All organic nanomedicine for PDT-PTT combination therapy of cancer cells in hypoxia.

Photodynamic and photothermal therapies are promising treatments for cancer, dermatological, and ophthalmological conditions. However, photodynamic therapy (PDT) is less effective in oxygen-deficient tumor environments. Combining PDT with photothermal therapy (PTT) can enhance oxygen supply and treatment efficacy.

Shedding light on imaging safety: Decoding the origin of photocytotoxicity in RhB-assisted fluorescence imaging.

Photocytotoxicity represents a significant limitation in the application of dye-assisted fluorescence imaging (FI), often resulting in undesirable cellular damage or even cell death, thereby restricting their practical utility. The prevalence of Rhodamine B (RhB) in FI underscores the importance of elucidating its photocytotoxicity effects to minimize photodamage. This study identifies the primary cause of photocytotoxicity stems from the generation of cytotoxic singlet oxygen in RhB, utilizing femtosecond transient absorption spectroscopy coupled with quantum chemical calculations.

Chemistry, Functionalization, and Applications of Recent Monoelemental Two-Dimensional Materials and Their Heterostructures.

The past decades have witnessed a rapid expansion in investigations of two-dimensional (2D) monoelemental materials (Xenes), which are promising materials in various fields, including applications in optoelectronic devices, biomedicine, catalysis, and energy storage. Apart from graphene and phosphorene, recently emerging 2D Xenes, specifically graphdiyne, borophene, arsenene, antimonene, bismuthene, and tellurene, have attracted considerable interest due to their unique optical, electrical, and catalytic properties, endowing them a broader range of intriguing applications. In this review, the structures and properties of these emerging Xenes are summarized based on theoretical and experimental results.

Water-Dispersible CsPbBr Perovskite Nanocrystals with Ultra-Stability and its Application in Electrochemical CO Reduction.

Thanks to the excellent optoelectronic properties, lead halide perovskites (LHPs) have been widely employed in high-performance optoelectronic devices such as solar cells and light-emitting diodes. However, overcoming their poor stability against water has been one of the biggest challenges for most applications. Herein, we report a novel hot-injection method in a Pb-poor environment combined with a well-designed purification process to synthesize water-dispersible CsPbBr nanocrystals (NCs).

Doubly resonant sum frequency spectroscopy of mixed photochromic isomers on surfaces reveals conformation-specific vibronic effects.

Doubly resonant infrared-visible sum-frequency generation (DR-IVSFG) spectroscopy, encompassing coupled vibrational and electronic transitions, provides a powerful method to gain a deep understanding of nuclear motion in photoresponsive surface adsorbates and interfaces. Here, we use DR-IVSFG to elucidate the role of vibronic coupling in a surface-confined donor-acceptor substituted azobenzene. Our study reveals some unique features of DR-IVSFG that have not been previously reported.

Optical Control of Nanoparticle Catalysis Influenced by Photoswitch Positioning in Hybrid Peptide Capping Ligands.

Here, we present an in-depth analysis of structural factors that modulate peptide-capped nanoparticle catalytic activity via optically driven structural reconfiguration of the biointerface present at the particle surface. Six different sets of peptide-capped Au nanoparticles were prepared, in which an azobenzene photoswitch was incorporated into one of two well-studied peptide sequences with known affinity for Au, each at one of three different positions: the N- or C-terminus or mid-sequence. Changes in the photoswitch isomerization state induce a reversible structural change in the surface-bound peptide, which modulates the catalytic activity of the material.

Dramatic Enhancement of Quantum Cutting in Lanthanide-Doped Nanocrystals Photosensitized with an Aggregation-Induced Enhanced Emission Dye.

Applications of multiphoton processes in lanthanide-doped nanophosphors (NPs) are often limited by relatively weak and narrow absorbance. Here, the concept of an ultimate photosensitization by aggregation-induced enhanced emission (AIEE) dyes to overcome this limitation is introduced. Because AIEE dyes do not suffer from concentration quenching, they can fully cover the NP surface at high density to maximize absorbance while passivating the surface.

Toward a modular multi-material nanoparticle synthesis and assembly strategy via bionanocombinatorics: bifunctional peptides for linking Au and Ag nanomaterials.

Materials-binding peptides represent a unique avenue towards controlling the shape and size of nanoparticles (NPs) grown under aqueous conditions. Here, employing a bionanocombinatorics approach, two such materials-binding peptides were linked at either end of a photoswitchable spacer, forming a multi-domain materials-binding molecule to control the in situ synthesis and organization of Ag and Au NPs under ambient conditions. These multi-domain molecules retained the peptides' ability to nucleate, grow, and stabilize Ag and Au NPs in aqueous media.

Remote Optically Controlled Modulation of Catalytic Properties of Nanoparticles through Reconfiguration of the Inorganic/Organic Interface.

We introduce here a concept of remote photoinitiated reconfiguration of ligands adsorbed onto a nanocatalyst surface to enable reversible modulation of the catalytic activity. This is demonstrated by using peptide-ligand-capped Au nanoparticles with a photoswitchable azobenzene unit integrated into the biomolecular ligand. Optical switching of the azobenzene isomerization state drives rearrangement of the ligand layer, substantially changing the accessibility and subsequent catalytic activity of the underlying metal surface.

Manipulating Magneto-Optic Properties of a Chiral Polymer by Doping with Stable Organic Biradicals.

We report the first example of tuning the large magneto-optic activity of a chiral polymer by addition of stable organic biradicals. The spectral dispersion of Verdet constant, which quantifies magneto-optic response, differs substantially between the base polymer and the nanocomposite. We employed a microscopic model, supported by atomistic calculations, to rationalize the behavior of this nanocomposite system.

Resonance Raman Probes for Organelle-Specific Labeling in Live Cells.

Raman microspectroscopy provides for high-resolution non-invasive molecular analysis of biological samples and has a breakthrough potential for dissection of cellular molecular composition at a single organelle level. However, the potential of Raman microspectroscopy can be fully realized only when novel types of molecular probes distinguishable in the Raman spectroscopy modality are developed for labeling of specific cellular domains to guide spectrochemical spatial imaging. Here we report on the design of a next generation Raman probe, based on BlackBerry Quencher 650 compound, which provides unprecedentedly high signal intensity through the Resonance Raman (RR) enhancement mechanism.

Plasmon-enhanced two-photon-induced isomerization for highly-localized light-based actuation of inorganic/organic interfaces.

Two-photon initiated photo-isomerization of an azobenzene moiety adsorbed on silver nanoparticles (Ag NPs) is demonstrated. The azobenzene is linked to a materials-binding peptide that brings it into intimate contact with the Ag NP surface, producing a dramatic enhancement of its two-photon absorbance. An integrated modeling approach, combining advanced conformational sampling with Quantum Mechanics/Capacitance Molecular Mechanics and response theory, shows that charge transfer and image charges in the Ag NP generate local fields that enhance two-photon absorption of the cis isomer, but not the trans isomer, of adsorbed molecules.

Rational design for enhancing inflammation-responsive in vivo chemiluminescence via nanophotonic energy relay to near-infrared AIE-active conjugated polymer.

H2O2-specific peroxalate chemiluminescence is recognized as a potential signal for sensitive in vivo imaging of inflammation but the effect of underlying peroxalate-emitter energetics on its efficiency has rarely been understood. Here we report a simple nanophotonic way of boosting near-infrared chemiluminescence with no need of complicated structural design and synthesis of an energetically favored emitter. The signal enhancement was attained from the construction of a nanoparticle imaging probe (∼26 nm in size) by dense nanointegration of multiple molecules possessing unique photonic features, i.

Optical Actuation of Inorganic/Organic Interfaces: Comparing Peptide-Azobenzene Ligand Reconfiguration on Gold and Silver Nanoparticles.

Photoresponsive molecules that incorporate peptides capable of material-specific recognition provide a basis for biomolecule-mediated control of the nucleation, growth, organization, and activation of hybrid inorganic/organic nanostructures. These hybrid molecules interact with the inorganic surface through multiple noncovalent interactions which allow reconfiguration in response to optical stimuli. Here, we quantify the binding of azobenzene-peptide conjugates that exhibit optically triggered cis-trans isomerization on Ag surfaces and compare to their behavior on Au.

Biolighted Nanotorch Capable of Systemic Self-Delivery and Diagnostic Imaging.

Sensitive imaging of inflammation with a background-free chemiluminescence (CL) signal has great potential as a clinically relevant way of early diagnosis for various inflammatory diseases. However, to date, its feasibility has been limitedly demonstrated in vivo with locally induced inflammation models by in situ injection of CL probes. To enable systemic disease targeting and imaging by intravenous administration of CL probes, hurdles need to be overcome such as weak CL emission, short glowing duration, or inability of long blood circulation.

Triggering nanoparticle surface ligand rearrangement via external stimuli: light-based actuation of biointerfaces.

Bio-molecular non-covalent interactions provide a powerful platform for material-specific self-organization in aqueous media. Here, we introduce a strategy that integrates a synthetic optically-responsive motif with a materials-binding peptide to enable remote actuation. Specifically, we linked a photoswitchable azobenzene moiety to either terminus of a Au-binding peptide.

Organelle specific imaging in live cells and immuno-labeling using resonance Raman probe.

Raman microspectroscopy is one of the most powerful tools in molecular sensing, offering a non-invasive and comprehensive characterization of the intracellular environment. To analyze and monitor molecular content in specific cellular compartments, different parts of cellular architecture must be unambiguously identified to guide Raman image/spectra acquisition. In this regards, the development of Raman molecular probes, producing spectrally distinct and intense signal is of outmost practical importance.

Poly(oxyethylene sugaramide)s: unprecedented multihydroxyl building blocks for tumor-homing nanoassembly.

Hydrogen bonding is a major intermolecular interaction for self-assembly occurring in nature. Here we report novel polymeric carbohydrates, i.e.

Conjugated polymer/photochromophore binary nanococktails: bistable photoswitching of near-infrared fluorescence for in vivo imaging.

Nanoscopic dense integration between solid-state emission and photochromism provides nanoprobes capable of photoswitching of bright NIR fluorescence with high on/off contrast, bistability and improved signal identification, being suitable for imaging applications in autofluorescence-rich in vivo environments.

Gadolinium-coordinated elastic nanogels for in vivo tumor targeting and imaging.

Coordination polymer gels have been recognized as promising hybrid nanoplatforms for imaging and therapeutic applications. Here we report functional metal-organic coordinated nanogels (GdNGs) for in vivo tumor imaging, whose non-crystalline and elastic nature allows for long blood circulation, as opposed to the rapid systemic clearance of common nanohybrids with rigid/crystalline frameworks. The deformable structure of GdNGs was constructed by random crosslinking of highly flexible polyethyleneimines (PEI) with gadolinium (Gd(3+)) coordination.

Tuning solid-state fluorescence to the near-infrared: a combinatorial approach to discovering molecular nanoprobes for biomedical imaging.

Dyes showing solid-state fluorescence (SSF) are intriguing molecules that can emit bright fluorescence in the condensed phase. Because they do not suffer from self-quenching of fluorescence, nanoscopic dense integration of those molecules produces particulate nanoprobes whose emission intensity can be boosted by raising the intraparticle dye density. In spite of the potential promise for imaging applications demanding intense emission signals, their excitation and emission spectra are generally limited to the visible region where biological tissues have less transparency.

Phthalocyanine-aggregated polymeric nanoparticles as tumor-homing near-infrared absorbers for photothermal therapy of cancer.

Phthalocyanine-aggregated Pluronic nanoparticles were constructed as a novel type of near-infrared (NIR) absorber for photothermal therapy. Tiny nanoparticles (~ 60 nm, FPc NPs) were prepared by aqueous dispersion of phthalocyanine-aggregated self-assembled nanodomains that were phase-separated from the melt mixture with Pluronic. Under NIR laser irradiation, FPc NPs manifested robust heat generation capability, superior to an individual cyanine dye and cyanine-aggregated nanoparticles.