EphA4/ephrinA3 reverse signaling mediated downregulation of glutamate transporter GLAST in Müller cells in an experimental glaucoma model.

Deficiency of glutamate transporter GLAST in Müller cells may be culpable for excessive extracellular glutamate, which involves in retinal ganglion cell (RGC) damage in glaucoma. We elucidated how GLAST was regulated in rat chronic ocular hypertension (COH) model. Western blot and whole-cell patch-clamp recordings showed that GLAST proteins and GLAST-mediated current densities in Müller cells were downregulated at the early stages of COH. In normal rats, intravitreal injection of the ephrinA3 activator EphA4-Fc mimicked the changes of GLAST in COH retinas. In purified cultured Müller cells, EphA4-Fc treatment reduced GLAST expression at mRNA and protein levels, which was reversed by the tyrosine kinase inhibitor PP2 or transfection with ephrinA3-siRNA (Si-EFNA3), suggesting that EphA4/ephrinA3 reverse signaling mediated GLAST downregulation. EphA4/ephrinA3 reverse signaling-induced GLAST downregulation was mediated by inhibiting PI3K/Akt/NF-κB pathways since EphA4-Fc treatment of cultured Müller cells reduced the levels of p-Akt/Akt and NF-κB p65, which were reversed by transfecting Si-EFNA3. In Müller cells with ephrinA3 knockdown, the PI3K inhibitor LY294002 still decreased the protein levels of NF-κB p65 in the presence of EphA4-Fc, and the mRNA levels of GLAST were reduced by LY294002 and the NF-κB inhibitor SN50, respectively. Pre-injection of the PI3K/Akt pathway activator 740 Y-P reversed the GLAST downregulation in COH retinas. Western blot and TUNEL staining showed that transfecting of Si-EFNA3 reduced Müller cell gliosis and RGC apoptosis in COH retinas. Our results suggest that activated EphA4/ephrinA3 reverse signaling induces GLAST downregulation in Müller cells via inhibiting PI3K/Akt/NF-κB pathways, thus contributing to RGC damage in glaucoma.

Cascaded, Feedback-Driven, and Spatially Localized Emergence of Constitutional Dynamic Networks Driven by Enzyme-Free Catalytic DNA Circuits.

The enzyme-free catalytic hairpin assembly (CHA) process is introduced as a functional reaction module for guided, high-throughput, emergence, and evolution of constitutional dynamic networks, CDNs, from a set of nucleic acids. The process is applied to assemble networks of variable complexities, functionalities, and spatial confinement, and the systems provide possible mechanistic pathways for the evolution of dynamic networks under prebiotic conditions. Subjecting a set of four or six structurally engineered hairpins to a promoter P1 leads to the CHA-guided emergence of a [2 × 2] CDN or the evolution of a [3 × 3] CDN, respectively. Reacting of a set of branched three-arm DNA-hairpin-functionalized junctions to the promoter strand activates the CHA-induced emergence of a three-dimensional (3D) CDN framework emulating native gene regulatory networks. In addition, activation of a two-layer CHA cascade circuit or a cross-catalytic CHA circuit and cascaded driving feedback-driven evolution of CDNs are demonstrated. Also, subjecting a four-hairpin-modified DNA tetrahedron nanostructure to an auxiliary promoter strand simulates the evolution of a dynamically equilibrated DNA tetrahedron-based CDN that undergoes secondary fueled dynamic reconfiguration. Finally, the effective permeation of DNA tetrahedron structures into cells is utilized to integrate the four-hairpin-functionalized tetrahedron reaction module into cells. The spatially localized miRNA-triggered CHA evolution and reconfiguration of CDNs allowed the logic-gated imaging of intracellular RNAs. Beyond the bioanalytical applications of the systems, the study introduces possible mechanistic pathways for the evolution of functional networks under prebiotic conditions.

Highly Efficient Wavelength-Resolved Electrochemiluminescence of Carbon Nitride Films for Ultrasensitive Multiplex MicroRNA Detection.

The development of electrochemiluminescence (ECL) emitters of different colors with high ECL efficiency (ΦECL) is appealing yet challenging for ultrasensitive multiplexed bioassays. Herein, we report the synthesis of highly efficient polymeric carbon nitride (CN) films with fine-tuned ECL emission from blue to green (410, 450, 470, and 525 nm) using the precursor crystallization method. More importantly, naked eye-observable and significantly enhanced ECL emission was achieved, and the cathodic ΦECL values were ca. 112, 394, 353, and 251 times those of the aqueous Ru(bpy)3Cl2/K2S2O8 reference. Mechanism studies showed that the density of surface-trapped electrons, the associated nonradiative decay pathways, and electron-hole recombination kinetics were crucial factors for the high ΦECL of CN. Based on high ΦECL and different colors of ECL emission, the wavelength-resolved multiplexing ECL biosensor was constructed to simultaneously detect miRNA-21 and miRNA-141 with superior low detection limits of 0.13 fM and 25.17 aM, respectively. This work provides a facile method to synthesize wavelength-resolved ECL emitters based on metal-free CN polymers with high ΦECL for multiplexed bioassays.

Carbon Nitride-Based Heterojunction Photoelectrodes with Modulable Charge-Transfer Pathways toward Selective Biosensing.

Photoelectrochemical (PEC) sensing enables the rapid, accurate, and highly sensitive detection of biologically important chemicals. However, achieving high selectivity without external biological elements remains a challenge because the PEC reactions inherently have poor selectivity. Herein, we report a strategy to address this problem by regulating the charge-transfer pathways using polymeric carbon nitride (pCN)-based heterojunction photoelectrodes. Interestingly, because of redox reactions at different semiconductor/electrolyte interfaces with specific charge-transfer pathways, each analyte demonstrated a unique combination of photocurrent-change polarity. Based on this principle, a pCN-based PEC sensor for the highly selective sensing of ascorbic acid in serum against typical interferences, such as dopamine, glutathione, epinephrine, and citric acid was successfully developed. This study sheds light on a general PEC sensing strategy with high selectivity without biorecognition units by engineering charge-transfer pathways in heterojunctions on photoelectrodes.

Delayed Polarization Saturation Induced Superior Energy Storage Capability of BiFeO3 -Based Ceramics Via Introduction of Non-Isovalent Ions.

Electrostatic capacitors are emerging as a highly promising technology for large-scale energy storage applications. However, it remains a significant challenge to improve their energy densities. Here, an effective strategy of introducing non-isovalent ions into the BiFeO3 -based (BFO) ceramic to improve energy storage capability via delaying polarization saturation is demonstrated. Accordingly, an ultra-high energy density of up to 7.4 J cm-3 and high efficiency ≈ 81% at 680 kV m-1 are realized, which is one of the best energy storage performances recorded for BFO-based ceramics. The outstanding comprehensive energy storage performance is attributed to inhibiting the polarization hysteresis resulting from generation ergodic relaxor zone and random field, and generating highly-delayed polarization saturation with continuously-increased polarization magnitudes with the electric field of supercritical evolution. The contributions demonstrate that delaying the polarization saturation is a consideration for designing the next generation of lead-free dielectric materials with ultra-high energy storage performance.

Elucidating Electrocatalytic Oxygen Reduction Kinetics via Intermediates by Time-Dependent Electrochemiluminescence.

Facile evaluation of oxygen reduction reaction (ORR) kinetics for electrocatalysts is critical for sustainable fuel-cell development and industrial H2 O2 production. Despite great success in ORR studies using mainstream strategies, such as the membrane electrode assembly, rotation electrodes, and advanced surface-sensitive spectroscopy, the time and spatial distribution of reactive oxygen species (ROS) intermediates in the diffusion layer remain unknown. Using time-dependent electrochemiluminescence (Td-ECL), we report an intermediate-oriented method for ORR kinetics analysis. Owing to multiple ultrasensitive stoichiometric reactions between ROS and the ECL emitter, except for electron transfer numbers and rate constants, the potential-dependent time and spatial distribution of ROS were successfully obtained for the first time. Such exclusively uncovered information would guide the development of electrocatalysts for fuel cells and H2 O2 production with maximized activity and durability.

Stimuli-responsive metal-organic framework nanoparticles for controlled drug delivery and medical applications.

Stimuli-responsive metal-organic framework nanoparticles, NMOFs, provide a versatile platform for the controlled release of drugs and biomedical applications. The porous structure of NMOFs, their biocompatibility, low toxicity, and efficient permeability turn the NMOFs into ideal carriers for therapeutic applications. Two general methods to gate the drug-loaded NMOFs and to release the loads were developed: by one method, the loaded NMOFs are coated or surface-modified with stimuli-responsive gates being unlocked in the presence of appropriate chemical (e.g., ions or reducing agents), physical (e.g., light or heat), or biomarker (e.g., miRNA or ATP) triggers. By a second approach, the drug-loaded NMOFs include encoded structural information or co-added agents to induce the structural distortion or stimulate the degradation of the NMOFs. Different chemical triggers such as pH changes, ions, ATP, or redox agents, and physical stimuli such as light or heat are applied to degrade the NMOFs, resulting in the release of the loads. In addition, enzymes, DNAzymes, and disease-specific biomarkers are used to unlock the gated NMOFs. The triggered release of drugs for cancer therapy, anti-blood clotting, and the design of autonomous insulin-delivery systems ("artificial pancreas") are discussed. Specifically, multi-drug carrier systems and functional NMOFs exhibiting dual and cooperative therapeutic functions are introduced. The future perspectives and applications of stimuli-responsive particles are addressed.

Extended Conjugation Tuning Carbon Nitride for Non-sacrificial H2 O2 Photosynthesis and Hypoxic Tumor Therapy.

Artificial photocatalysis offers a clean approach for producing H2 O2 . However, the poor selectivity and activity of H2 O2 production hamper traditional industrial applications and emerging photodynamic therapy (PDT)/chemodynamic therapy (CDT). Herein, we report a C5 N2 photocatalyst with a conjugated C=N linkage for selective and efficient non-sacrificial H2 O2 production in both normoxic and hypoxic systems. The strengthened delocalization of π-electrons by linkers in C5 N2 downshifted the band position, thermodynamically eliminating side H2 evolution reaction and kinetically promoting water oxidation. As a result, C5 N2 had a competitive solar-to-chemical conversion efficiency of 0.55 % in overall H2 O2 production and exhibited by far the highest activity under hypoxic conditions (698 µM h-1 ). C5 N2 was further applied to hypoxic PDT/CDT with outstanding performance in apparent cancer cell death and synchronous bioimaging. The study sheds light on the photosynthesis of H2 O2 by carbon nitrides for health applications.

Mimicking Functions of Native Enzymes or Photosynthetic Reaction Centers by Nucleoapzymes and Photonucleoapzymes.

The covalent linkage of catalytic units to aptamer sequence-specific nucleic acids exhibiting selective binding affinities for substrates leads to functional scaffolds mimicking native enzymes, nucleoapzymes. The binding of the substrates to the aptamer and their structural orientation with respect to the catalytic units duplicate the functions of the active center of enzymes. The possibility of linking the catalytic sites directly, or through spacer units, to the 5'-end, 3'-end, and middle positions of the aptamers allows the design of nucleoapzyme libraries, revealing structure-functions diversities, and these can be modeled by molecular dynamics simulations. Catalytic sites integrated into nucleoapzymes include DNAzymes, transition metal complexes, and organic ligands. Catalytic transformations driven by nucleoapzymes are exemplified by the oxidation of dopamine or l-arginine, hydroxylation of tyrosine to l-DOPA, hydrolysis of ATP, and cholic acid-modified esters. The covalent linkage of photosensitizers to the tyrosinamide aptamer leads to a photonucleoapzyme scaffold that binds the N-methyl-N'-(3-aminopropane)-4,4'-bipyridinium-functionalized tyrosinamide to the aptamer. By linking the photosensitizer directly, or through a spacer bridge to the 5'-end or 3'-end of the aptamer, we demonstrate a library of supramolecular photosensitizer/electron acceptor photonucleoapzymes mimicking the functions of photosystem I in the photosynthetic apparatus. The photonucleoapzymes catalyze the photoinduced generation of NADPH, in the presence of ferredoxin-NADP+-reductase (FNR), or the photoinduced H2 evolution catalyzed by Pt nanoparticles. The future prospects of nucleoapzymes and photonucleoapzymes are discussed.

Dictated Emergence of Nucleic Acid-Based Constitutional Dynamic Networks by DNA Replication Machineries.

The emergence of nucleic acid-based constitutional dynamic networks, CDNs, from a pool of nucleic acids is a key process for the understanding and modality of the evolution of biological networks. We present a versatile method that applies a library of nucleic acids coupled to biocatalytic DNA machineries as functional modules for the emergence of CDNs of diverse composition, complexity, and structural diversity. A set of four DNA template/blocker scaffolds coupled to the polymerase/dNTP replication machinery leads, in the presence of a primer, P1, to the gated replication of the scaffolds and to the displacement of four components that reconfigure into a [2 × 2] CDN. Using six template/blocker scaffolds and the polymerase/dNTPs, the P1-guided emergence of a [3 × 3] CDN is demonstrated. In addition, by further engineering the template/blocker scaffolds, the hierarchical control over the composition of the P1-guided emergence of [3 × 3] CDNs is accomplished. Also, sequence-engineered template/blocker scaffolds, coupled to the polymerase/dNTP machinery, lead, in the presence of two primers P1 and/or P2, to the selective emergence of two different [2 × 2] CDNs or to a [3 × 3] CDN. Also, a set of six appropriately engineered template/blocker scaffolds, coupled to the polymerase/dNTP machinery, leads to the emergence of a CDN composed of four equilibrated DNA tetrahedra constituents. Finally, by further sequence engineering of the set of template/blocker scaffolds and their coupling to a nicking/polymerization/dNTP replication machinery, the amplified high-throughput emergence of CDNs is demonstrated.

Dissipative Gated and Cascaded DNA Networks.

Nucleic acid based, out-of-equilibrium, dissipative networks driven by nucleic acid fuels coupled to the nicking enzyme, Nt.BbvCI, are presented. One set of experiments includes a functional module consisting of a duplex and two fluorophore-labeled strands. The fuel-triggered activation of the functional module leads to a supramolecular intermediate composed of a template bound to the two fluorophore-labeled strands. Nicking of the fuel strand by Nt.BbvCI yields "waste" products, resulting in the regeneration of original system. The transient dissipative behavior of the systems is probed by following the FRET signal generated by the fluorophore labels associated with the intermediate supramolecular complex. The second set of experiments introduces two functional modules activated in parallel by the fuel strand. Using two inhibitors, I1 or I2, the selective gated dissipative operation of the networks is demonstrated. Finally, experiments presenting the intercommunication and cascading of two dissipative networks are introduced. Subjecting the networks to the fuel strands leads to intercommunication between the networks by strand-transfer and strand-feedback processes, allowing the cascaded dissipative operation of the assembly. The experimental results of the different dissipative systems are accompanied by kinetic models and computational simulations. The computational simulations provide useful means to predict the dissipative transient patterns of the systems at different auxiliary conditions.

Gated Dissipative Dynamic Artificial Photosynthetic Model Systems.

Gated dissipative artificial photosynthetic systems modeling dynamically modulated environmental effects on the photosynthetic apparatus are presented. Two photochemical systems composed of a supramolecular duplex scaffold, a photosensitizer-functionalized strand (photosensitizer is Zn(II)protoporphyrin IX, Zn(II)PPIX, or pyrene), an electron acceptor bipyridinium (V2+)-modified strand, and a nicking enzyme (Nt.BbvCI) act as functional assemblies driving transient photosynthetic-like processes. In the presence of a fuel strand, the transient electron transfer quenching of the photosensitizers, in each of the photochemical systems, is activated. In the presence of a sacrificial electron donor (mercaptoethanol) and continuous irradiation, the resulting electron transfer process in the Zn(II)PPIX/V2+ photochemical module leads to the transient accumulation and depletion of the bipyridinium radical-cation (V·+) product, and in the presence of ferredoxin-NADP+ reductase and NADP+, to the kinetically modulated photosynthesis of NADPH. By subjecting the mixture of two photochemical modules to one of two inhibitors, the gated transient photoinduced electron transfer in the two modules is demonstrated. Such gated dissipative process highlights its potential as an important pathway to protect artificial photosynthetic module against overdose of irradiance and to minimize photodamage.

Triggered Dimerization and Trimerization of DNA Tetrahedra for Multiplexed miRNA Detection and Imaging of Cancer Cells.

The reversible and switchable triggered reconfiguration of tetrahedra nanostructures from monomer tetrahedra structures into dimer or trimer structures is introduced. The triggered bridging of monomer tetrahedra by K+ -ion-stabilized G-quadruplexes or T-A•T triplexes leads to dimer or trimer tetrahedra structures that are separated by crown ether or basic pH conditions, respectively. The signal-triggered dimerization/trimerization of DNA tetrahedra structures is used to develop multiplexed miRNA-sensing platforms, and the tetrahedra mixture is used for intracellular sensing and imaging of miRNAs.

Positive abundance-elevational range size relationship weakened from temperate to subtropical ecosystems.

Describing the patterns and revealing the underlying mechanisms responsible for variations in community structure remain a central focus in ecology. However, important gaps remain, including our understanding of species abundance. Most studies on abundance-based relationships are from either temperate ecosystems or tropical ecosystems, and few have explicitly tested abundance-based relationships across a temperate to tropical ecotone. Here, we use a comprehensive dataset of breeding birds across elevation spanning a temperate to subtropical gradient in the Himalayas-Hengduan Mountains of China to examine the relationship between species abundance and (a) elevational range size, (b) body size, (c) elevational range centre and (d) endemicity. We tested a priori predictions for abundance-elevational range size relationship, abundance-body size relationship and abundance-elevational range centre relationship, and explored how these relationships change along this temperate to subtropical mountain ecosystem. We found that species abundance was significantly positively correlated with elevational range size across the study sites, demonstrating the key importance of elevational range size towards species abundance. Body size and elevational range centre are weakly correlated with abundance. A novel finding of our study is that the abundance-elevational range size relationship gradually weakened from temperate to subtropical ecosystems, adding to a growing body of evidence suggesting that abundance-elevational range size tracks a temperate to tropical ecotone. Our study demonstrates that abundance range-size relationship can transition across ecotones where faunas of different evolutionary origins converge. Furthermore, measuring abundance relationships across different environmental variables at the same spatial scale with comparable biogeography is a key strategy that can reveal the underlying mechanisms behind abundance patterns.

Nucleic Acid Based Constitutional Dynamic Networks: From Basic Principles to Applications.

Inspired by nature where intracellular dynamic interactions between DNA, RNA and proteins processed within complex networks leading to programmed reaction patterns, extensive research efforts are directed to mimic these processes by chemical means, "Systems Chemistry". The present perspective introduces nucleic acids as functional modules to construct constitutional dynamic networks, CDNs, mimicking natural networks. The base sequences comprising nucleic acids provide a rich "tool box" to assemble signal-triggered reconfigurable CDNs revealing adaptive and hierarchically adaptive properties, intercommunication between CDNs, and feedback-driven reaction pathways similar to natural systems. Pathways for the evolution of CDNs and the formation of networks of enhanced complexities are discussed. Different applications of constitutional dynamic networks are introduced including programmed catalysis, CDN-guided optical and catalytic functions of nanoparticle aggregates, and CDN-dictated stiffness and self-healing functions of hydrogels. Future perspectives of the field in designing dissipative transient CDNs, CDNs-guided transcription/translation synthesis of selective proteins, and the challenging integration of CDNs into cell-like containments aiming to assemble "artificial cells" are addressed.

Triggered Interconversion of Dynamic Networks Composed of DNA-Tetrahedra Nanostructures.

Constitutional dynamic networks (CDNs) consisting of DNA tetrahedra allow the dynamically triggered adaptive control over the compositions and structures of the constituents. In one system, a CDN consisting of four tetrahedra constituents is orthogonally triggered by two alternative triggers, T1 or T2, to reconfigure into two different CDNs, revealing adaptive control-over the tetrahedra compositions in the two CDNs. In the presence of the counter triggers T1' or T2', the parent CDN is regenerated. In the second system, the assembly of a CDN consisting of four dimeric tetrahedra exhibiting variable sizes and shapes is described. The orthogonal triggering of the CDN by two different triggers T3 or T4, leads to the adaptive reconfiguration of the CDN into new equilibrated CDNs exhibiting control-over the compositions and shapes of the dimeric tetrahedra comprising the CDNs. Mg2+-ion-dependent DNAzyme units conjugated to the tetrahedra nanostructures and complementary electrophoretic experiments provide means to quantitatively evaluate the compositions of the different CDN systems. By the functionalization of the four-tetrahedra-based CDN system with two fluorophor donor-acceptor pairs and the orthogonal reconfiguration of the CDN in the presence of two alternative triggers, the control-over the FRET functions of the CDN systems is demonstrated.

Photosensitized H2 Evolution and NADPH Formation by Photosensitizer/Carbon Nitride Hybrid Nanoparticles.

The broadband C3N4 semiconductor absorbs in the UV region, λ = 330-380 nm, a feature limiting its application for light-to-energy conversion. The unique surface adsorption properties of C3N4 allow, however, the binding of a photosensitizer, operating in the visible-solar spectrum to the surface of C3N4. Coupling of the energy levels of the photosensitizer with the energy levels of C3N4 allows effective photoinduced electron-transfer quenching and subsequent charge separation in the hybrid structures. Two methods to adsorb a photosensitizer on the C3N4 nanoparticles are described. One is exemplified by the adsorption of Zn(II)-protoporphyrin IX on C3N4 using π-π interactions. The second method utilizes the specific binding interactions of single-stranded nucleic acids on C3N4 and involves the binding of a Ru(II)-tris-bipyridine-modified nucleic acid on the C3N4 nanoparticles. Effective electron-transfer quenching of the photoexcited photosensitizers by C3N4 proceeds in the two hybrid systems. The two hybrid photosystems induce the effective photosensitized reduction of N,N'-dimethyl-4,4'-bipyridinium, MV2+, to MV+•, in the presence of Na2EDTA as a sacrificial electron donor. The generation of MV+• is ca. 5-fold higher as compared to the formation of MV+• in the presence of the photosensitizer alone (in the absence of C3N4). The effective generation of MV+• in the photosystems is attributed to the efficient quenching of the photosensitizers, followed by effective charge separation of the electrons in the conduction band of C3N4 and the holes in the oxidized photosensitizer. The subsequent transfer of the conduction-band electrons to MV2+ and the oxidation of Na2EDTA by the oxidized photosensitizers lead to the effective formation of MV+•. The photogenerated MV+• by the two hybrid photosystems is used to catalyze H2 evolution in the presence of Pt nanoparticle catalysts and to mediate the reduction of NADP+ to NADPH, in the presence of ferredoxin-NADP+ reductase, FNR. The ability to couple the photogenerated NADPH to drive NADP+-dependent biocatalytic transformations is demonstrated.

Anti-VEGF-Aptamer Modified C-Dots-A Hybrid Nanocomposite for Topical Treatment of Ocular Vascular Disorders.

The vascular endothelial growth factor (VEGF) induces pathological angiogenetic ocular diseases. It is a scientific challenge to develop carriers for the controlled release of inhibitors for VEGF present in the back of the eye domain. Carbon dots (C-dots) functionalized with the VEGF aptamer are introduced and the hybrid nanoparticles are used for ocular nanomedicine. The C-dots are applied as effective carriers of the anti-VEGF aptamer across the cornea, yielding therapeutic levels upon topical administration. The hybrids show no toxicity for both in vitro and in vivo murine animal model, and further enable noninvasive intraocular concentration monitoring through the C-dots inherent fluorescence. In addition, the hybrid C-dots effectively inhibit VEGF-stimulated angiogenesis in choroidal blood vessels. This inhibition is comparable to two commercially available anti-VEGF drugs, bevacizumab and aflibercept. The hybrid aptamer-modified C-dots provide a versatile nanomaterial to treat age-related macular degeneration and diabetic retinopathy.

Molecular engineering of polymeric carbon nitride: advancing applications from photocatalysis to biosensing and more.

As a promising two-dimensional (2D) conjugated polymer, polymeric carbon nitride (CN) is attracting dramatically increasing interest due to its unusual properties, facile synthesis from abundant and inexpensive starting materials, and promising applications ranging from (photo)catalysis, and photoelectrochemistry, to biosensors. The polymeric feature and facile synthesis of CN allow easy engineering of its structure at the molecular level. For instance, the moderate reactivity of CN at the interface, together with the aromatic π-conjugated framework and intralayer hydrogen bonds, provides ample possibilities to control its molecular structure and properties to meet task-specific applications. This review summarizes and highlights a panorama of the latest advancements related to the design and construction of the molecular structure of CN, such as by doping and copolymerization, engineering of the polymerization degree, coordination interaction, covalent and noncovalent functionalization, and modulation of intralayer hydrogen bonding. Beyond photocatalysis, the emerging applications of CN are also briefly discussed with a special emphasis on sensing, bioimaging and biotherapy, smart responsive systems and photoelectrochemical devices. This review ends with perspectives on the challenges and future prospects of molecular engineering of CN.

Switchable Triggered Interconversion and Reconfiguration of DNA Origami Dimers and Their Use for Programmed Catalysis.

The switchable reconfiguration of a mixture of two dimers of DNA origami tiles, AB and CD, into a mixture of two DNA origami dimers composed of AD and CB, using a collection of fuel and antifuel strands, is presented. The reversible reconfiguration of the mixture of dimers AB and CD into AD and CB, is followed by labeling each of the tiles with 0, 1, 2, and 3 4× hairpins labels and by imaging the dimer structures by atomic force microscopy. Subjecting the reconfigurable dimer mixtures to a collection of Mg2+-ion-dependent DNAzyme subunits and the substrates consisting of the ROX/BHQ2-modified substrate and the FAM/BHQ1-modified substrate leads to the triggered and programmed switchable operation, in the presence of appropriate fuel and antifuel strands. In the presence of the AB and CD mixture, the DNAzyme subunits cleaving the ROX/BHQ2-modified substrate is switched on, leading to the fluorescence of ROX. The reconfiguration of the AB and CD dimer mixture to the AD and CB dimer mixture leads to the assembly of the DNAzyme subunits that switches on the cleavage of the FAM/BHQ1-modified substrate and to the fluorescence of FAM. By the cyclic and reversible reconfiguration of the AB and CD dimer mixture to the AD and CB dimer mixture, in the presence of the appropriate fuel and antifuel strands, the switchable catalytic operation of two Mg2+-ion-dependent DNAzymes, leading to the fluorescence of ROX or FAM, is demonstrated.