Cofactor-free oxidase-mimetic nanomaterials from self-assembled histidine-rich peptides.

Natural oxidases mainly rely on cofactors and well-arranged amino acid residues for catalysing electron-transfer reactions but suffer from non-recovery of their activity upon externally induced protein unfolding. However, it remains unknown whether residues at the active site can catalyse similar reactions in the absence of the cofactor. Here, we describe a series of self-assembling, histidine-rich peptides, as short as a dipeptide, with catalytic function similar to that of haem-dependent peroxidases. The histidine residues of the peptide chains form periodic arrays that are able to catalyse H2O2 reduction reactions efficiently through the formation of reactive ternary complex intermediates. The supramolecular catalyst exhibiting the highest activity could be switched between inactive and active states without loss of activity for ten cycles of heating/cooling or acidification/neutralization treatments, demonstrating the reversible assembly/disassembly of the active residues. These findings may aid the design of advanced biomimetic catalytic materials and provide a model for primitive cofactor-free enzymes.

Superoscillation focusing with suppressed sidebands by destructive interference.

Optical superoscillation, a phenomenon that the local optical field can oscillate much faster than that allowed by its highest harmonic, can significantly overcome the Abbe diffraction limit. However, as the spot size is compressed below the superoscillation criteria of 0.38λ/NA, huge sidebands will inevitably appear around the central lobe with intensity hundreds of times higher than that of the central lobe. Here, we propose an approach to realize superoscillation by using destructive interference. The central lobe size can be compressed beyond the superoscillation criteria without formation of strong sidebands by destructive interference between focused fields. Such a super-resolution metalens can find its application in label-free far-field super-resolution microscopy.

Programmable Dynamic Shapes with a Swarm of Light-Powered Colloidal Motors.

We report robust control over the dynamic assembly, disassembly, and reconfiguration of light-activated molybdenum disulfide (MoS2 ) colloidal motor swarms with features not possible in equilibrium systems. A photochemical reaction produces chemical gradients across the MoS2 colloidal motors to drive them to move. Under illumination of a gradient light, these colloidal motors display a positive phototactic motion. Mesoscale simulations prove that the self-diffusiophoresis induced by the locally consumed oxygen gradient across MoS2 colloidal motors dominates the phototactic process. By programming the structured illumination, the collective migration and well-defined shapes of colloidal motor swarms can be externally regulated. The successful realization of programmable swarm transformation of colloidal motors like the emergent behaviors of living systems in nature provides a direct proof-of-concept for active soft materials and systems, with adaptive and interactive functions.

Broadband quarter-wave birefringent meta-mirrors for generating sub-diffraction vector fields.

Independent manipulation of phase and polarization of optical fields is of great interest in various applications, including vector-field generation, optical tweezers, and nanolithography. The integration of phase and polarization manipulation on a single optical device may greatly simplify optical systems and eases optical alignment. In this Letter, a family of reflective cross-shaped quarter-wave birefringent metasurfaces is proposed to achieve full control of polarization and phase of reflected waves. Based on the proposed metasurfaces, two meta-mirrors are designed with integrated functions of polarization conversion and sub-diffraction focusing. Numerical investigations also reveal the achromatic focusing performance of the two meta-mirrors. The proposed metasurfaces with independent manipulation of polarization and phase provide flexible building blocks for constructing complicated vector optical fields.

Assembled Vitamin B2 Nanocrystals with Optical Waveguiding and Photosensitizing Properties for Potential Biomedical Application.

Great success has been achieved in recent years in the development of synthetic or assembled nanobiomaterials. Among these, biomolecule-based nanoarchitectures with special optical property are of particular interest. Here, we demonstrate that vitamin B2 nanocrystals assembled as nanorods can be obtained with precise control. Excitingly, such one-dimensional nanostructures not only exhibit intrinsic optical waveguiding properties but also the ability to sensitize oxygen to produce reactive oxygen species. With these properties, we applied the obtained vitamin B2 nanorods under remotely localized light illumination into single tumour cells in vitro for anticancer photodynamic therapy. Further, vitamin B2 nanorods were explored for in vivo photodynamic therapy by using a tumour model. With such bionanostructures, new features and functions of vitamin B2 and its derivatives have been developed.

Optimization-free approach for generating sub-diffraction quasi-non-diffracting beams.

Sub-diffraction quasi-non-diffracting beams with sub-wavelength transverse size are attractive for applications such as optical nano-manipulation, optical nano-fabrication, optical high-density storage, and optical super-resolution microscopy. In this paper, we proposed an optimization-free design approach and demonstrated the possibility of generating sub-diffraction quasi-non-diffracting beams with sub-wavelength size for different polarizations by a binary-phase Fresnel planar lens. More importantly, the optimization-free method significantly simplifies the design procedure and the generation of sub-diffracting quasi-non-diffracting beams. Utilizing the concept of normalized angular spectrum compression, for wavelength λ0 = 632.8 nm, a binary-phase Fresnel planar lens was designed and fabricated. The experimental results show that the sub-diffraction transverse size and the non-diffracting propagation distances are 0.40λ0-0.54λ0 and 90λ0, 0.43λ0-0.54λ0 and 73λ0, and 0.34λ0-0.41λ0 and 80λ0 for the generated quasi-non-diffracting beams with circular, longitudinal, and azimuthal polarizations, respectively.

Generating a three-dimensional hollow spot with sub-diffraction transverse size by a focused cylindrical vector wave.

A three-dimensional (3D) hollow spot is of great interest for a wide variety of applications such as microscopy, lithography, data storage, optical manipulation, and optical manufacturing. Based on conventional high-numerical-aperture objective lenses, various methods have been proposed for the generation of 3D hollow spots for different polarizations. However, conventional optics are bulky, costly, and difficult to integrate. More importantly, they are diffraction-limited in nature. Owing to their unique properties of small size, light weight, and ease of integration, planar lenses have become attractive as components in the development of novel optical devices. Utilizing the concept of super-oscillation, planar lenses have already shown great potential in the generation of sub-diffraction, or even of super-oscillatory features, in propagating optical waves. In this paper, we propose a binary-phase planar lens with an ultra-long focal length (300λ) for the generation of a 3D hollow spot with a cylindrical vector wave. In addition, we experimentally demonstrate the formation of such a hollow spot with a sub-diffraction transverse size of 0.546λ (smaller than the diffraction limit of 0.5λ/NA, where NA denotes the lens numerical aperture) and a longitudinal size of 1.585λ. The ratio of central minimum intensity to the central ring peak intensity is less than 3.7%. Such a planar lens provides a promising way to achieve tight 3D optical confinement for different uses that might find applications in super-resolution microscopy, nano-lithography, high-density data storage, nano-particle optical manipulation, and nano-optical manufacturing.

Self-Propelled Nanomotors for Thermomechanically Percolating Cell Membranes.

We report a near-infrared (NIR) light-powered Janus mesoporous silica nanomotor (JMSNM) with macrophage cell membrane (MPCM) cloaking that can actively seek cancer cells and thermomechanically percolate cell membrane. Upon exposure to NIR light, a heat gradient across the Janus boundary of the JMSNMs is generated by the photothermal effect of the Au half-shells, resulting in a self-thermophoretic force that propels the JMSNMs. In biological medium, the MPCM camouflaging can not only prevent dissociative biological blocks from adhering to JMSNMs but also improve the seeking sensitivity of the nanomotors by specifically recognizing cancer cells. The biofriendly propulsion and recognition capability enable JMSNMs to achieve the active seeking and bind to the membrane of cancer cells. Subsequent illumination with NIR then triggers the photothermal effect of MPCM@JMSNMs to thermomechanically perforate the cytomembranes for guest molecular injection. This approach integrates the functions of active seeking, cytomembranes perforating, and thermomechanical therapy in nanomotors, which may pave the way to apply self-propelled motors in biomedical fields.

Magnetic Mesoporous Silica Nanoparticles Cloaked by Red Blood Cell Membranes: Applications in Cancer Therapy.

Targeted drug delivery is an emerging technological strategy that enables nanoparticle systems to be responsive for tumor therapy. Magnetic mesoporous silica nanoparticles (MMSNs) were cloaked with red blood cell membrane (RBC). This integrates long circulation, photosensitizer delivery, and magnetic targeting for cancer therapy. In vivo experiments demonstrate that RBC@MMSNs can avoid immune clearance and achieve magnetic field (MF)-induced high accumulation in a tumor. When light irradiation is applied, singlet oxygen rapidly generates from hypocrellin B (HB)-loaded RBC@MMSN and leads to the necrosis of tumor tissue. Such a RBC-cloaked magnetic nanocarrier effectively integrates immunological adjuvant, photosensitizer delivery, MF-assisted targeting photodynamic therapy, which provides an innovative strategy for cancer therapy.

Synthesis of sub-diffraction quasi-non-diffracting beams by angular spectrum compression.

Quasi-non-diffracting beams are attractive for various applications, including optical manipulation, super-resolution microscopes, and materials processing. However, it is a great challenge to design and generate super-long quasi-non-diffracting beams with sub-diffraction and sub-wavelength size. In this paper, a method based on the idea of compressing a normalized angular spectrum is developed, which makes it possible and provides a practical tool for the design of a quasi-non-diffracting beam with super-oscillatory sub-wavelength transverse size. It also presents a clear physical picture of the formation of super-oscillatory quasi-non-diffracting beams. Based on concepts of a local grating and super-oscillation, a lens was designed and fabricated for a working wavelength of λ = 632.8 nm. The validity of the idea of normalized angular spectrum compression was confirmed by both numerical investigations and experimental studies. An optical hollow needle with a length of more than 100λ was experimentally demonstrated, in which an optical hollow needle was observed with a sub-diffraction and sub-wavelength transverse size within a non-diffracting propagation distance of 94λ. Longer non-diffracting propagation distance is expected for a lens with larger radius and shorter effective wavelength.

Near Infrared Light-Powered Janus Mesoporous Silica Nanoparticle Motors.

We describe fuel-free, near-infrared (NIR)-driven Janus mesoporous silica nanoparticle motors (JMSNMs) with diameters of 50, 80, and 120 nm. The Janus structure of the JMSNMs is generated by vacuum sputtering of a 10 nm Au layer on one side of the MSNMs. Upon exposure to an NIR laser, a localized photothermal effect on the Au half-shells results in the formation of thermal gradients across the JMSNMs; thus, the generated self-thermophoresis can actively drive the nanomotors to move at an ultrafast speed, for instance, up to 950 body lengths/s for 50 nm JMSNMs under an NIR laser power of 70.3 W/cm(2). The reversible "on/off" motion of the JMSNMs and their directed movement along the light gradient can be conveniently modulated by a remote NIR laser. Moreover, dynamic light scattering measurements are performed to investigate the coexisting translational and rotational motion of the JMSNMs in the presence of both self-thermophoretic forces and strong Brownian forces. These NIR-powered nanomotors demonstrate a novel strategy for overcoming the necessity of chemical fuels and exhibit a significant improvement in the maneuverability of nanomotors while providing potential cargo transportation in a biofriendly manner.

Far-field sub-diffraction focusing lens based on binary amplitude-phase mask for linearly polarized light.

Planar lenses are attractive photonic devices due to its minimized size and easy to integrate. However, planar lenses designed in traditional ways are restricted by the diffraction limit. They have difficulties in further reducing the focal spot size beyond the diffraction limit. Super-oscillation provides a possible way to solve the problem. However, lenses based on super-oscillation have always been affected by huge sidelobes, which resulted in limited field of view and difficulties in real applications. To address the problem, in the paper, a far-field sub-diffraction lens based on binary amplitude-phase mask was demonstrated under illumination of linearly polarized plane wave at wavelength 632.8 nm. The lens realized a long focal length of 148λ (94 µm), and the full width at half maximum of the focal line was 0.406λ, which was super-oscillatory. More important is that such a flat lens has small sidelobes and wide field of view. Within the measured range of [-132λ, + 120λ], the maximum sidelobe observed on the focal plane was less than 22% of the central peak. Such binary amplitude-phase planar lens can also be extended to long focal length far-field sub-diffraction focusing lens for other spectrum ranges.

Direct Observation of the Distribution of Gelatin in Calcium Carbonate Crystals by Super-Resolution Fluorescence Microscopy.

Biological organic-inorganic hybrid materials often achieve excellent properties and provide inspiration for the design of advanced materials. The organic phase plays a key role in determining the properties of biogenic materials, and the spatial arrangement of organic and inorganic phases provides direct evidence for interaction between the two phases. Super-resolution fluorescence microscopy was used to visualize the gelatin distribution in two different crystalline polymorphs of calcium carbonate (vaterite and calcite) and to investigate the process by which gelatin is excluded from the crystals. The results demonstrated that gelatin is distributed through vaterite microspheres in the form of nanoparticles, whereas it tends to accumulate on the edges of the calcite rhombohedra.

A Self-Assembled DNA Origami-Gold Nanorod Complex for Cancer Theranostics.

A self-assembled DNA origami (DO)-gold nanorod (GNR) complex, which is a dual-functional nanotheranostics constructed by decorating GNRs onto the surface of DNA origami, is demonstrated. After 24 h incubation of two structured DO-GNR complexes with human MCF7 breast cancer cells, significant enhancement of cell uptake is achieved compared to bare GNRs by two-photon luminescence imaging. Particularly, the triangle shaped DO-GNR complex exhibits optimal cellular accumulation. Compared to GNRs, improved photothermolysis against tumor cells is accomplished for the triangle DO-GNR complex by two-photon laser or NIR laser irradiation. Moreover, the DO-GNR complex exhibits enhanced antitumor efficacy compared with bare GNRs in nude mice bearing breast tumor xenografts. The results demonstrate that the DO-GNR complex can achieve optimal two-photon cell imaging and photothermal effect, suggesting a promising candidate for cancer diagnosis and therapy both in vitro and in vivo.

Motion-based, high-yielding, and fast separation of different charged organics in water.

We report a self-propelled Janus silica micromotor as a motion-based analytical method for achieving fast target separation of polyelectrolyte microcapsules, enriching different charged organics with low molecular weights in water. The self-propelled Janus silica micromotor catalytically decomposes a hydrogen peroxide fuel and moves along the direction of the catalyst face at a speed of 126.3 µm s(-1) . Biotin-functionalized Janus micromotors can specifically capture and rapidly transport streptavidin-modified polyelectrolyte multilayer capsules, which could effectively enrich and separate different charged organics in water. The interior of the polyelectrolyte multilayer microcapsules were filled with a strong charged polyelectrolyte, and thus a Donnan equilibrium is favorable between the inner solution within the capsules and the bulk solution to entrap oppositely charged organics in water. The integration of these self-propelled Janus silica micromotors and polyelectrolyte multilayer capsules into a lab-on-chip device that enables the separation and analysis of charged organics could be attractive for a diverse range of applications.

Near-Infrared-Activated Nanocalorifiers in Microcapsules: Vapor Bubble Generation for In†Vivo Enhanced Cancer Therapy.

Photothermal therapy based on gold nanostructures has been widely investigated as a state-of-the-art noninvasive therapy approach. Because single nanoparticles cannot harvest sufficient energy, self-assemblies of small plasmonic particles into large aggregates are required for enhanced photothermal performance. Self-assembled gold nanorods in lipid bilayer-modified microcapsules are shown to localize at tumor sites, generate vapor bubbles under near-infrared light exposure, and subsequently damage tumor tissues. The polyelectrolyte multilayer enables dense packing of gold nanorods during the assembly process, which leads to the formation of vapor bubbles around the excited capsules. The resulting vapor bubbles achieve a high efficiency of suppressing tumor growth compared to single gold nanorods. In vivo experiments demonstrated the ability of soft-polymer multilayer microcapsules to cross the biological barriers of the body and localize at target tissues.

Self-propelled Janus mesoporous silica nanomotors with sub-100 nm diameters for drug encapsulation and delivery.

The synthesis of an innovative self-propelled Janus nanomotor with a diameter of about 75 nm that can be used as a drug carrier is described. The Janus nanomotor is based on mesoporous silica nanoparticles (MSNs) with chromium/platinum metallic caps and propelled by decomposing hydrogen peroxide to generate oxygen as a driving force with speeds up to 20.2 µm s(-1) (about 267 body lengths per second). The diffusion coefficient (D) of nanomotors with different H2 O2 concentrations is calculated by tracking the movement of individual particles recorded by means of a self-assembled fluorescence microscope and is significantly larger than free Brownian motion. The traction of a single Janus MSN nanomotor is estimated to be about 13.47×10(-15) N. Finally, intracellular localization and drug release in vitro shows that the amount of Janus MSN nanomotors entering the cells is more than MSNs with same culture time and particle concentrations, meanwhile anticancer drug doxorubicin hydrochloride loaded in Janus MSNs can be slowly released by biodegradation of lipid bilayers in cells.

Model-free robust motion control for biological optical microscopy using time-delay estimation with an adaptive RBFNN compensator.

The field of large numerical aperture microscopy has witnessed significant advancements in spatial and temporal resolution, as well as improvements in optical microscope imaging quality. However, these advancements have concurrently raised the demand for enhanced precision, extended range, and increased load-bearing capacity in objective motion carrier (OMC). To address this challenge, this study introduces an innovative OMC that employs a ball screw mechanism as its primary driving component. Furthermore, a robust nonlinear motion control strategy has been developed, which integrates fast nonsingular terminal sliding mode, experimental estimation techniques, and adaptive radial basis neural network, to mitigate the impact of nonlinear friction within the ball screw mechanism on motion precision. The stability of the closed-loop control system has been rigorously demonstrated through Lyapunov theory. Compared with other enhanced sliding mode control strategies, the maximum error and root mean square error of this controller are improved by 33% and 34% respectively. The implementation of the novel OMC has enabled the establishment of a high-resolution bio-optical microscope, which has proven its effectiveness in the microscopic imaging of retinal organoids.

The power of super-resolution microscopy in modern biomedical science.

Super-resolution microscopy (SRM) technology that breaks the diffraction limit has revolutionized the field of cell biology since its appearance, which enables researchers to visualize cellular structures with nanometric resolution, multiple colors and single-molecule sensitivity. With the flourishing development of hardware and the availability of novel fluorescent probes, the impact of SRM has already gone beyond cell biology and extended to nanomedicine, material science and nanotechnology, and remarkably boosted important breakthroughs in these fields. In this review, we will mainly highlight the power of SRM in modern biomedical science, discussing how these SRM techniques revolutionize the way we understand cell structures, biomaterials assembly and how assembled biomaterials interact with cellular organelles, and finally their promotion to the clinical pre-diagnosis. Moreover, we also provide an outlook on the current technical challenges and future improvement direction of SRM. We hope this review can provide useful information, inspire new ideas and propel the development both from the perspective of SRM techniques and from the perspective of SRM's applications.

High glucose enhances thrombin responses via protease-activated receptor-4 in human vascular smooth muscle cells.

OBJECTIVE: Diabetes is associated with vascular remodeling and increased thrombin generation. Thrombin promotes vascular smooth muscle cell (SMC) mitogenesis and migration via protease-activated receptors (PAR)-1, PAR-3, and PAR-4. We investigated the effect of high glucose on expression and function of vascular thrombin receptors. METHODS AND RESULTS: In human vascular SMCs, high glucose (25 versus 5.5 mmol/L) induced a rapid and sustained increase in PAR-4 mRNA, protein, and cell surface expression. PAR-1 and PAR-3 expression were not changed. High glucose pretreatment (48 hours) enhanced thrombin or PAR-4-activating peptide but not PAR-1-activating peptide evoked intracellular calcium mobilization, migration, and tumor necrosis factor α gene expression. This enhancement of thrombin-stimulated migration and gene expression by high glucose was abolished by endogenous PAR-4 knockdown. PAR-4 regulation was prevented by inhibition of protein kinase (PK)C-ß and -δ isoforms or nuclear factor (NF)κB. Nuclear translocation of NFκB in high glucose-stimulated SMCs led to PKC-dependent NFκB binding to the PAR-4 promoter in a chromatin immunoprecipitation assay. Furthermore, in situ hybridization and immunohistochemistry confirmed high abundance of PAR-4 in human diabetic vessels as compared with nondiabetic vessels. CONCLUSIONS: High glucose enhances SMC responsiveness to thrombin through transcriptional upregulation of PAR-4, mediated via PKC-ß, -δ, and NFκB. This may play an important role in the vascular complications of diabetes.