PDMAEMA/Polyester Miktopolymers: Synthesis via In-Out Approach, Physicochemical Characterization and Enzymatic Degradation

Kupczak, Maria; Mielańczyk, Anna; Neugebauer, Dorota

doi:10.3390/ma14051277

Cited by 6 publications

(4 citation statements)

References 35 publications

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“…In our previous works concerning the degradation of PDMAEMA/polyester block copolymers, we have shown that enzymatic degradation using Novozyme 435 primarily involved the ester bonds in PDMAEMA side chains, and the rate of polyester degradation decreased with the increase in the chain length of PDMAEMA [ 24 ]. Whereas in the case of PDMAEMA/polyester miktoarm stars obtained via an in–out approach, enzymatic degradation performed using lipase from Pseudomonas cepacia showed an increased degradation rate for the polymer with PCL arms [ 25 ].…”

Section: Introductionmentioning

confidence: 99%

“…Our previous research was focused on the synthesis of miktoarm star-shaped polymers via a coupling-onto [ 26 ] or in–out method [ 25 ]. In this study, a series of well-defined miktoarm star-shaped copolymers based on DMAEMA and cyclic esters were obtained by facile one-pot synthesis using a combination of techniques such as ATRP, ROP, and click reaction.…”

Section: Introductionmentioning

confidence: 99%

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From Facile One-Pot Synthesis of Semi-Degradable Amphiphilic Miktoarm Polymers to Unique Degradation Properties

Kupczak,

Mielańczyk,

Fronczyk

et al. 2024

Materials

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We report a one-pot synthesis of well-defined A5B and A8B miktoarm star-shaped polymers where N,N-dimethylaminoethyl methacrylate (DMAEMA) and various cyclic esters such as ε-caprolactone (ε-CL), lactide (LA) and glycolide (GA) were used for the synthesis. Miktopolymers were obtained by simultaneously carrying out atom transfer radical polymerization (ATRP) of DMAEMA, ring-opening polymerization (ROP) of cyclic esters, and click reaction between the azide group in gluconamide-based (GLBr5-Az) or lactonamide-based (GLBr8-Az) ATRP initiators and 4-pentyn-1-ol. The relatively low dispersity indices of the obtained miktoarm stars (Đ = 1.2–1.6) indicate that control over the polymerization processes was sustained despite almost complete monomers conversions (83–99%). The presence of salts from phosphate-buffered saline (PBS) in polymer solutions affects the phase transition, increasing cloud point temperatures (TCP) values. The critical aggregation concentration (CAC) values increased with a decreasing number of average molecular weights of the hydrophobic fraction. Hydrolytic degradation studies revealed that the highest reduction of molecular weight was observed for polymers with PCL and PLGCL arm. The influence of the composition on the miktopolymers hydrophilicity was investigated via water contact angle (WCA) measurement. Thermogravimetric analysis (TGA) disclosed that the number of arms and their composition in the miktopolymer affects its weight loss under the influence of temperature.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

From Facile One-Pot Synthesis of Semi-Degradable Amphiphilic Miktoarm Polymers to Unique Degradation Properties

Kupczak,

Mielańczyk,

Fronczyk

et al. 2024

Materials

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“…Our previous studies involved comprehensive degradation studies on enzymatic degradation using lipase from Pseudomonas cepacia [24]. Herein, we performed a degradation study of PCL-b-PDMAEMA, PLA-b-PDMAEMA and PLGC-b-PDMAEMA copolymers under simulated physiological conditions, namely, hydrolytic degradation in PBS at different pHs, and enzymatic degradation using Novozyme 435.…”

Section: Introductionmentioning

confidence: 99%

The Influence of Polymer Composition on the Hydrolytic and Enzymatic Degradation of Polyesters and Their Block Copolymers with PDMAEMA

2021

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Well-defined, semi-degradable polyester/polymethacrylate block copolymers, based on ε-caprolactone (CL), d,l-lactide (DLLA), glycolide (GA) and N,N′-dimethylaminoethyl methacrylate (DMAEMA), were synthesized by ring-opening polymerization (ROP) and atom transfer radical polymerization. Comprehensive degradation studies of poly(ε-caprolactone)-block-poly(N,N′-dimethylaminoethyl methacrylate) (PCL-b-PDMAEMA) on hydrolytic degradation and enzymatic degradation were performed, and those results were compared with the corresponding aliphatic polyester (PCL). The solution pH did not affect the hydrolytic degradation rate of PCL (a 3% Mn loss after six weeks). The presence of a PDMAEMA component in the copolymer chain increased the hydrolysis rates and depended on the solution pH, as PCL-b-PDMAEMA degraded faster in an acidic environment (36% Mn loss determined) than in a slightly alkaline environment (27% Mn loss). Enzymatic degradation of PCL-b-PDMAEMA, poly(d,l-lactide)-block-poly(N,N′-dimethylaminoethyl methacrylate) (PLA-b-PDMAEMA) and poly(lactide-co-glycolide-co-ε-caprolactone)-block-poly(N,N′-dimethylaminoethyl methacrylate) (PLGC-b-PDMAEMA) and the corresponding aliphatic polyesters (PCL, PLA and PLGC) was performed by Novozyme 435. In enzymatic degradation, PLGC degraded almost completely after eleven days. For polyester-b-PDMAEMA copolymers, enzymatic degradation primarily involved the ester bonds in PDMAEMA side chains, and the rate of polyester degradation decreased with the increase in the chain length of PDMAEMA. Amphiphilic copolymers might be used for biomaterials with long-term or midterm applications such as nanoscale drug delivery systems with tunable degradation kinetics.

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“…Because PDMAEMA usage is limited by the lack of biodegradability in vivo model (143), since PDMAEMA has an immune suppressive effect, if not degradable, it might cause immunosuppression and increase the risk of infection or tumorigenesis. Previous studies have reported that PLGA is a biocompatible and biodegradable polymer (144).…”

Section: Chapter VI Discussionmentioning

confidence: 99%

Generation of tolerogenic dendritic cells from Fcgr2b deficient lupus-prone mice for the model of SLE therapy

Khiewkamrop

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Tolerogenic dendritic cells (tolDCs) are DCs with an immunoregulatory function, which can induce regulatory T cells (Tregs) and suppress the immune response. Currently, tolDCs-based treatment has become a promising therapeutic approach for organ transplantation and autoimmune disease. FcgRIIB is an inhibitory receptor widely expressed in B cells, myeloid cells, and DCs. The ablation of FcgRIIB in the murine model shows a spontaneous development of a lupus-like disease and might affect other immune cell regulation. There was limited information on tolDC induction in FcgRIIB defective mice. Thus, in this study, we studied the generation of tolDCs from the bone marrow-derived dendritic cells (BMDCs) of�Fcgr2b-/-�mice by various tolerogenic agents. As expected, when compared with wide-type (WT) control, bone marrow-derived DCs of�Fcgr2b-/-�mice showed higher activation and pro-inflammatory cytokine�productionupon LPS stimulation when compared with wide-type (WT) control. Tolerogenic agents can partially reduce the activation and cytokine production of LPS-stimulated�Fcgr2b-/-�BMDCs. Mainly, dexamethasone-treated�Fcgr2b-/-�BMDCs exhibited a notable decrease in pro-inflammatory cytokine production and showed an increase in IL-10 production in response to LPS stimulation. Furthermore, we demonstrated that dexamethasone-conditioned�Fcgr2b-/-�tolDCs could mediate Treg expansion�ex vivo. For the�in vivo�treatment of lupus disease, dexamethasone-conditioned�Fcgr2b-/-�tolDCs were adoptively transferred to�Fcgr2b-/-�lupus-prone mice, mediated Foxp3+�Treg expansion in the spleens and suppressed anti-double strand DNA autoantibodies in the serum. In addition, to generate tolDCs�in vivo�more conveniently, dexamethasone-loaded nanoparticles (DexaNPs) designed to target DCs were subcutaneously injected into�Fcgr2b-/-�lupus-prone mice. The DexaNPs-treated mice showed a significantly enhanced expression of PD-L1 on CD11c+�DCs, increased FoxP3+�Treg numbers, and decreased serum anti-double strand DNA autoantibodies.� ��In conclusion, our study demonstrated that dexamethasone is the most potent drug that can induce tolerogenic DCs and lead to better clinical outcome in�Fcgr2b-/-�lupus-prone mice. This may be helpful for DC-based treatment in SLE patients but not limited to�FcgrIIb�gene polymorphism.��

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PDMAEMA/Polyester Miktopolymers: Synthesis via In-Out Approach, Physicochemical Characterization and Enzymatic Degradation

Cited by 6 publications

References 35 publications

From Facile One-Pot Synthesis of Semi-Degradable Amphiphilic Miktoarm Polymers to Unique Degradation Properties

From Facile One-Pot Synthesis of Semi-Degradable Amphiphilic Miktoarm Polymers to Unique Degradation Properties

The Influence of Polymer Composition on the Hydrolytic and Enzymatic Degradation of Polyesters and Their Block Copolymers with PDMAEMA

Generation of tolerogenic dendritic cells from Fcgr2b deficient lupus-prone mice for the model of SLE therapy

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