Installing logic-gate responses to a variety of biological substances in supramolecular hydrogel–enzyme hybrids

Abstract

Soft materials that exhibit stimuli-responsive behaviour under aqueous conditions (such as supramolecular hydrogels composed of self-assembled nanofibres) have many potential biological applications. However, designing a macroscopic response to structurally complex biochemical stimuli in these materials still remains a challenge. Here we show that redox-responsive peptide-based hydrogels have the ability to encapsulate enzymes and still retain their activities. Moreover, cooperative coupling of enzymatic reactions with the gel response enables us to construct unique stimuli-responsive soft materials capable of sensing a variety of disease-related biomarkers. The programmable gel-sol response (even to biological samples) is visible to the naked eye. Furthermore, we built Boolean logic gates (OR and AND) into the hydrogel-enzyme hybrid materials, which were able to sense simultaneously plural specific biochemicals and execute a controlled drug release in accordance with the logic operation. The intelligent soft materials that we have developed may prove valuable in future medical diagnostics or treatments.

Sequentially Programmable and Cellularly Selective Assembly of Fluorescent Polymerized Vesicles for Monitoring Cell Apoptosis

“…To the best of our knowledge, this work represents the first example of programmable self‐assembly in living cells under sequentially integrated control of both endogenous and exogenous stimuli, i.e., enzymatic reaction and photopolymerization, respectively. Such programmable self‐assembly, relying on operations involving two or more stimuli arranged in a specific sequence,24, 25 can foreseeably improve selectivity and modularity of in situ and/or in vivo prepared smart biomaterials that can and will only respond to multiple stimuli in a predefined cascade 26, 27, 28. Moreover, fluorescence generation accompanied with the programmable self‐assembly endowed us capability of visualizing on site and in time information on biological structures and processes.…”

Reactive Oxygen Species (ROS) Responsive Polymers for Biomedical Applications

“…Reproduced with permission. [ 55 ] 2014, Macmillan Publishers Limited. strategy for fabrication of ROS-responsive materials, which enables the networks with ROS elimination capacity and extends the retention time of the antioxidants.…”

“…Hamachi and co-workers designed and synthesized a kind of redoxresponsive peptide-based hydrogels that are capable of sensing a variety of disease-related biomarkers. [ 55 ] They constructed di-and tripeptides that contained boronoaryl methoxycarbonyl (BAmoc) group at the N terminal and the BAmoc-peptides self-assembled to form a nanofi bre network (gel). Among the synthesized peptides, BPmocF 3 (BPmoc, boronophenylmethoxycarbonyl; F, phenylalanine) showed the lowest critical gel concentration (0.05 wt%).…”

“…Poly(propylene sulfi de) [19][20][21][22] Selenium-containing polymers [26,28,29] [ 25,30] Telluriumcontaining polymers [35][36][37] Poly(thioketal) [38][39][40]46] [ [41][42][43][44][45]55] Phenylboronic acid/ ester containing polymers Poly(L-methionine) [49] Poly(L-proline) [53,54] Macromolecular Bioscience www.mbs-journal.de and SN38 resulted in enhanced proliferation inhibition of tumor cells via inducing cell apoptosis. In addition to drug carrier, the thioether-containing particles themselves can also show inherent therapeutic properties against oxidative stress.…”

On Half-Adders Based on Fusion of Signal Carriers: Excitation, Fluidics, and Electricity

“…Most circuits implemented in laboratory experiments so far are one-bit half-adders. Half-adders and their component gates are realised using enzymatic networks [38,33,10,30,27], photonic molecular devices [7,8,25], quantum logic inside a single molecule [18], molecular structural circuits [19,32], acellular slime mould [40,3,28,41], nuclear magnetic resonance [36], ribosomes and mRNAs [35], peptide networks [9], and excitable chemical media [23,21,16,22]. In excitable chemical media signal careers are excitation waves; the signals are modified via interaction between the excitation waves or wave-fragments.…”