Stimuli‐Responsive Nucleic Acid‐Based Polyacrylamide Hydrogel‐Coated Metal–Organic Framework Nanoparticles for Controlled Drug Release

The synthesis of doxorubicin‐loaded metal–organic framework nanoparticles (NMOFs) coated with a stimuli‐responsive nucleic acid‐based polyacrylamide hydrogel is described. The formation of the hydrogel is stimulated by the crosslinking of two polyacrylamide chains, P_A and P_B, that are functionalized with two nucleic acid hairpins ( 4 ) and ( 5 ) using the strand‐induced hybridization chain reaction. The resulting duplex‐bridged polyacrylamide hydrogel includes the anti‐ATP (adenosine triphosphate) aptamer sequence in a caged configuration. The drug encapsulated in the NMOFs is locked by the hydrogel coating. In the presence of ATP that is overexpressed in cancer cells, the hydrogel coating is degraded via the formation of the ATP–aptamer complex, resulting in the release of doxorubicin drug. In addition to the introduction of a general means to synthesize drug‐loaded stimuli‐responsive nucleic acid‐based polyacrylamide hydrogel‐coated NMOFs hybrids, the functionalized NMOFs resolve significant limitations associated with the recently reported nucleic acid‐gated drug‐loaded NMOFs. The study reveals substantially higher loading of the drug in the hydrogel‐coated NMOFs as compared to the nucleic acid‐gated NMOFs and overcomes the nonspecific leakage of the drug observed with the nucleic‐acid‐protected NMOFs. The doxorubicin‐loaded, ATP‐responsive, hydrogel‐coated NMOFs reveal selective and effective cytotoxicity toward MDA‐MB‐231 breast cancer cells, as compared to normal MCF‐10A epithelial breast cells.     

Donor/Acceptor‐Modified Electrodes for Photoelectrochemical and Photobioelectrochemical Applications

A 7‐pyrrolidino‐7‐benzylamino‐8,8‐dicyanoquinodimethane, PBEDQ, ( 1 ), donor–acceptor–modified electrode yields, in the presence of hydroquinone, ( 2 ), an anodic photocurrent with quantum efficiency of 1.5%. The PBEDQ‐functionalized electrode yields, in the presence of the electron acceptor diquat, ( 3 ), a cathodic photocurrent with a quantum efficiency corresponding to 2.1%. The electron transfer cascades leading to the anodic or cathodic photocurrents in the different systems are discussed. It is further demonstrated that the integration of 1,4‐dihydronicotinamide adenine dinucleotide, NADH, as electron donor, with the PBEDQ‐modified electrode leads to an anodic photocurrent. This allowed the assembly of a photobioelectrochemical integrated electrode composed of the photoactive PBEDQ donor–acceptor compound, NAD⁺ as cofactor, and the NAD⁺‐dependent glucose dehydrogenase, GDH. Irradiation of the integrated electrode in the presence of glucose results in the GDH–biocatalyzed oxidation of glucose to gluconic acid with the concomitant generation of NADH that acts as electron donor for the photoactive donor–acceptor PBEDQ units, leading to the generation of steady‐state anodic photocurrent. The photocurrent intensities are controlled by the concentrations of glucose. The integrated PBEDQ/NAD⁺/GDH electrodes introduces a functional photobioelectrochemical electrode for the detection of glucose, and demonstrates the assembly of a functional photo‐biofuel cell that uses light and a biomass product (glucose) for the generation of electric power.     

Characterization of nanostructured surfaces generated by reconstitution of the porin MspA from Mycobacterium smegmatis

Nanostructures with long-term stability at the surface of gold electrodes are generated by reconstituting the porin MspA from Mycobacterium smegmatis into a specially designed monolayer of long-chain lipid surfactant on gold. Tailored surface coverage of gold electrodes with long-chain surfactants is achieved by electrochemically assisted deposition of organic thiosulfates (Bunte salts). The subsequent reconstitution of the octameric-pore MspA is guided by its extraordinary self-assembling properties. Importantly, electrochemical reduction of copper(II) yields copper nanoparticles within the MspA nanopores. Electrochemical impedance spectroscopy, reflection electron microscopy, and atomic force microscopy (AFM) show that: 1) the MspA pores within the self-assembled monolayer (SAM) are monodisperse and electrochemically active, 2) MspA reconstitutes in SAMs and with a 10-nm thickness, 3) AFM is a suitable method to detect pores within SAMs, and 4) the electrochemical reduction of Cu2+ to Cu0 under overpotential conditions starts within the MspA pores.     

Dynamic dispersion compensation in a 10-Gb/s optical system using anovel voltage tuned nonlinearly chirped fiber Bragg grating

We experimentally demonstrate dynamic dispersion compensation using a novel nonlinearly chirped fiber Bragg grating in a 10-Gb/s system. A single piezoelectric transducer continuously tunes the induced dispersion from 300 to 1000 ps/nm. The system achieves a bit-error rate=10^-9 after both 50 and 104 km of single-mode fiber by dynamically tuning the dispersion of the grating between 500 and 1000 ps/nm, respectively. The power penalty after 104 km is reduced from 3.5 to <1 dB     

Tunable compensation of channel degrading effects using nonlinearlychirped passive fiber Bragg gratings

Several channel-degrading effects are present in nonstatic and dynamically reconfigurable wavelength-division-multiplexed systems and networks due to various types of dispersion in the optical transmission fiber. These effects must be addressed by tunable methods so that data signals do not fade with time. The relevant effects for which we demonstrate tunable compensation include: chromatic dispersion accumulated in a single channel and in multiple channels, polarization mode dispersion, and periodic RF power fading. We utilize a nonlinearly chirped fiber Bragg grating that provides a dispersive function that can be varied continuously by tuning a single mechanical stretching element     

Following aptamer-thrombin binding by force measurements

The rupture forces between an aptamer (1)-functionalized AFM tip and a thrombin-modified Au surface are analyzed. The rupture force for a single aptamer/thrombin complex is determined as approximately 4.45 pN. The analysis of the system reveals that the rupture forces correspond to the melting of the G-quadruplex structure of the aptamer bound to the thrombin. This melting of the G-quadruplex leads to the dissociation of the aptamer/thrombin complex.     

Photosystem I (PSI)/Photosystem II (PSII)‐Based Photo‐Bioelectrochemical Cells Revealing Directional Generation of Photocurrents

Layered assemblies of photosystem I, PSI, and/or photosystem II, PSII, on ITO electrodes are constructed using a layer‐by‐layer deposition process, where poly N,N′‐dibenzyl‐4,4′‐bipyridinium (poly‐benzyl viologen, PBV²⁺) is used as an inter‐protein “glue”. While the layered assembly of PSI generates an anodic photocurrent only in the presence of a sacrificial electron donor system, such as dichlorophenol indophenol (DCPIP)/ascorbate, the PSII‐modified electrode leads, upon irradiation, to the formation of an anodic photocurrent (while evolving oxygen), in the absence of any sacrificial component. The photocurrent is generated by transferring the electrons from the PSII units to the PBV²⁺ redox polymer. The charge‐separated species allow, then, the injection of the electrons to the electrode, with the concomitant evolution of O₂. A layered assembly, consisting of a PSI layer attached to a layer of PSII by the redox polymer PBV²⁺, leads to an anodic photocurrent that is 2‐fold higher, as compared to the anodic photocurrent generated by a PSII‐modified electrode. This observation is attributed to an enhanced charge separation in the two‐photosystem assembly. By the further nano‐engineering of the two photosystems on the electrode using two different redox polymers, vectorial electron transfer to the electrode is demonstrated, resulting in a ca. 6‐fold enhancement in the photocurrent. The reversed bi‐layer assembly, consisting of a PSII layer linked to a layer of PSI by the PBV²⁺ redox polymer, yields, upon irradiation, an inefficient cathodic current. This observation is attributed to a mixture of photoinduced electron transfer reactions of opposing effects on the photocurrent directions in the two‐photosystem assembly.