Probing the nanostructure, interfacial interaction, and dynamics of chitosan-based nanoparticles by multiscale solid-state NMR.
Chitosan-based nanoparticles (NPs) are widely used in drug and gene delivery, therapy, and medical imaging, but a molecular-level understanding of the internal morphology and nanostructure size, interface, and dynamics, which is critical for building fundamental knowledge for the precise design and efficient biological application of the NPs, remains a great challenge. Therefore, the availability of a multiscale (0.1-100 nm) and nondestructive analytical technique for examining such NPs is of great importance for nanotechnology. Herein, we present a new multiscale solid-state NMR approach to achieve this goal for the investigation of chitosan-poly(N-3-acrylamidophenylboronic acid) NPs. First, a recently developed (13)C multiple cross-polarization magic-angle spinning (MAS) method enabled fast quantitative determination of the NPs' composition and detection of conformational changes in chitosan. Then, using an improved (1)H spin-diffusion method with (13)C detection and theoretical simulations, the internal morphology and nanostructure size were quantitatively determined. The interfacial coordinated interaction between chitosan and phenylboronic acid was revealed by one-dimensional MAS and two-dimensional (2D) triple-quantum MAS (11)B NMR. Finally, dynamic-editing (13)C MAS and 2D (13)C-(1)H wide-line separation experiments provided details regarding the componential dynamics of the NPs in the solid and swollen states. On the basis of these NMR results, a model of the unique nanostructure, interfacial interaction, and componential dynamics of the NPs was proposed.
Key Laboratory of Functional Polymer Materials of the Ministry of Education and College of Chemistry, State Key Laboratory of Medicinal Chemical Biology, Nankai University and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin) , Tianjin 300071, China.
Fenfen
F
Wang
Rongchun
R
Zhang
Qiang
Q
Wu
Tiehong
T
Chen
Pingchuan
P
Sun
An-Chang
AC
Shi
D001897:Boronic Acids / Q000737:chemistry; D048271:Chitosan / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D053758:Nanoparticles / Q000737:chemistry / Q000648:ultrastructure*; D049329:Nanostructures / Q000737:chemistry / Q000648:ultrastructure*
C419826:3-acrylamidophenylboronic acid; D001897:Boronic Acids; D048271:Chitosan
chitosan; coordinated interaction; morphology; nanoparticles; solid-state NMR