hemolytic activities of up to 8.97 ± 0.1% were recorded. The inhibition of biofilm formation was investigated against E. coli and S. aureus (%), which was supported by phase contrast microscopy.

Eco-Conscious Approach to Thermoresponsive Star-Comb and Mikto-Arm Polymers via Enzymatically Assisted Atom Transfer Radical Polymerization Followed by Ring-Opening Polymerization.

This study explores the synthesis, characterization, and application of a heterofunctional initiator derived from 2-hydroxypropyl cyclodextrin (HP-β-CD), having eight bromoester groups and thirteen hydroxyl groups allowing the synthesis of mikto-arm star-shaped polymers. The bromoesterification of HP-β-CD was achieved using α-bromoisobutyryl bromide as the acylation reagent, modifying the cyclodextrin (CD) molecule as confirmed by electrospray ionization mass spectrometry (ESI-MS), nuclear magnetic resonance (NMR), attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy analysis, and differential scanning calorimetry (DSC) thermograms. The initiator's effectiveness was further demonstrated by obtaining star-comb and mikto-arm polymers via an enzymatically assisted atom transfer radical polymerization (ATRP) method and subsequent ring-opening polymerization (ROP). The ATR polymerization quality and control depended on the type of monomer and was optimized by the way of introducing the initiator into the reaction mixture. In the case of ATRP, high conversion rates for poly(ethylene oxide) methyl ether methacrylate (OEOMA), with molecular weights (Mn) of 500 g/mol and 300 g/mol, were achieved. The molecular weight distribution of the obtained polymers remained in the range of 1.23-1.75. The obtained star-comb polymers were characterized by different arm lengths. Unreacted hydroxyl groups in the core of exemplary star-comb polymers were utilized in the ROP of ε-caprolactone (CL) to obtain a hydrophilic mikto-arm polymer. Cloud point temperature (TCP) values of the synthesized polymers increased with arm length, indicating the polymers' reduced hydrophobicity and enhanced solvation by water. Atomic force microscopy (AFM) analysis revealed the ability of the star-comb polymers to create fractals. The study elucidates advancements in the synthesis and utilization of hydrophilic sugar-based initiators for enzymatically assisted ATRP in an aqueous solution for obtaining complex star-comb polymers in a controlled manner.

OPEFB pretreatment using the low-cost N,N,N-dimethylbutylammonium hydrogen sulfate ionic liquid under varying conditions

This study investigates the effects of temperature and period on the pretreatment of OPEFB using the low-cost N,N,N-dimethylbutylammonium hydrogen sulfate ionic liquid ([DMBA][HSO4] IL) with 20 wt% of water. The results demonstrate that higher pretreatment temperatures (120, 150, and 170 °C) and longer periods (0.5, 1, and 2 h) enhanced lignin recovery, resulting in increased purity of the recovered pulp and subsequently enhanced glucose released during enzymatic hydrolysis. However, at 170 °C, prolonging the period led to cellulose degradation and the formation of pseudo-lignin deposited on the pulps, resulting in a decreasing-trend in glucose released. Finally, the analysis of extracted lignin reveals that increasing pretreatment severity intensified lignin depolymerisation and condensation, leading to a decrease in number average molecular weight (Mn), weight average molecular weight (Mw) and polydispersity index (Đ) values.