Supporting Information:I. Detailed process for the synthesis of the core NPs. Synthesis of hexagonal phase (β) NaGdF 4 :Yb,Er core NPs:The synthesis of the core NPs with a size of ~ 4.5 nm in this work were similar to previously report by van Veggel et al. 1 In a typical procedure, GdCl 3 (0.8 mmol), YbCl 3 (0.18 mmol), ErCl 3 (0.02 mmol), OA (4 mL) and ODE (15 mL) were mixed together and heated to 140 °C under vacuum until a clear solution formed, after that, the solution was cooled to room temperature. A solution of NaOH (2.5 mmol) and NH 4 F (4 mmol) in methanol (10 mL) was added and the mixture was stirred for a few hours. The reaction mixture was then heated at 70 °C to remove the methanol. Afterward, the solution was heated to 270 °C and maintained for 45 min under a gentle argon flow. Subsequently, the solution was cooled to room temperature and the NPs precipitated, centrifuged and washed twice with ethanol. The NPs were finally dispersed in 10 mL of cyclohexane for further use. Synthesis of cubic phase (α) small core NPs with (NaYbF 4 :Er) and without (NaYF 4 ) dopants:The trifluoroacetates (TFA) of Y, Yb, Tm, and Er were prepared by the procedure reported by Roberts et al. 2 The syntheses of the core NPs in this work were similar to that reported previously by Chen et al. 3 In a typical procedure (NaYbF 4 :Er, ~ 9 nm), 1.00 mmol of Na-TFA, 0.90 mmol of Yb-TFA, and 0.10 mmol of Er-TFA were dispersed in 16.0 mL of OA and 8.0 mL of OAM. The result solution was then heated at 120 °C under vacuum with magnetic stirring for 30 min to remove water and oxygen. Finally, the solution was heated to 275 °C at a rate of about 15 °C/min under Ar gas protection and kept at this temperature under vigorous stirring for about 30 min. Finally, the mixture was cooled to room temperature precipitated,
The low-efficiency cellular uptake property of current nanoparticles greatly restricts their application in the biomedical field. Herein, we demonstrate that novel virus-like mesoporous silica nanoparticles can easily be synthesized, showing greatly superior cellular uptake property. The unique virus-like mesoporous silica nanoparticles with a spiky tubular rough surface have been successfully synthesized via a novel single-micelle epitaxial growth approach in a low-concentration-surfactant oil/water biphase system. The virus-like nanoparticles’ rough surface morphology results mainly from the mesoporous silica nanotubes spontaneously grown via an epitaxial growth process. The obtained nanoparticles show uniform particle size and excellent monodispersity. The structural parameters of the nanoparticles can be well tuned with controllable core diameter (∼60–160 nm), tubular length (∼6–70 nm), and outer diameter (∼6–10 nm). Thanks to the biomimetic morphology, the virus-like nanoparticles show greatly superior cellular uptake property (invading living cells in large quantities within few minutes, <5 min), unique internalization pathways, and extended blood circulation duration (t1/2 = 2.16 h), which is much longer than that of conventional mesoporous silica nanoparticles (0.45 h). Furthermore, our epitaxial growth strategy can be applied to fabricate various virus-like mesoporous core–shell structures, paving the way toward designed synthesis of virus-like nanocomposites for biomedicine applications.
DNA is traditionally known as a central genetic biomolecule in living systems. From an alternative perspective, DNA is a versatile molecular building-block for the construction of functional materials, in particular biomaterials, due to its intrinsic biological attributes, molecular recognition capability, sequence programmability, and biocompatibility. The topologies of DNA building-blocks mainly include linear, circular, and branched types. Branched DNA recently has been extensively employed as a versatile building-block to synthesize new biomaterials, and an assortment of promising applications have been explored. In this review, we discuss the progress on DNA functional materials assembled from branched DNA. We first briefly introduce the background information on DNA molecules and sketch the development history of DNA functional materials constructed from branched DNA. In the second part, the synthetic strategies of branched DNA as building-blocks are categorized into base-pairing assembly and chemical bonding. In the third part, construction strategies for the branched DNA-based functional materials are comprehensively summarized including tile-mediated assembly, DNA origami, dynamic assembly, and hybrid assembly. In the fourth part, applications including diagnostics, protein engineering, drug and gene delivery, therapeutics, and cell engineering are demonstrated. In the end, an insight into the challenges and future perspectives is provided. We envision that branched DNA functional materials can not only enrich the DNA nanotechnology by ingenious design and synthesis but also promote the development of interdisciplinary fields in chemistry, biology, medicine, and engineering, ultimately addressing the growing demands on biological and medical-related applications in the real world.
In this work, we have successfully developed a novel multifunctional near-infrared (NIR)-stimulus controlled drug release system based on gold nanocages as photothermal cores, mesoporous silica shells as supporters to increase the anticancer drug loading and thermally responsive poly(N-isopropylacrylamide) (PNIPAM) as NIR-stimuli gatekeepers (Au-nanocage@mSiO2@ PNIPAM). The unique Au-nanocage@mSiO2 nanocarrier was elaborately fabricated by utilizing yolk-shell Ag-nanocube@mSiO2 nanostructure as a template by means of spatially confined galvanic replacement. The Au nanocage cores can effectively absorb and convert light to heat upon irradiation with a NIR laser, resulting in the collapse of the PNIPAM shell covering the exterior of mesoporous silica, and exposes the pores of mesoporous silica shell, realizing the triggered release of entrapped DOX drugs. The in vitro studies have clearly demonstrated the feasibility and advantage of the novel nanocarriers for remote-controlled drug release systems.
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