Rational design of a supramolecular hydrogel with customizable pH-responsiveness on the basis of pH-induced ionization/protonation transition of BSA.

Developing customizable pH-responsiveness for supramolecular hydrogels is of great significance and has drawn tremendous attention. Through systematic simulation analysis, we formulated a simple supramolecular hydrogel (i.e., poly(AAm-co-NaSS)/BSA on the basis of electrostatic interaction between the sulfonate groups of poly(AAm-co-NaSS) and the protonated side groups of BSA, and proposed a novel pH-responsive mode for it: changing the internal electric charge composition of the hydrogel through pH-induced ionization/protonation transition of BSA, thereby regulating the structural stability/shrinkage/extension of the supramolecular network. On basis of this theory, the pH-responsiveness of the poly(AAm-co-NaSS)/BSA hydrogel, in principle, could be pre-designed by adjusting the initial BSA/NaSS ratio. In this regard, we fabricated a poly(AAm-co-NaSS)/BSA hydrogel prototype with a BSA/NaSS ratio of 1/57 and investigated its rheological/swelling/disassembling behavior under different pH conditions (1.7, 4.7, 7.7, 10.7, and 13.7). In addition, we also prepared two capecitabine-loaded poly(AAm-co-NaSS)/BSA hydrogel prototypes with BSA/NaSS ratios of 1/57 and 1/102 respectively at pH 4.0, and compared their drug release behavior in SGF and SIF. Finally, the experimental results fitted well with our theoretical expectations, which testified the rationality of our assumption. Thus, we believed that the poly(AAm-co-NaSS)/BSA supramolecular hydrogel could find diverse applications in the future.

Binary Double Network-like Structure: An Effective Energy-Dissipation System for Strong Tough Hydrogel Design.

Currently, hydrogels simultaneously featuring high strength, high toughness, superior recoverability, and benign anti-fatigue properties have demonstrated great application potential in broad fields; thus, great efforts have been made by researchers to develop satisfactory hydrogels. Inspired by the double network (DN)-like theory, we previously reported a novel high-strength/high-toughness hydrogel which had two consecutive energy-dissipation systems, namely, the unzipping of coordinate bonds and the dissociation of the crystalline network. However, this structural design greatly damaged its stretchability, toughness recoverability, shape recoverability, and anti-fatigue capability. Thus, we realized that a soft/ductile matrix is indispensable for an advanced strong tough hydrogel. On basis of our previous work, we herein reported a modified energy-dissipation model, namely, a "binary DN-like structure" for strong tough hydrogel design for the first time. This structural model comprises three interpenetrated polymer networks: a covalent/ionic dually crosslinked tightened polymer network (stiff, first order network), a constrictive crystalline polymer network (sub-stiff, second order network), and a ductile/flexible polymer network (soft, third order network). We hypothesized that under low tension, the first order network served as the sacrificing phase through decoordination of ionic crosslinks, while the second order and third order networks together functioned as the elastic matrix phase; under high tension, the second order network worked as the energy dissipation phase (ionic crosslinks have been destroyed at the time), while the third order network played the role of the elastic matrix phase. Owing to the "binary DN-like" structure, the as-prepared hydrogel, in principle, should demonstrate enhanced energy dissipation capability, toughness/shape recoverability, and anti-fatigue/anti-tearing capability. Finally, through a series of characterizations, the unique "binary DN-like" structure was proved to fit well with our initial theoretical assumption. Moreover, compared to other energy-dissipation models, this structural design showed a significant advantage regarding comprehensive properties. Therefore, we think this design philosophy would inspire the development of advanced strong tough hydrogel in the future.

Spectroscopic and theoretical study on the interaction between diperoxovanadate and oxazole.

Detailed investigations were carried out to explore the interaction systems of NH(4)VO(3)/H(2)O(2)/oxazole in aqueous solution under physiological conditions by a combined use of multinuclear NMR ((1)H, (13)C, (14)N and (51)V), diffusion ordered spectroscopy (DOSY), variable temperature NMR, electrospray ionization mass spectrometry (ESI-MS), spin-lattice relaxation and density functional calculations. The results indicated the formation of a new peroxovanadate species [OV(O(2))(2)(oxazole)](-) with oxazole coordinating to vanadium through nitrogen atom. The solution structure of the new species was predicted from theoretical calculations.

Interactions between diperoxovanadate complex and amide ligands in aqueous solution.

Multinuclear ((1)H, (13)C, (14)N, and (51)V) NMR spectroscopy has been used to study the reactions between the diperoxovanadate complex K(3)[OV(O(2))(2)(C(2)O(4))] x H(2)O (abbr. bpV(ox)) and ethylenediamine or diethylamine in aqueous solution. The interaction between bpV(ox) and diethylamine was very weak and no new complex was formed. However, bpV(ox) reacted with ethylenediamine giving a new product in which ethylenediamine attached to the vanadium atom via one nitrogen atom in a monodentate manner. Diffusion ordered spectroscopy (DOSY) measurements and theoretical calculations proved the formation of new product in bpV(ox) and ethylenediamine. The vanadium atoms in both [OV(O(2))(2)(C(2)O(4))](3-) and [OV(O(2))(2)(en)](-) species are six coordinated in solution state.