Self-Regulatory Micro- and Macroscale Patterning of ATP-Mediated Nanobioconjugate

Abstract

Directional interactions and the assembly of a nanobioconjugate in clusters at a specific location are important for patterning and microarrays in biomedical research. Herein, we report that self-assembly and spatial control in surface patterning of the surfactant-functionalized nanoparticles can be governed in micro-and macroscale environments by two factors, synergistic enzyme−substrate−nanoparticle affinity and the phoretic effect. First, we show that aggregation of cationic gold nanoparticles (GNP) can be modulated by multivalent anionic nanoparticle binding of an adenosine-based nucleotide and enzyme, alkaline phosphatase. We further demonstrate two different types of their autonomous aggregation pattern: (i) by introducing an enzyme gradient that modulates the synergistic nonequilibrium interactivity of the nanoparticle, nucleotide, and enzyme both in microfluidic conditions and at the macroscale; and (ii) the surface deposition pattern from evaporating droplets via the coffee ring effect. Here, temporal control over the width and site of the patterning area inside the microfluidic channel under catalytic and noncatalytic conditions has also been demonstrated. Finally, we show a change in capillary phoresis parameters responsible for the coffee ring due to introduction of ATP-loaded GNP in the blood serum, showing applicability in low-cost disease diagnostics. Overall, an enzyme-actuated surface nanobiopatterning method has been demonstrated that has potential application in controlled micro-and macroscale area patterning with a diverse cascade catalytic surface and spatiotemporal multisensory-based application.

Fenton-like Degradation of Methylene Blue on Attapulgite Clay Composite by Loading of Iron–Oxide: Eco-Friendly Preparation and Its Catalytic Activity

“…The zeta potential of R-ATP, P-ATP, P-ATP@Fe 3 O 4 , A-ATP, and A-ATP@Fe 3 O 4 is displayed in Figure 7 b to determine their proximal surface charge [ 41 , 42 , 43 ]. With the treatment and modification of R-ATP by H 2 O 2 , HCl, and Fe 3 O 4 nanoparticles, the zeta potential of R-ATP, P-ATP, P-ATP@Fe 3 O 4 , A-ATP, and A-ATP@Fe 3 O 4 gradually becomes negative under neutral conditions.…”

Co-assembly-mediated biosupramolecular catalysis: thermodynamic insights into nucleobase specific (oligo)nucleotide attachment and cleavage

“…We envisage that this knowledge can not only highlight the importance of the distinctive behavior of the confined enzyme toward substrate-specific catalysis but also showed a way to develop future multienzymatic cascade systems that can be modulated by oligonucleotide inputs. 54–58 Additionally, this biosupramolecular approach can be of importance in oligonucleotide-based therapeutics as it shows possibility of gaining both dormant or non-cleavable and active or quickly digestible sequences, and future studies will follow up with more complex oligo-sequences having therapeutic importance. 42,43,58–61…”

Spatiotemporally tuned colloidal phoretic leap in an altering multivalent interaction field

“…Spatial cues at macroscopic scales are important in natural systems in the form of signaling gradients such as the extracellular matrix and for bone/cartilage development, and have also recently been applied in synthetic systems to understand reaction-diffusion kinetics and spatially segregated chemistry and morphogenesis. [50][51][52][53][54] We therefore investigated the ability of nucleotide gradients to drive diffusiophoretic motion in a macroscale system in absence of any continuous flow. Our macroscale experimental set up as shown in Figure 3a.…”