Shou-Jun Xiao

A proximity-based programmable DNA nanoscale assembly line

Our ability to synthesize nanometre-scale chemical species, such as nanoparticles with desired shapes and compositions, offers the exciting prospect of generating new functional materials and devices by combining them in a controlled fashion into larger structures. Self-assembly can achieve this task efficiently, but may be subject to thermodynamic and kinetic limitations: reactants, intermediates and products may collide with each other throughout the assembly time course to produce non-target species instead of target species. An alternative approach to nanoscale assembly uses information-containing molecules such as DNA to control interactions and thereby minimize unwanted cross-talk between different components. In principle, this method should allow the stepwise and programmed construction of target products by linking individually selected nanoscale components—much as an automobile is built on an assembly line. Here we demonstrate that a nanoscale assembly line can be realized by the judicious combination of three known DNA-based modules: a DNA origami tile that provides a framework and track for the assembly process, cassettes containing three independently controlled two-state DNA machines that serve as programmable cargo-donating devices and are attached in series to the tile, and a DNA walker that can move on the track from device to device and collect cargo. As the walker traverses the pathway prescribed by the origami tile track, it sequentially encounters the three DNA devices, each of which can be independently switched between an ‘ON’ state, allowing its cargo to be transferred to the walker, and an ‘OFF’ state, in which no transfer occurs. We use three different types of gold nanoparticle species as cargo and show that the experimental system does indeed allow the controlled fabrication of the eight different products that can be obtained with three two-state devices.

Dynamic patterning programmed by DNA tiles captured on a DNA origami substrate

The aim of nanotechnology is to put specific atomic and molecular species where we want them, when we want them there. Achieving such dynamic and functional control could lead to programmable chemical synthesis and nanoscale systems that are responsive to their environments. Structural DNA nanotechnology offers a powerful route to this goal by combining stable branched DNA motifs with cohesive ends to produce programmed nanomechanical devices and fixed or modified patterned lattices. Here, we demonstrate a dynamic form of patterning in which a pattern component is captured between two independently programmed DNA devices. A simple and robust error-correction protocol has been developed that yields programmed targets in all cases. This capture system can lead to dynamic control either on patterns or on programmed elements; this capability enables computation or a change of structural state as a function of information in the surroundings of the system.

Selfassembly of Metallic Nanoparticle Arrays by DNA Scaffolding

We report the self-assembly of metallic nanoparticle arrays using DNA crystals as a programmable molecular scaffolding. Gold nanoparticles, 1.4 nm in diameter, are assembled in two-dimensional arrays with interparticle spacings of 4 and 64 nm. The nanoparticles form precisely integrated components, which are covalently bonded to the DNA scaffolding. These results show that heterologous chemical systems can be assembled into precise, programmable geometrical arrangements by DNA scaffolding, thereby representing a critical step toward the realization of DNA nanotechnology.

Rolling Circle Amplification‐Based DNA Origami Nanostructrures for Intracellular Delivery of Immunostimulatory Drugs

Several single-stranded scaffold DNA, obtained from rolling circle amplification (RCA), are folded by different staples to form DNA nanoribbons. These DNA nanoribbons are rigid, simple to design, and cost-effective drug carriers, which are readily internalized by mammalian cells and show enhanced immunostimulatory activity.

Efficient adsorption of both methyl orange and chromium from their aqueous mixtures using a quaternary ammonium salt modified chitosan magnetic composite adsorbent

A quaternary ammonium salt modified chitosan magnetic composite adsorbent (CS-CTA-MCM) was prepared by combination of Fe3O4 nanoparticles. Various techniques were used to characterize the molecular structure, surface morphology, and magnetic feature of this composite adsorbent. CS-CTA-MCM was employed for the removal of Cr(VI) and methyl orange (MO), an anionic dye, from water in respective single and binary systems. Compared with chitosan magnetic adsorbent (CS-MCM) without modification, CS-CTA-MCM shows evidently improved adsorption capacities for both pollutants ascribed to the additional quaternary ammonium salt groups. Based on the adsorption equilibrium study, MO bears more affinity to CS-CTA-MCM than Cr(VI) causing a considerable extent of preferential adsorption of dye over metal ions in their aqueous mixture. However, at weak acidic solutions, Cr(VI) adsorption is evidently improved due to more efficient Cr(VI) forms, i.e. dichromate and monovalent chromate, binding to this chitosan-based adsorbent. Thus chromium could be efficient removal together with MO at suitable pH conditions. The adsorption isotherms and kinetics indicate that adsorptions of Cr(VI) and MO by CS-CTA-MCM both follow a homogeneous monolayer chemisorption process. This magnetic adsorbent after saturated adsorption could be rapidly separated from water and easily regenerated using dilute NaOH aqueous solutions then virtually reused with little adsorption capacity loss.

Nonfouling Polypeptide Brushes via Surface-initiated Polymerization of Nε-oligo(ethylene glycol)succinate-L-lysine N-carboxyanhydride

This contribution describes the preparation of nonfouling polypeptide brushes via surface-initiated ring-opening polymerization of oligo(ethylene glycol) modified L-lysine N-carboxyanhydrides. Circular dichroism experiments indicated that these surface-anchored polypeptide chains assume an α-helical conformation, which does not change between pH 4 and 9. Furthermore, nonspecific adsorption of fluorescent labeled bovine serum albumin and fibrinogen on glass slides modified with these brushes was greatly reduced compared to unmodified glass substrates.

Biochemical Modification of Titanium Surfaces

Surfaces play an important role in the response of the biological environment to the artificial material device. One reason is the fact that the physical, chemical and biochemical properties of the implant surface control performance-relevant processes such as protein adsorption, cell-surface interaction and cell/tissue development at the interface between the body and the biomaterial [1]. This is true in general and for the diverse applications of titanium discussed in this book. Different aspects of this interaction are treated in different chapters: the role of inorganic (e.g. oxide) surface films, in Chaps. 7 and 8; the importance of surface topography for cell-surface interaction and for osteointegration, in Chaps. 11,15 and 17, respectively; and the role of surface chemistry in the interaction with blood, in Chap. 14.

Preparation of chitosan-graft-polyacrylamide magnetic composite microspheres for enhanced selective removal of mercury ions from water ☆

A novel magnetic composite microsphere based on polyacrylamide (PAM)-grafted chitosan and silica-coated Fe3O4 nanoparticles (CS-PAM-MCM) was successfully synthesized by a simple method. The molecular structure, surface morphology, and magnetic characteristics of the composite microsphere were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), vibrating-sample magnetometer (VSM), and scanning electron microscopy (SEM). The prepared CS-PAM-MCM was applied as an efficient adsorbent for the removal of copper(II), lead(II), and mercury(II) ions from aqueous solutions in respective single, binary, and ternary metal systems. Compared with chitosan magnetic composite microsphere (CS-MCM) without modification, CS-PAM-MCM showed improved adsorption capacity for each metal ion and highly selective adsorption for Hg from Pb and Cu. This improvement is attributed to the formation of stronger interactions between Hg and the amide groups of PAM branches for chelating effects. The adsorption isotherms of Hg/Cu and Hg/Pb binary metal systems onto CS-PAM-MCM are both well-described by extended and modified Langmuir models, indicating that the removal of the three aforementioned metal ions may follow a similar adsorption manner; that is, through a homogeneous monolayer chemisorption process. Furthermore, these magnetic adsorbents could be easily regenerated in EDTA aqueous solution and reused virtually without any adsorption capacity loss.

Domain structures of phospholipid monolayer Langmuir-Blodgett films determined by atomic force microscopy

Atomic Force Microscopy (AFM) has been used to show the formation of solid-phase domains from fluid-phase domains on compression of DiPalmitoyl-PhosphatidylCholine (DPPC) monolayer Langmuir-Blodgett (LB) films. The chiral structures on the solid substrates were observed for the first time. By applying the friction force technique, we were able to distinguish the different regions of LB films according to their elastic properties. The influence of rates of compression on the domain shape as well as the microstructure within the domain were also studied.

RCA strands as scaffolds to create nanoscale shapes by a few staple strands.

Thousands of nucleotide(nt)-long single strand DNAs, generated from rolling-circle-amplification (RCA), were used as scaffolds to create DNA nanoscale wires and plates with a few short staple strands by following the origami design principle with a crossover at 1.5 turns. The core sequence of the circle template, for producing tens and hundreds of tandemly repeated copies of it by RCA, was designed according to Seemans sequence design principle for nucleic acid structural engineering (Seeman, N. C. J. Biomol. Struct. Dyn. 1990, 8, 573). The significance for folding the RCA products into nanoscale shapes lies in the design flexibility of both staple and scaffold strand codes, simplicity of a few short staple strands to fold the periodic sequence of RCA products, and lower cost.