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Due to the severity and high prevalence of cancer, as well as its complex pathological condition, new strategies for cancer treatment and diagnostics are required. As such, it is important to design a toolbox that integrates multiple functions on a single smart platform. Theranostic hydrogels offer an innovative and personalized method to tackle cancer while also considering patient comfort, thereby facilitating future implementation and translation to the clinic. In terms of theranostic systems used in cancer therapy, nanoparticles are widely used as diagnostic and therapeutic tools. Nanoparticles can achieve systemic circulation, evade host defenses, and deliver drugs and signaling agents at the targeted site, to diagnose and treat the disease at a cellular and molecular level. In this context, hydrogel microneedles have a high potential for multifunctional operation in medical devices, while avoiding the complications associated with the systemic delivery of therapeutics. Compared with oral administration and subcutaneous injection, microneedles offer advantages such as better patient compliance, faster onset of action, and improved permeability and efficacy. In addition, they comprise highly biocompatible polymers with excellent degradability and tunable properties. Nanoparticles and microneedles thus offer the possibility to expand the theranostic potential through combined synergistic use of their respective features. We review herein recent advances concerning processing methods and material requirements within the realm of hydrogel microneedles as theranostic platforms, various approaches toward cancer therapy, and the incorporation of nanoparticles for added functionality. [ABSTRACT FROM AUTHOR]

Handedness is an essential attribute of chiral nanocrystals, having a major influence on their properties. During chemical growth, the handedness of nanocrystals is usually tuned by selecting the corresponding enantiomer of chiral molecules involved in asymmetric growth, often known as chiral inducers. We report that, even using the same chiral inducer enantiomer, the handedness of chiral gold nanocrystals can be reversed by using Au nanorod seeds with either single crystalline or pentatwinned structure. This effect holds for chiral growth induced both by amino acids and by chiral micelles. Although it was challenging to discern the morphological handedness for L‐cystine‐directed particles, even using electron tomography, both cases showed circular dichroism bands of opposite sign, with nearly mirrored chiroptical signatures for chiral micelle‐directed growth, along with quasi‐helical wrinkles of inverted handedness. These results expand the chiral growth toolbox with an effect that might be exploited to yield a host of interesting morphologies with tunable optical properties. [ABSTRACT FROM AUTHOR]

4D printing is the 3D printing of objects that change chemically or physically in response to an external stimulus over time. Photothermally responsive shape memory materials are attractive for their ability to undergo remote activation. While photothermal methods using gold nanorods (AuNRs) are used for shape recovery, 3D patterning of these materials into objects with complex geometries using degradable materials is not addressed. Here, the fabrication of 3D printed shape memory bioplastics with photo‐activated shape recovery is reported. Protein‐based nanocomposites based on bovine serum albumin (BSA), poly (ethylene glycol) diacrylate (PEGDA), and AuNRs are developed for vat photopolymerization. These 3D printed bioplastics are mechanically deformed under high loads, and the proteins served as mechano‐active elements that unfolded in an energy‐dissipating mechanism that prevented fracture of the thermoset. The bioplastic object maintained its metastable shape‐programmed state under ambient conditions. Subsequently, up to 99% shape recovery is achieved within 1 min of irradiation with near‐infrared (NIR) light. Mechanical characterization and small angle X‐ray scattering (SAXS) analysis suggest that the proteins mechanically unfold during the shape programming step and may refold during shape recovery. These composites are promising materials for the fabrication of biodegradable shape‐morphing devices for robotics and medicine. [ABSTRACT FROM AUTHOR]

The tumor microenvironment (TME) is a dynamic pseudoorgan that shapes the development and progression of cancers. It is a complex ecosystem shaped by interactions between tumor and stromal cells. Although the traditional focus has been on the paracrine communication mediated by protein messengers, recent attention has turned to the metabolic secretome in tumors. Metabolic enzymes, together with exchanged substrates and products, have emerged as potential biomarkers and therapeutic targets. However, traditional techniques for profiling secreted metabolites in complex cellular contexts are limited. Surface-enhanced Raman scattering (SERS) has emerged as a promising alternative due to its nontargeted nature and simplicity of operation. Although SERS has demonstrated its potential for detecting metabolites in biological settings, its application in deciphering metabolic interactions within multicellular systems like the TME remains underexplored. In this study, we introduce a SERS-based strategy to investigate the secreted purine metabolites of tumor cells lacking methylthioadenosine phosphorylase (MTAP), a common genetic event associated with poor prognosis in various cancers. Our SERS analysis reveals that MTAP-deficient cancer cells selectively produce methylthioadenosine (MTA), which is taken up and metabolized by fibroblasts. Fibroblasts exposed to MTA exhibit: i) molecular reprogramming compatible with cancer aggressiveness, ii) a significant production of purine derivatives that could be readily recycled by cancer cells, and iii) the capacity to secrete purine derivatives that induce macrophage polarization. Our study supports the potential of SERS for cancer metabolism research and reveals an unprecedented paracrine crosstalk that explains TME reprogramming in MTAP-deleted cancers. [ABSTRACT FROM AUTHOR]

Chiral plasmonic nanoparticles (and their assemblies) interact with biomolecules in a variety of different ways, resulting in distinct optical signatures when probed by circular dichroism spectroscopy. These systems show promise for biosensing applications and offer several advantages over achiral plasmonic systems. Arguably the most notable advantage is that chiral nanoparticles can differentiate between molecular enantiomers and can, therefore, act as sensors for enantiomeric purity. Furthermore, chiral nanoparticles can couple more effectively to chiral biomolecules in biological systems if they have a matching handedness, improving their effectiveness as biomedical agents. In this article, we review the different types of interactions that occur between chiral plasmonic nanoparticle systems and biomolecules, and discuss how circular dichroism spectroscopy can probe these interactions and inform how to optimize systems for biosensing and biomedical applications. [ABSTRACT FROM AUTHOR]

The Nobel Prize in Chemistry 2023 has been awarded to Moungi G. Bawendi, Louis E. Brus, and Alexei I. Ekimov for the discovery and synthesis of quantum dots. Quantum dots are semiconductor materials structured on the nanoscale that exhibit variable electronic and optical properties depending on their size. The discoveries and synthesis of quantum dots have been fundamental for the study of nanocrystals and their application in various fields. Additionally, the applications of nanocrystals in optoelectronic devices and television screens are mentioned, as well as their use in species detection in solution, photocatalysis, quantum information processing, and nanomedicine. The article concludes that the discovery of the relationship between optical properties and size in semiconductor nanocrystals has opened up many possibilities for study and practical application. [Extracted from the article]

Chiral metal nanoparticles (NPs) offer a powerful means of inducing and harnessing optical activity. However, due to the incomplete knowledge of the underlying growth mechanisms, there is still limited control over the achievable morphological detail and, consequently, over the resulting optical activity. Therefore, theoretical modeling is needed to guide experimental development toward optimizing the plasmonic chiroptical response. Toward filling this gap, herein an extensive parametric analysis is presented, via computer‐aided‐design (CAD) models and full‐wave electrodynamic simulations, which aims at systematically analyzing the influence of structural changes on the plasmonic circular dichroism (CD) spectra of rod‐shaped gold NPs comprising helical indentations on achiral nanorod cores. From this analysis, interesting patterns in the plasmon‐mediated resonant behavior are identified and cause–effect relationships are drawn that may serve as a go‐to recipe for the understanding and fabrication of these NPs and their applications, such as spectroscopic (bio)detection including CD spectral shifts and surface‐enhanced Raman optical activity. [ABSTRACT FROM AUTHOR]

Anti-Stokes photoluminescence (PL) is light emission at a higher photon energy than the excitation, with applications in optical cooling, bioimaging, lasing, and quantum optics. Here, we show how plasmonic nano-cavities activate anti-Stokes PL in WSe2 monolayers through resonant excitation of a dark exciton at room temperature. The optical near-fields of the plasmonic cavities excite the out-of-plane transition dipole of the dark exciton, leading to light emission from the bright exciton at higher energy. Through statistical measurements on hundreds of plasmonic cavities, we show that coupling to the dark exciton leads to a near hundred-fold enhancement of the upconverted PL intensity. This is further corroborated by experiments in which the laser excitation wavelength is tuned across the dark exciton. We show that a precise nanoparticle geometry is key for a consistent enhancement, with decahedral nanoparticle shapes providing an efficient PL upconversion. Finally, we demonstrate a selective and reversible switching of the upconverted PL via electrochemical gating. Our work introduces the dark exciton as an excitation channel for anti-Stokes PL in WSe2 and paves the way for large-area substrates providing nanoscale optical cooling, anti-Stokes lasing, and radiative engineering of excitons. Here, the authors perform statistical measurements on hundreds of plasmonic nano-cavities embedding WSe2 monolayers, and show the activation of anti-Stokes photoluminescence in WSe2 through resonant excitation of a dark exciton at room temperature. [ABSTRACT FROM AUTHOR]

Hyperthermia, as the process of heating a malignant site above 42 °C to trigger cell death, has emerged as an effective and selective cancer therapy strategy. Various modalities of hyperthermia have been proposed, among which magnetic and photothermal hyperthermia are known to benefit from the use of nanomaterials. In this context, we introduce herein a hybrid colloidal nanostructure comprising plasmonic gold nanorods (AuNRs) covered by a silica shell, onto which iron oxide nanoparticles (IONPs) are subsequently grown. The resulting hybrid nanostructures are responsive to both external magnetic fields and near-infrared irradiation. As a result, they can be applied for the targeted magnetic separation of selected cell populations – upon targeting by antibody functionalization – as well as for photothermal heating. Through this combined functionality, the therapeutic effect of photothermal heating can be enhanced. We demonstrate both the fabrication of the hybrid system and its application for targeted photothermal hyperthermia of human glioblastoma cells. [ABSTRACT FROM AUTHOR]