Glucosamine Modified the Surface of pH-Responsive Poly(2-(diethylamino)ethyl Methacrylate) Brushes Grafted on Hollow Mesoporous Silica Nanoparticles as Smart Nanocarrier

Abstract

This work presents the synthesis of pH-responsive poly(2-(diethylamino) ethyl methacrylate) (PDEAEMA) brushes anchored on hollow mesoporous silica nanoparticles (HMSN-PDEAEMA) via a surface-initiated ARGET ATRP technique. The average size of HMSNs was ca. 340 nm, with a 90 nm mesoporous silica shell. The dry thickness of grafted PDEAEMA brushes was estimated to be ca 30 nm, as estimated by SEM and TEM. The halogen group on the surface of PDEAMA brushes was successfully derivatized with glucosamine, as confirmed by XPS. The effect of pH on the size of the hybrid nanoparticles was investigated by DLS. The size of fabricated nanoparticle decreased from ca. 950 nm in acidic media to ca. 500 nm in basic media due to the deprotonation of tertiary amine in the PDEAEMA. The PDEAEMA modified HMSNs nanocarrier was efficiently loaded with doxorubicin (DOX) with a loading capacity of ca. 64%. DOX was released in a relatively controlled pH-triggered manner from hybrid nanoparticles. The cytotoxicity studies demonstrated that DOX@HMSN-PDEAEMA-Glucosamine showed a strong ability to kill breast cancer cells (MCF-7 and MCF-7/ADR) at low drug concentrations, in comparison to free DOX.

Folic Acid-Terminated Poly(2-Diethyl Amino Ethyl Methacrylate) Brush-Gated Magnetic Mesoporous Nanoparticles as a Smart Drug Delivery System

“…9%.X-ray photoelectron spectroscopy was performed to study the surface modification of Fe 3 O 4 @MSN-PDEAEMA (Figure5). The C1s spectrum of the PDEAEMA brush grafted on Fe 3 O 4 @MSNs was fitted with three peaks at 284.8 eV, 286.1 eV, and 288.6 eV with a ratio of 4.5:3.8:1, corresponding to the C-H, C-(N, O), and O=C-O, respectively, in good agreement with a theoretical ratio of 5:4:1 (Figure5A)[52,53]. After aminating the end group of the polymer chains, there is no difference in C1s spectrum of PDEAEMA, as shown in Figure5B.…”

“…These peaks disappeared after CTAB extraction. After a polymerization process, a new peak appears at 1720 cm −1 corresponding to C=O groups compared to Fe 3 O 4 @MSN-Br.The successful decoration of magnetic mesoporous silica was evaluated by thermogravimetic analysis (TGA) when heating in an N 2 atmosphere to 1000 • C. It was noticed that there was an increase in the weight loss after each synthetic step, which confirms the surface modification of Fe 3 O 4 @MSNs (Figure4)[37,52,53]. The weight loss of Fe 3 O 4 @MSN-NH 2 with the surfactant has three mass loss steps.…”

Poly(oligo(ethylene glycol) methyl ether methacrylate) Capped pH-Responsive Poly(2-(diethylamino)ethyl methacrylate) Brushes Grafted on Mesoporous Silica Nanoparticles as Nanocarrier

“…Despite the potential advantages of MSNs for drug delivery applications, pure MSNs tend to aggregate when directly exposed to biological environments, leading to uncontrolled drug release patterns [ 19 , 20 ]. These drawbacks could be minimized by using biocompatible polymers to coat the surface of silica nanoparticles in order to form different structures such as yolk–shell [ 21 ], core–shell [ 22 ], and brushes [ 23 ]. The combination of such polymers and silica nanoparticles not only addresses the aforementioned limitations but can also endow these particles with encapsulated guest molecules and subsequently release them at a later stage in an optimal way [ 24 ].…”

“…For instance, base polymers, such as poly( N , N diethylaminoethyl methacrylate), poly( N , N -dimethylaminoethyl methacrylate), and poly(b-amino ester), undergo structural changes when the amine groups become protonated. Protonation of the tertiary amino groups of poly(2-(diethylamino)ethyl methacrylate) (PDEAEMA) in an acidic medium triggered the swelling of the polymer due to the phase change from hydrophobic to hydrophilic with decreasing the environmental pH [ 22 ]. Alswieleh et al successfully incorporated poly(2-(tert-butylamino)ethyl methacrylate) brushes into mesoporous silica nanoparticles via surface-initiated atom transfer radical polymerization (SI-ATRP).…”

“…500 to ca. 980 nm when the pH decreased from 9 to 6.5, leading to the release of doxorubicin (DOX) from the nanosystem with a controlled manner [ 22 ]. Alswieleh et al synthesized a diblock copolymer consisting of poly(ethylene glycol) methyl ether methacrylate and 2-(tert-butylamino)ethyl methacrylate grafted into the outer surface of MSNs via the atom transfer radical polymerization method.…”