The global burden of cancer is increasing rapidly, and nanomedicine offers promising prospects for enhancing the life expectancy of cancer patients. Janus nanoparticles (JNPs) have garnered considerable attention due to their asymmetric geometry, enabling multifunctionality in drug delivery and theranostics. However, achieving precise control over the self-assembly of JNPs in solution at the nanoscale level poses significant challenges. Herein, a low-temperature reversed-phase microemulsion system was used to obtain homogenous Mn3O4-Ag2S JNPs, which showed significant potential in cancer theranostics. Structural characterization revealed that the Ag2S (5-10 nm) part was uniformly deposited on a specific surface of Mn3O4 to form a Mn3O4-Ag2S Janus morphology. Compared to the single-component Mn3O4 and Ag2S particles, the fabricated Mn3O4-Ag2S JNPs exhibited satisfactory biocompatibility and therapeutic performance. Novel diagnostic and therapeutic nanoplatforms can be guided using the magnetic component in JNPs, which is revealed as an excellent T1 contrast enhancement agent in magnetic resonance imaging (MRI) with multiple functions, such as photo-induced regulation of the tumor microenvironment via producing reactive oxygen species and second near-infrared region (NIR-II) photothermal excitation for in vitro tumor-killing effects. The prime antibacterial and promising theranostics results demonstrate the extensive potential of the designed photo-responsive Mn3O4-Ag2S JNPs for biomedical applications.

To unveil and shape the molecular connectivity in (metallo)porphyrin-carbon nanotube hybrids are of main relevance for the multiple medicinal, photoelectronic, catalytic, and photocatalytic applications of these materials. Multi-walled carbon nanotubes (MWCNTs) were modified through 1,3-dipolar cycloaddition reactions with azomethine ylides generated in situ and carrying pentafluorophenyl groups, followed by immobilization of the β-amino-tetraphenylporphyrinate Zn(II). The functionalities were confirmed via XPS and FTIR, whereas Raman spectroscopy showed disruptions on the graphitic carbon nanotube surface upon both steps. The functionalization extension, measured via TGA mass loss and corroborated via XPS, was 0.2 mmol·g-1. Photophysical studies attest to the presence of the different porphyrin-carbon nanotube connectivity in the nanohybrid. Significantly different emission spectra and fluorescence anisotropy of 0.15-0.3 were observed upon variation of excitation wavelength. Vis-NIR absorption and flash photolysis experiments showed energy/charge transfer in the photoactivated nanohybrid. Moreover, evidence was found for direct reaction of amino groups with a carbon nanotube surface in the presence of molecular dipoles such as the zwitterionic sarcosine amino acid.

A novel magnetic-controlled electrochemical sensor has been fabricated by combined photo-responsive surface molecular imprinted polymers (P-SMIPs) and electrochemical sensor. In particular, the P-SMIPs were obtained by living radical polymerization of photo-responsive functional monomer onto the magnetic Fe3O4 modified multi-walled carbon nanotubes nanocomposites. The magnetic glassy carbon electrode was introduced to make the anchoring and removal of P-SMIPs onto the magnetic-controlled glassy carbon electrode easy to manipulate. Driven by UV/vis light, the platform performs releasing and absorption of metronidazole basing on conformational variations of the photo-responsive monomer at the receptor sites part in the P-SMIPs. This process can be tested by the photo-responsive variations of metronidazole electrochemical signal. As the consequence, extracting of P-SMIPs sensor can be conveniently triggered by the controllable UV light intervention measure, leading to effectively improve in both analytes mass transfer rate to the receiving media and extraction efficiency. The experimental result indicated that the excellent recoveries of metronidazole were varied between 77.9% and 89.9% with RSDs ≤4.87% in the biological samples. Therefore, the P-SMIPs sensor shows satisfactory potential in reusable extractions that can be recycled several times with no significant loss of activity, and this utilization strategy can be extended to other analytes, achieving manifold applications of pharmaceutical and environmental.

Soft robotic system, a new era of material science, is rapidly developing with advanced processing technology in soft matters, featured with biomimetic nature. An important bottom-up approach is through the implementation of molecular machines into polymeric materials, however, the synchronized molecular motions, acumination of strain across multiple length-scales, and amplification into macroscopic actuations remained highly challenging. This review presents the significances, key design strategies, and outlook of the hierarchical supramolecular systems of molecular machines to develop novel types of supramolecular-based soft robotic systems.

Molecular spin-crossover (SCO) compounds constitute a promising class of photoactive materials exhibiting efficient photo-induced phase transitions (PIPTs), driven by cooperative elastic interactions between the switchable molecules. Taking advantage of the unique, picture-perfect reproducibility of the spin-transition properties in the compound [Fe(HB(1,2,4-triazol-1-yl)3 )2 ], we have dissected the spatiotemporal dynamics of the PIPT within the thermodynamic metastability (hysteretic) region of a single crystal, using pump-probe optical microscopy. Beyond a threshold laser excitation density, complete PIPTs were evidenced, with conversion rates up to 200 switched molecules per absorbed photon. We show that the PIPT takes place through the sequential activation of two (molecular and macroscopic) switching mechanisms, occurring on sub-μs and ms timescales, governed by the intramolecular and free energy barriers of the system, respectively. The main finding here is that the thermodynamic metastability has strictly no influence on the sub-ms switching dynamics. Indeed, before this ms timescale, the response of the crystal to the laser excitation involves a gradual, molecular conversion process, as if there was no hysteresis loop. Consequently, in this regime, even a 100% photo-induced conversion may not give rise to a PIPT. These results provide new insight on the intrinsic dynamical limits of the PIPT in SCO solids (and other types of bistable materials), which is an important issue, from a technological perspective, for achieving fast and efficient photo-control of the functionalities of condensed matter. This article is protected by copyright. All rights reserved.

Stimuli-responsive materials that can be reversibly switched by light are of immense interest. Among them, photo-responsive spin crossover (SCO) complexes have great promises to combine the photoactive inputs with multifaceted outputs into switchable materials and devices. However, the reversible control the spin-state change by photochromic guests is still challenging. Herein, we report an unprecedented guest-driven light-induced spin change (GD-LISC) in a Hofmann-type metal-organic framework (MOF), [Fe(bpn){Ag(CN)2 }2 ]⋅azobenzene. (1, bpn=1,4-bis(4-pyridyl)naphthalene). The reversible trans-cis photoisomerization of azobenzene guest upon UV/Vis irradiation in the solid-state results in the remarkable magnetic changes in a wide temperature range of 10-180 K. This finding not only establishes a new switching mechanism for SCO complexes, but also paves the way toward the development of new generation of photo-responsive magnetic materials.

Typically, the morphologies of the self-assembled nanostructures from block copolymers are limited to spherical micelles, wormlike micelles and vesicles. Now, a new generation of materials with unique shape and structures, cylindrical soft matter particles (tubisomes), are obtained from the hierarchical self-assembly of cyclic peptide-bridged amphiphilic diblock copolymers. The capacity of obtained photo-responsive tubisomes as potential drug carriers is evaluated. The supramolecular tubisomes pave an alternative way for fabricating polymeric tubular structures, and will expand the toolbox for the rational design of functional hierarchical nanostructures.

Arbitrary shape (re)programming is appealing for fabricating untethered shape-morphing photo-actuators with intricate configurations and features. We present re-programmable light-responsive thermoplastic actuators with arbitrary initial shapes through spray-coating of polyethylene terephthalate (PET) with an azobenzene-doped light-responsive liquid crystal network (LCN). The initial geometry of the actuator is controlled by thermally shaping and fixing the thermoplastic PET, allowing arbitrary shapes, including origami-like folds and left- and right-handed helicity within a single sample. The thermally fixed geometries can be reversibly actuated through light exposure, with fast, reversible area-specific actuation such as winding, unwinding and unfolding. By shape re-programming, the same sample can be re-designed and light-actuated again. The strategy presented here demonstrates easy fabrication of mechanically robust, recyclable, photo-responsive actuators with highly tuneable geometries and actuation modes.