3D Printed Ion-Responsive Personalized Transdermal Patch.

Microneedle patches are easy-to-use medical devices for transdermal administration. However, the insufficient insertion of microneedles due to the gap between planar patches and contoured skin affects drug delivery. Herein, we formulate a prepolymer for high-fidelity three-dimensional (3D) printed personalized transdermal patches. With the excellent photoinitiation ability of 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine (Tz), a high-fidelity and precise microneedle patch is successfully fabricated. Upon irradiation of the white illuminator, the doped gold nanoparticles (AuNPs) in the patch release heat and promisingly induce sweat production. With the introduction of Na+, the dominant component of sweat, the curvature of the produced transdermal patch is observed due to the ion-induced network rearrangement. The alkanethiol-stabilized AuNP with an end group of a carboxyl group causes controlled drug release behavior. Furthermore, the irradiation-induced photothermal heating of AuNP can facilitate the sustainability of drug release thanks to the substantially increased particle size of AuNP. These findings demonstrate that the developed prepolymer is a promising candidate for the production of transdermal patches fitting the curvature of the body surface.

Plasmonic Optical Wells-Based Enhanced Rate PCR.

Rapid, sensitive, inexpensive point-of-care molecular diagnostics are crucial for the efficient control of spreading viral diseases and biosecurity of global health. However, the gold standard, polymerase chain reaction (PCR) is time-consuming and expensive and needs specialized testing laboratories. Here, we report a low-cost yet fast, selective, and sensitive Plasmonic Optical Wells-Based Enhanced Rate PCR: POWER-PCR. We optimized the efficient optofluidic design of 3D plasmonic optical wells via the computational simulation of light-to-heat conversion and thermophoretic convection in a self-created plasmonic cavity. The POWER-PCR chamber with a self-passivation layer can concentrate incident light to accumulate molecules, generate rapid heat transfer and thermophoretic flow, and minimize the quenching effect on the naked Au surface. Notably, we achieved swift photothermal cycling of nucleic acid amplification in POWER-PCR on-a-chip in 4 min 24 s. The POWER-PCR will provide an excellent solution for affordable and sensitive molecular diagnostics for precision medicine and preventive global healthcare.

S-Nitrosylated CuS Hybrid Hydrogel Patches with Robust Antibacterial and Repair-Promoting Activity for Infected Wound Healing.

Development of wound dressing with robust antibacterial and repair-promoting activity has always been an urgent biomedical task during the past years. The therapeutic effect of current hydrogel dressings containing single bioactive agent like nanoparticle or gas is still unsatisfactory for the treatment of infected wound. Herein, a CuS/NO co-loaded hydrogel (CuS/NO Gel) is proposed, which is constructed by sequential polymerization, reduction, and S-nitrosylation of CuS hybrid hydrogel with disulfide bonds. These CuS/NO Gel patches show good mechanical stability, high photothermal activity and excellent biocompatibility. When being applied to treat infected wound, CuS/NO Gel can not only eliminate infection effectively by the synergistic effect of mild photothermal heating and boosted NO release in infection phase, but also promote vascularization and collagen deposition due to the synchronous supply of Cu ion nutrients and low concentration NO signaling molecules in wound repair phase. Compared to hydrogel dressings with individual active agent (CuS Gel or NO Gel), CuS/NO Gel exhibits better antibacterial and repair-promoting activity both in vitro and in vivo. Therefore, this CuS/NO Gel holds great promise in the future clinical treatment against infected wound.

Optoplasmonic Effects in Highly Curved Surfaces for Catalysis, Photothermal Heating, and SERS.

Surface curvature can be used to focus light and alter optical processes. Here, we show that curved surfaces (spheres, cylinders, and cones) with a radius of around 5 µm lead to maximal optoplasmonic properties including surface-enhanced Raman scattering (SERS), photocatalysis, and photothermal processes. Glass microspheres, microfibers, pulled fibers, and control flat substrates were functionalized with well-dispersed and dense arrays of 45 nm Au NP using polystyrene-block-poly-4-vinylpyridine (PS-b-P4VP) and chemically modified with 4-mercaptobenzoic acid (4-MBA, SERS reporter), 4-nitrobenzenethiol (4-NBT, reactive to plasmonic catalysis), or 4-fluorophenyl isocyanide (FPIC, photothermal reporter). The various curved substrates enhanced the plasmonic properties by focusing the light in a photonic nanojet and providing a directional antenna to increase the collection efficacy of SERS photons. The optoplasmonic effects led to an increase of up to 1 order of magnitude of the SERS response, up to 5 times the photocatalytic conversion of 4-NBT to 4,4'-dimercaptoazobenzene when the diameter of the curved surfaces was about 5 µm and a small increase in photothermal effects. Taken together, the results provide evidence that curvature enhances plasmonic properties and that its effect is maximal for spherical objects around a few micrometers in diameter, in agreement with a theoretical framework based on geometrical optics. These enhanced plasmonic effects and the stationary-phase-like plasmonic substrates pave the way to the next generation of sensors, plasmonic photocatalysts, and photothermal devices.

Nanoengineering Natural Leather for Dynamic Thermal Management and Electromagnetic Interference Shielding.

Unpredictable and extreme weather conditions, along with increasing electromagnetic pollution, have resulted in a significant threat to human health and productivity, causing irreversible damage to society's well-being and economy. However, existing personal temperature management and electromagnetic protection materials lack adaptability to dynamic environmental changes. To address this, a unique asymmetric bilayer leather/a-MWCNTs/CA fabric is developed by vacuum-infiltrating interconnected a-MWCNTs networks into natural leather's microfiber backbone and spraying porous acetic acid (CA) on the reverse side. Such fabric achieves simultaneous passive radiation cooling, heating, and anti-electromagnetic interference functions without external energy input. The fabric's cooling layer has high solar reflectance (92.0%) and high infrared emissivity (90.2%), providing an average subambient radiation cooling effect of 10 °C, while the heating layer has high solar absorption (98.0%), enabling excellent passive radiative heating and effective compensation for warming via Joule heating. Additionally, the fabric's 3D conductive a-MWCNTs network provides electromagnetic interference shielding effectiveness of 35.0 dB mainly through electromagnetic wave absorption. This multimode electromagnetic shielding fabric can switch between cooling and heating modes to adapt to dynamic cooling and heating scenarios, providing a new avenue for sustainable temperature management and electromagnetic protection applications.

Monolithic robust hybrid sponge with enhanced light adsorption and ultrafast photothermal heating rate for rapid oil cleaning.

It remains a significant challenge to develop a photothermal adsorbent with a heating response as fast as a joule-heating adsorbent and simultaneously possessing excellent mechanical stability and reusability for rapid oil cleaning. Here, we report a novel monolithic design to fabricate a photothermal hybrid sponge for rapid oil cleaning by integrating graphite interlayer compounds as photothermal units into the three-dimensional photothermal network of carbon nanotubes. This unique monolithic design enabled the hybrid sponge to present excellent photothermal performance: firstly, the superhydrophobic hybrid sponge has low thermal resistance resulting from the defectless surface; secondly, the photothermal units were weaved in the photothermal network, preventing detachment in the cycling and providing ultrafast photothermal heating rate. The hybrid sponge rises to 81 °C in merely 25 s under irradiation (1 Sun), superior to most photothermal oil adsorbents reported so far. This study provides a new structural design for constructing photothermal adsorbents with a fast-heating response for rapid crude oil cleaning.

Colloidal Multiscale Assembly via Photothermally Driven Convective Flow for Sensitive In-Solution Plasmonic Detections.

The assembly of metal nanoparticles and targets to be detected in a small light probe volume is essential for achieving sensitive in-solution surface-enhanced Raman spectroscopy (SERS). Such assemblies generally require either chemical linkers or templates to overcome the random diffusion of the colloids unless the aqueous sample is dried. Here, a facile method is reported to produce 3D multiscale assemblies of various colloids ranging from molecules and nanoparticles to microparticles for sensitive in-solution SERS detection without chemical linkers and templates by exploiting photothermally driven convective flow. The simulations suggest that colloids sub 100 nm in diameter can be assembled by photothermally driven convective flow regardless of density; the assembly of larger colloids up to several micrometers by convective flow is significant only if their density is close to that of water. Consistent with the simulation results, the authors confirm that the photothermally driven convective flow is mainly responsible for the observed coassembly of plasmonic gold nanorods with either smaller molecules or larger microparticles. It is further found that the coassembly with the plasmonic nanoantennae leads to dramatic Raman enhancements of molecules, microplastics, and microbes by up to fivefold of magnitude compared to those measured in solution without the coassembly.

Sandwich-Structured Carbon Paper/Metal-Organic Framework Monoliths for Flexible Solar-Powered Atmospheric Water Harvesting On Demand.

Solar-powered atmospheric water harvesting (AWH) with metal-organic frameworks (MOFs) has been recognized as an attractive way to alleviate water shortage stress in rural arid areas given the naturally abundant solar energy. However, the existing solar-powered AWH technologies only allow a singular water production mode: either solar heating-driven AWH which usually results in rather poor water productivity due to the limited availability of sufficient sunlight or conductive heating-driven all-day AWH with significantly improved water productivity but requiring additional electricity provided with a photovoltaic module. This greatly limits the flexibility in managing AWH based on climate conditions, water productivity, and energy cost. Herein, a sandwich-structured MOF monolith (denoted as CACS) with dual heating capacity, localized solar heating (LSH) and electrical heating (LEH), is presented. Compared with LSH, the use of LEH leads to more rapid and uniform heating of CACS monoliths, thereby driving a significantly enhanced water desorption efficiency with faster kinetics. Using the CACS monolith as an AWH sorbent, a new type of atmospheric water harvester is developed and able to produce water in multiple working modes: LSH-, LEH-, and LSH-/LEH-driven AWH, thereby enabling flexible AWH on demand: direct use of sunlight for LSH-driven AWH during the sunlight-sufficient day and/or LEH-driven all-day AWH powered by a photovoltaic module particularly during the sunlight-absent/-insufficient time (night or cloudy day). When working at the LSH-/LEH-driven AWH mode, the resulting prototype delivers 1.4 LH2O kgMOF-1 day-1 of water productivity with 2.3 kW·h L-1H2O of energy consumption, corresponding to 5.4 times higher water productivity than the LSH-driven AWH working mode alone and 17.9% of energy saving at the cost of 22.2% of water productivity reduction compared with the LEH-driven AWH working mode alone. The current work, therefore, demonstrates a novel solar-powered AWH strategy that enables all-day water production with flexible choices on AWH working modes in terms of climate conditions, desired water productivity, and energy cost.

Stimulation of Local Cytosolic Calcium Release by Photothermal Heating for Studying Intra- and Intercellular Calcium Waves.

A methodology is described that allows for localized Ca2+ release by photoexcitation. For this, cells are loaded with polymer capsules with integrated plasmonic nanoparticles, which reside in endo-lysosomes. The micrometer-sized capsules can be individually excited by near-infrared light from a light pointer, causing photothermal heating, upon which there is a rise in the free cytosolic Ca2+ concentration ([Ca2+ ]i ). The [Ca2+ ]i can be analyzed with a Ca2+ indicator fluorophore. In this way, it is possible to excite local lysosomal Ca2+ release in a desired target cell.

Nanoliquid Dressing with Enhancing Anti-Infection Performance under the Moderate Photothermal Effect for Wound Treatment.

Nonhealing wounds have become a major healthcare burden worldwide. Chronic wound healing is universally hampered by the presence of bacterial infections that form biofilms. Therefore, in this study, a novel nanoliquid dressing based on a mild photothermal heating strategy was designed to provide safe healing of biofilm-infected wounds. Dilute nitric acid (HNO3) solution was employed to induce a redox process triggered by copper sulfide (CuS) nanoplates in the nanoliquid dressing. This redox process was further promoted by the mild photothermal effect (≤47.5 °C) that generated a sufficient amount of reactive oxygen species, resulting in less thermal injury to normal tissues. Correspondingly, with the safe concentration of CuS nanoplates (0.4 mg/mL), excellent bactericidal efficiencies up to 98.3 and 99.3% against ampicillin-resistant Escherichia coli (Ampr E. coli) and Staphylococcus aureus (S. aureus) were achieved, respectively. Moreover, the nanoliquid dressing exhibited a near-infrared enhanced destructive effect on mature biofilms. According to in vivo wound healing experiments in mice, the nanoliquid dressing increased the healing rate and reduced the inflammatory response. This study provides a novel insight into treating the biofilm-infected chronic wounds in the "post-antibiotic era".

Plasmonic Nanocomposite Implants for Interstitial Thermotherapy: Experimental and Computational Analysis.

The ferromagnetic implant (thermoseeds) technique offers desirable features for interstitial thermotherapy. However, its efficacy has been reported to be limited by issues that are related to the properties of the metal alloys that are used to fabricate them and the high number of thermoseeds needed to achieve therapeutic temperature levels. Here, we present the results of a combination of experimental and computational analysis of plasmonic nanocomposite implants (photoseeds)-a combination of Au nanoparticles (NPs) and poly-dimethylsiloxane (PDMS)-as a model material. We performed structural and optical characterization of the Au NPs and repared Au-PDMS nanocomposites, followed by an elucidation of the heat generation capabilities of the Au-PDMS photoseeds in aqueous solution and in-vitro cancer cell suspension. Based on the experimental results, we developed a three-dimensional (3D) finite element method (FEM) model to predict in-vivo thermal damage profiles in breast tissue. The optical absorbance of the Au-PDMS photoseeds were increasing with the concentration of Au NPs. The photothermal measurements and the in-vivo predictions showed that the photothermal properties of the photoseeds, characteristics of the laser sources, and the duration of heating can be tuned to achieve therapeutic temperature levels under in-vitro and in-vivo conditions. Collectively, the results demonstrate the feasibility of using photoseeds for interstitial thermotherapy.

Quantitative Assessment of Endosomal Escape of Various Endocytosed Polymer-Encapsulated Molecular Cargos upon Photothermal Heating.

Encapsulated molecular cargos are efficiently endocytosed by cells. For cytosolic delivery, understanding the dynamic process of cargos release from the carrier vehicles used for encapsulation and the lysosomes where the carrier vehicles are trapped (which in general is the bottleneck), followed by diffusion in the cytosol is important for improving drug/gene delivery strategies. A methodology is reported to image this process on a millisecond scale and to quantitatively analyze the data. Polyelectrolyte capsules with embedded gold nanostars to encapsulate 43 fluorescent molecular cargos with diverse properties, ranging from small fluorophores to fluorescently labeled proteins, siRNA, etc., are used. By short laser irradiation intracellular release of the molecular cargos from endocytosed capsules into the cytosol is triggered, and their intracellular spreading is imaged. Most of the released molecular cargos evenly distribute inside the entire cell, while others are enriched in certain cell compartments. The time the different molecular cargos take to distribute within cells, i.e., the spreading time, is used as a quantifier. Quantitative analysis reveals that intracellular spread cannot be described by free diffusion, but is determined by interaction of the molecular cargo with intracellular components.

Cryopreservation and Laser Nanowarming of Zebrafish Embryos Followed by Hatching and Spawning.

This study shows for the first time the ability to rewarm cryopreserved zebrafish embryos that grow into adult fish capable of breeding normally. The protocol employs a single injection of cryoprotective agents (CPAs) and gold nanorods (GNRs) into the yolk and immersion in a precooling bath to dehydrate the perivitelline space. Then embryos are encapsulated within CPA and GNR droplets, plunged into liquid nitrogen, cryogenically stabilized, and rewarmed by a laser pulse. Postlaser nanowarming, embryos (n = 282) exhibit intact structure by 1 h (40%), continued development after 3 h (22%), movement after 24 h (11%), hatching after 48 h (9%), and swimming after Day 5 (3%). Finally, from fish that survives till Day 5, two larvae are grown to adulthood and spawned, yielding survival comparable to an unfrozen control. Future efforts will focus on improving the survival to adulthood and developing methods to cryopreserve large numbers of embryos for research, aquaculture, and biodiversity preservation.

Fluorescent Polymer-MoS2-Embedded Microgels for Photothermal Heating and Colorimetric Monitoring.

Photothermal heating with accurate monitoring of local temperature in complex biological fluids is crucial for therapeutic accuracy. Herein, photothermal microgels are developed to heat microscopic volumes through photothermal conversion and report the local temperature with a colorimetric response. The microgels consist of poly(ethylene glycol)-based hydrogels, which integrate temperature-responsive block-copolymer-grafted MoS2 nanosheets (BCP-grafted MoS2 NSs). The MoS2 NSs are used as a fluorescence quencher as well as an efficient photothermal agent, with their surface decorated with three distinct temperature-responsive BCPs containing blue-, green-, and red-fluorescent dyes. Upon irradiation of near-infrared light, MoS2 NSs convert the radiation into heat, and the BCPs change their conformation depending on the local temperature, selectively activating Förster resonance energy transfer of the three dyes. The use of three distinct BCPs and dyes enables the measurement of temperature in a wide range (i.e., from 25 to 50 °C). Importantly, the hydrogel matrix excludes molecules larger than the limiting mesh size so that BCP-grafted MoS2 NSs remain free from contamination against large adhesive proteins such as albumin, thus maintaining their sensitivity even in complex fluids.

Experimental and Theoretical Observation of Photothermal Chirality in Gold Nanoparticle Helicoids.

Single-particle spectroscopy is central to the characterization of plasmonic nanostructures and understanding of light-matter interactions in chiral nanosystems. Although chiral plasmonic nanostructures are generally characterized by their circular differential extinction and scattering, single-particle absorption studies can extend our understanding of light-matter interactions. Here, we introduce an experimental observation of photothermal chirality which originated from circular differential absorption of chiral plasmonic nanostructures. Using luminescence ratio thermometry, we identify the optical and photothermal handedness and an absolute temperature difference of 6 K under the right and left circularly polarized light. We observe a circular differential extinction parameter (gext) of -0.13 in colloidally prepared gold helicoids and compare our findings with numerical simulations using finite element methods. The simulated data showed that circular differential absorption and the maximum temperature of a small cluster of helical nanoparticles are polarization-dependent. We observed an intensity-dependent photothermal g-factor from chiral helicoids that decreases slightly at higher temperatures. We also measure a range of optical g-factors from several gold helicoids, which are attributed to the heterogeneity of helicoids in nanoparticles during synthesis. The principles of differential photothermal response of chiral nanomaterials and heat generation described here can be potentially used for thermal photocatalysis, energy conversion, and electronic applications.

Croconaine Rotaxane Dye with 984 nm Absorption: Wavelength-Selective Photothermal Heating.

Croconaines are an emerging class of near-infrared dyes that are useful for various sensing, photothermal, optoelectronic, and photoacoustic applications. Previous work encapsulated a dumbbell-shaped croconaine dye whose structure contains two thiophene flanking units inside a tetralactam macrocycle and produced a croconaine rotaxane 1 with a narrow 824 nm absorption band. Herein, a new rotaxane 2 is reported that encapsulates a croconaine dye with two thienothiophene flanking units. The new croconaine rotaxane 2 exhibits a narrow 984 nm absorption band that is distinct from the 824 nm absorption of rotaxane 1. Photothermal heating experiments showed that an 830 nm diode laser selectively heats a solution containing rotaxane 1, with no heating of a solution containing rotaxane 2. Conversely, a 980 nm diode laser selectively heats a solution containing rotaxane 2, with no heating of a solution containing rotaxane 1. The new croconaine rotaxane 2 shows no fatigue after four cycles of laser heating and cooling.

Light-Induced Thermal Gradients in Ruthenium Catalysts Significantly Enhance Ammonia Production.

Industrial scale catalytic chemical synthesis demands both high reaction rates and high product yields. In exothermic chemical reactions, these conflicting objectives require a complex balance of optimized catalysts, high temperatures, high pressures, and multiple recycling steps, as in the energy-intensive Haber-Bosch process for ammonia synthesis. Here we report that illumination of a conventional ruthenium-based catalyst produces ammonia with high reaction rates and high conversion yields. Indeed, using continuous wave light-emitting diodes that simulate concentrated solar illumination, ammonia is copiously produced without any external heating or elevated pressures. The possibility of nonthermal plasmonic effects are excluded by carefully comparing the catalytic activity under direct and indirect illumination. Instead, thermal gradients, created and controlled by photothermal heating of the illuminated catalyst surface, are shown to be responsible for the high reaction rates and conversion yields. This nonisothermal environment enhances both by balancing the conflicting requirements of kinetics and thermodynamics, heralding the use of optically controlled thermal gradients as a universal, scalable strategy for the catalysis of many exothermic chemical reactions.

Photothermally Assisted Thinning of Silicon Nitride Membranes for Ultrathin Asymmetric Nanopores.

Sculpting solid-state materials at the nanoscale is an important step in the manufacturing of numerous types of sensor devices, in particular solid-state nanopore sensors. Here we present mechanistic insight into laser-induced thinning of low-stress silicon nitride (SiN x) membranes and films. In a recent study, we observed that focusing a visible wavelength laser beam on a SiN x membrane results in efficient localized heating, and we used this effect to control temperature at a solid-state nanopore sensor. A side-effect of the observed heating was that the pores expand/degrade under prolonged high-power illumination, prompting us to study the mechanism of this etching process. We find that SiN x can be etched under exposure to light of ∼107 W/cm2 average intensity, with etch rates that are influenced by the supporting electrolyte. Combining this controlled etching with dielectric breakdown, an electrokinetic process for making pores, nanopores of arbitrary dimensions as small as 1-2 nm in diameter and thickness can easily be fabricated. Evidence gathered from biomolecule-pore interactions suggests that the pore geometries obtained using this method are more funnel-like, rather than hourglass-shaped. Refined control over pore dimensions can expand the range of applications of solid-state nanopores, for example, biopolymer sequencing and detection of specific biomarkers.

Photothermal Heating and Cooling of Nanostructures.

A vast range of insulating, semiconducting, and metallic nanomaterials have been studied over the past several decades with the aim of understanding how continuous-wave or pulsed laser radiation can influence their chemical functionality and local environment. Many fascinating observations have been made during laser irradiation including, but not limited to, the superheating of solvents, mass-transport-mediated morphology evolution, photodynamic therapy, morphology dependent resonances, and a range of phase transformations. In addition to laser heating, recent experiments have demonstrated the laser cooling of nanoscale materials through the emission of upconverted, anti-Stokes photons by trivalent rare-earth ions. This Focus Review outlines the analytical modeling of photothermal heat transport with an emphasis on the experimental validation of anti-Stokes laser cooling. This general methodology can be applied to a wide range of photothermal applications, including nanomedicine, photocatalysis, and the synthesis of new materials. The review concludes with an overview of recent advances and future directions for anti-Stokes cooling.

Targeted and controlled drug delivery by multifunctional mesoporous silica nanoparticles with internal fluorescent conjugates and external polydopamine and graphene oxide layers.

This study demonstrated the targeted delivery and controlled release of cisplatin drug molecules from doubly decorated mesoporous silica nanoparticles (MSNs), which were internally grafted with fluorescent conjugates and externally coated with polydopamine (PDA) and graphene oxide (GO) layers. The brush-like internal conjugates conferred fluorescent functionality and high capacity of cisplatin loading into MSNs, as well as contributing to a sustained release of the cisplatin through a porous channel with the assistance of external PDA layer. A consolidated double-layer formed by electrostatic interactions between the GO nanosheet and the PDA layer induced more controlled release kinetics which was well predicted by Higuchi model. In addition, Our MSNs exhibited stimuli (pH, NIR irradiation)-responsive controlled release as a potential chemo-photothermal agent against cancer cells. In a cell test, multifunctional MSNs showed a low toxicity itself, but gave a high cytotoxicity against human epithelial neuroblastoma cells (SH-SY5Y) after loading cisplatin. Notably, GO-wrapped MSNs exhibited very effective drug delivery because GO wrapping enhanced their dispensability in aqueous solution, photothermal heating effect, and efficient endocytosis into cells. Furthermore, monoclonal antibody (anti-human epidermal growth factor receptor)-conjugated MSNs showed a higher specificity, which resulted in more enhanced anticancer effects in vitro. The current study demonstrated a reliable synthesis of multifunctional MSNs, endowed with fluorescent imaging, stimuli-responsive controlled release, higher specificity, and efficient cytotoxicity toward cancer cells. STATEMENT OF SIGNIFICANCE: The current study demonstrated the reliable synthesis of multifunctional mesoporous silica nanoparticles (MSNs) with internal fluorescent conjugates and external polydopamine and graphene oxide (GO) layers. The combination of internal conjugates and external coating layers produced an effective pore closure effect, leading to controlled and sustained release of small drug molecules. Notably, GO wrapping improved the dispensability and cellular uptake of the MSNs, as well as enhanced drug-controlled release. Our multifunctional MSNs revealed very efficient drug delivery effects against human epithelial neuroblastoma cells by demonstrating several strengths: i) fluorescent imaging, ii) sustained and controlled release of small drug molecules, iii) efficient cellular uptake, cytotoxicity and specificity, and v) stimuli (pH, NIR irradiation)-responsive controlled release as a potential chemo-photothermal agent.