The hydrolytic behavior of N,N′-(dimethylamino)ethyl acrylate-functionalized polymeric stars

Rolph, Marianne S.; Pitto-Barry, Anaïs; O’Reilly, Rachel K.

doi:10.1039/c7py00219j

Cited by 16 publications

(22 citation statements)

References 46 publications

(72 reference statements)

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“…Clearly, the stability of the ester moiety of the polymethacrylates, which is attached directly to the backbone, is much higher than the one reported for ester moieties placed in the side chains of methacrylic polymers well separated from the backbone [62,63,64]. This remarkable finding goes along with previous reports that polymethacrylates are much less sensitive to hydrolysis than their polyacrylate analogs [32,33,34,35,37]. This may be explained by steric effects.…”

Section: Resultsmentioning

confidence: 52%

“…Accordingly, the literature assessments of the stability of antifouling polymers often represent mere assumptions, or are based on singular observations for which the precise experimental conditions are often not disclosed. According to the data available, polyacrylates seem to be rather susceptible to hydrolysis, much more than polymethacrylates [32,33,34,35,36,37]. Moreover, for the case of the monomers, methacrylamides were shown to resist hydrolysis better than methacrylates do [28,29].…”

Section: Introductionmentioning

confidence: 99%

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Exploring the Long-Term Hydrolytic Behavior of Zwitterionic Polymethacrylates and Polymethacrylamides

2018

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The hydrolytic stability of polymers to be used for coatings in aqueous environments, for example, to confer anti-fouling properties, is crucial. However, long-term exposure studies on such polymers are virtually missing. In this context, we synthesized a set of nine polymers that are typically used for low-fouling coatings, comprising the well-established poly(oligoethylene glycol methylether methacrylate), poly(3-( N -2-methacryloylethyl- N,N -dimethyl) ammoniopropanesulfonate) (“sulfobetaine methacrylate”), and poly(3-( N -3-methacryamidopropyl- N,N -dimethyl)ammoniopropanesulfonate) (“sulfobetaine methacrylamide”) as well as a series of hitherto rarely studied polysulfabetaines, which had been suggested to be particularly hydrolysis-stable. Hydrolysis resistance upon extended storage in aqueous solution is followed by 1 H NMR at ambient temperature in various pH regimes. Whereas the monomers suffered slow (in PBS) to very fast hydrolysis (in 1 M NaOH), the polymers, including the polymethacrylates, proved to be highly stable. No degradation of the carboxyl ester or amide was observed after one year in PBS, 1 M HCl, or in sodium carbonate buffer of pH 10. This demonstrates their basic suitability for anti-fouling applications. Poly(sulfobetaine methacrylamide) proved even to be stable for one year in 1 M NaOH without any signs of degradation. The stability is ascribed to a steric shielding effect. The hemisulfate group in the polysulfabetaines, however, was found to be partially labile.

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Section: Resultsmentioning

confidence: 52%

Section: Introductionmentioning

confidence: 99%

Exploring the Long-Term Hydrolytic Behavior of Zwitterionic Polymethacrylates and Polymethacrylamides

2018

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“…Release must occur to allow the dsRNA to become available so to trigger RNAi . Considerable efforts have been directed at overcoming this problem, in particular, poly(2-(dimethylamino)ethyl acrylate) (PDMAEA) has been reported as having a self-catalyzed hydrolysis property, with autodegradation to poly(acrylic acid) and 2-(dimethylamino)ethanol when in aqueous solution. − In addition, PDMAEA has a high transfection efficiency into HeLa cells when complexed with RNA, can facilitate complete release of RNA and exhibits very low toxicity. ,− We thus envisaged that PDMAEA could be a good candidate to protect the dsRNA in soil and delay degradation prior to release.…”

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confidence: 99%

Efficient Binding, Protection, and Self-Release of dsRNA in Soil by Linear and Star Cationic Polymers

et al. 2018

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Double stranded RNA (dsRNA) exhibits severe degradation within 3 days in live soil, limiting its potential application in crop protection. Herein we report the efficient binding, protection, and self-release of dsRNA in live soil through the usage of a cationic polymer. Soil stability assays show that linear poly(2-(dimethylamino)ethyl acrylate) can delay the degradation of dsRNA by up to 1 week while the star shaped analogue showed an increased stabilization of dsRNA by up to 3 weeks. Thus, the architecture of the polymer can significantly affect the lifetime of dsRNA in soil. In addition, the hydrolysis and dsRNA binding and release profiles of these polymers were carefully evaluated and discussed. Importantly, hydrolysis could occur independently of environmental conditions (e.g., different pH, different temperature) showing the potential for many opportunities in agrochemicals where protection and subsequent self-release of dsRNA in live soil is required.

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“…These results indicated that the alkalinee nvironmentp roduced by the tertiarya mine group could accelerate the ester bond cleavage in water;h owever,t his effect was weakened in PBS. For compound 1a under different amountso fH 2 O 2 in PBS (pH 7.4), we found that the charger eversal rates were similar andt he final zeta potentialw ere all around À6mV ( Figure 1d;s ee the Supporting Information, Figure S31), which indicates that the ultrafast cleavage of the ester bond in compound 1a was little affected by the concentrationo fs timulis ignals and was only related to the formationo ft he HBC structure.O nt he basis of these results, it could be found that the ester hydrolysis rate in compound 1a and b was not only much faster than the methods reported, [14,22,25,29,35] which created an alkaline environment by using the tertiarya mines residues,b ut was also much faster than b-thiopropionate esters, which are acid-sensitive. [30,31] Dynamics of the ester bond hydrolysis in compounds1 -3…”

Section: Chargea Lteration Of Compounds 1-3mentioning

confidence: 78%

Hydrogen‐Bond Cyclization Programming of Ultrasensitive Esters and Its Application in Gene Delivery

Yan

et al. 2019

Chemistry A European J

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The ester bond as au niversal linker has recently been applied in gene delivery systemso wing to its efficient gene release by electrostatic repulsiona fter its cleavage. However,t he ester bond is nonlabile and is difficult to cleave in cells. This work reports am ethodinw hich as econdary amine was introduced to the b-positiono ft he ester bond to generate ah ydrogen-bond cyclization( HBC)s tructure that can make the ester bond hydrolysis ultrafast. A series of molecules comprisingu ltrasensitive esters that can be activated by H 2 O 2 were synthesized, andi tw as found that those ablet of orm an HBC structure showed complete ester hydrolysis within 5hin both water and phosphate-buf-fered saline solution,w hich was severalt imes faster than other methods reported. Then, as eries of amphiphilic poly-(amidoamine) dendrimers were constructed,c omprising the ultrasensitive ester groups for gene delivery; it was found that they could effectively releaseg enes under quite al ow concentration of H 2 O 2 (< 200 mm)a nd transport them into the nucleus within 2h in Hela cells with high safety.T heir gene transfection efficiencies were higher than that of PEI 25k . The results demonstrated that the hydrogen-bond-induced ultrasensitive esters could be powerfully applied to construct gene delivery systems.[a] S.Supporting Information and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.Preparation of HEPES buffer (10 mm,p H7.4):4 -(2-hydroxyethyl)-1-piperazineethanesulfonic acid (238.2 mg) was dissolved in D 2 O (90 mL), and aqueous NaOH (1 m)was added dropwise until the solution reached pH 7.4. The volume was maintained to 100 mL, the solution was filtered, and the filtrate was stored at 4 8C. ROS-responsiveness of nanoparticles of Dendrimer-4The charge reversal of Dendrimer-4 was measured by using DLS. Dendrimer-4 was dissolved in H 2 O 2 (80 mm)a taconcentration of 2mgmL À1 in PBS (pH 7.4). The solution was incubated at 37 8C with shaking. Samples were analyzed at timed intervals, and their zeta potentials were measured. Dendrimer-4 was also dissolved in

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The hydrolytic behavior of N,N′-(dimethylamino)ethyl acrylate-functionalized polymeric stars

Abstract: Well-defined N,N′-(dimethylamino)ethyl acrylate (DMAEA) functionalized polymeric stars have been synthesized via an arm-first approach.

Cited by 16 publications

References 46 publications

Exploring the Long-Term Hydrolytic Behavior of Zwitterionic Polymethacrylates and Polymethacrylamides

Exploring the Long-Term Hydrolytic Behavior of Zwitterionic Polymethacrylates and Polymethacrylamides

Efficient Binding, Protection, and Self-Release of dsRNA in Soil by Linear and Star Cationic Polymers

Hydrogen‐Bond Cyclization Programming of Ultrasensitive Esters and Its Application in Gene Delivery

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