Photosensitive Polymeric Janus Micromotor for Enzymatic Activity Protection and Enhanced Substrate Degradation.

Immobilizing enzymes into microcarriers is a strategy to improve their long-term stability and reusability, hindered by (UV) light irradiation. However, in such approaches, enzyme-substrate interaction is mediated by diffusion, often at slow kinetics. In contrast, enzyme-linked self-propelled motors can accelerate this interaction, frequently mediated by the convection mechanism. This work reports on a new photosensitive polymeric Janus micromotor (JM) for UV-light protection of enzymatic activity and efficient degradation of substrates accelerated by the JMs. The JMs were assembled with UV-photosensitive modified chitosan, co-encapsulating fluorescent-labeled proteins and enzymes as models and magnetite and platinum nanoparticles for magnetic and catalytic motion. The JMs absorbed UV light, protecting the enzymatic activity and accelerating the enzyme-substrate degradation by magnetic/catalytic motion. Immobilizing proteins in photosensitive JMs is a promising strategy to improve the enzyme's stability and hasten the kinetics of substrate degradation, thereby enhancing the enzymatic process's efficiency.

Single-Cell Chemistry of Photoactivatable Platinum Anticancer Complexes.

The Pt(IV) prodrug trans, trans, trans-[Pt(pyridine)2(N3)2(OH)2] (Pt1) and its coumarin derivative trans, trans, trans-[Pt(pyridine)2(N3)2(OH)(coumarin-3-carboxylate)] (Pt2) are promising agents for photoactivated chemotherapy. These complexes are inert in the dark but release Pt(II) species and radicals upon visible light irradiation, resulting in photocytotoxicity toward cancer cells. Here, we have used synchrotron techniques to investigate the in-cell behavior of these prodrugs and visualize, for the first time, changes in cellular morphology and Pt localization upon treatment with and without light irradiation. We show that photoactivation of Pt2 induces remarkable cellular damage with extreme alterations to multiple cellular components, including formation of vacuoles, while also significantly increasing the cellular accumulation of Pt species compared to dark conditions. X-ray absorption near-edge structure (XANES) measurements in cells treated with Pt2 indicate only partial reduction of the prodrug upon irradiation, highlighting that phototoxicity in cancer cells may involve not only Pt(II) photoproducts but also photoexcited Pt(IV) species.

Gold-Platinum Nanodots with High-Peroxidase-like Activity and Photothermal Conversion Efficiency for Antibacterial Therapy.

Combined therapeutic strategies for bacterial infection have attracted worldwide attention owing to their faster and more effective therapy with fewer side effects compared with monotherapy. In this work, gold-platinum nanodots (AuPtNDs) are simply and quickly synthesized by a one-step method. They not only exhibit powerful peroxidase-like activity but also confer a higher affinity for hydrogen peroxide (H2O2), which is 3.4 times that of horseradish peroxidase. Under 808 nm laser irradiation, AuPtNDs also have excellent photothermal conversion efficiency (50.53%) and strong photothermal stability. Excitingly, they can combat bacterial infection through the combination of chemodynamic and photothermal therapy. In vitro antibacterial results show that the combined antibacterial strategy has a broad-spectrum antibacterial property against both Escherichia coli (Gram negative, 97.1%) and Staphylococcus aureus (Gram positive, 99.3%). Animal experiments further show that nanodots can effectively promote the healing of bacterial infection wounds. In addition, owing to good biocompatibility and low toxicity, they are hardly traceable in the main organs of mice, which indicates that they can be well excreted through metabolism. These results reveal the application potential of AuPtNDs as a simple and magic multifunctional nanoparticle in antibacterial therapy and open up new applications for clinical anti-infective therapy in the near future.

Oxoplatin-B, a cisplatin-based platinum(IV) complex with photoactive BODIPY for mitochondria specific "chemo-PDT" activity.

Oxoplatin-B, a platinum(IV) complex [Pt(NH3)2Cl2(L1)(OH)] (1) of 4-methylbenzoic acid (HL1) functionalized with 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) was prepared, characterized and its antitumor activity studied. [Pt(NH3)2Cl2(L2)(OH)] (2) of 4-methylbenzoic acid (HL2) was studied as a control. Complex 1 showed an absorption band at 500 nm (ɛ = 4.34 × 104 M-1 cm-1) and an emission band at 515 nm (λex = 488 nm, ΦF = 0.64) in 1% dimethyl sulfoxide/Dulbecco's Modified Eagle's Medium (pH = 7.2). Visible light-induced (400-700 nm) generation of singlet oxygen was evidenced from 1,3-diphenylisobenzofuran titration study. Complex 1 showed photo-induced cytotoxicity in visible light (400-700 nm, 10 J cm-2) against human breast cancer (MCF-7), cervical cancer (HeLa) and lung cancer (A549) cells (IC50: 1.1-3.8 µM) while being less toxic in normal cells. Confocal imaging showed mitochondrial localization with additional evidence from platinum content from isolated mitochondria and 5,5,6,6'-tetrachloro-1,1',3,3' tetraethylbenzimi-dazoylcarbocyanine iodide (JC-1) assay. Cellular apoptosis was observed from Annexin-V-FITC (fluorescein isothiocyanate)/propidium iodide assay.

Shuttle-Shape Carrier-Free Platinum-Coordinated Nanoreactors with O2 Self-Supply and ROS Augment for Enhanced Phototherapy of Hypoxic Tumor.

The synergistic nanotheranostics of reactive oxygen species (ROS) augment or phototherapy has been a promising method within synergistic oncotherapy. However, it is still hindered by sophisticated design and fabrication, lack of a multimodal synergistic effect, and hypoxia-associated poor photodynamic therapy (PDT) efficacy. Herein, a kind of porous shuttle-shape platinum (IV) methylene blue (Mb) coordination polymer nanotheranostics-loaded 10-hydroxycamptothecin (CPT) is fabricated to address the abovementioned limitations. Our nanoreactors possess spatiotemporally controlled O2 self-supply, self-sufficient singlet oxygen (1O2), and outstanding photothermal effect. Once they are taken up by tumor cells, nanoreactors as a cascade catalyst can efficiently catalyze degradation of the endogenous hydrogen peroxide (H2O2) into O2 to alleviate tumor hypoxia. The production of O2 can ensure enhanced PDT. Subsequently, under both stimuli of external red light irradiation and internal lysosomal acidity, nanoreactors can achieve the on-demand release of CPT to augment in situ mitochondrial ROS and highly efficient tumor ablation via phototherapy. Moreover, under the guidance of near-infrared (NIR) fluorescent imaging, our nanoreactors exhibit strongly synergistic potency for treatment of hypoxic tumors while reducing damages against normal tissues and organs. Collectively, shuttle-shape platinum-coordinated nanoreactors with augmented ROS capacity and enhanced phototherapy efficiency can be regarded as a novel tumor theranostic agent and further promote the research of synergistic oncotherapy.

Investigating the influence of relativistic effects on absorption spectra for platinum complexes with light-activated activity against cancer cells.

We report the first systematic investigation of relativistic effects on the UV-vis spectra of two prototype complexes for so-called photo-activated chemotherapy (PACT), trans-trans-trans-[Pt(N3)2(OH)2(NH3)2] and cis-trans-cis-[Pt(N3)2(OH)2(NH3)2]. In PACT, design of new drugs requires in-depth understanding of the photo-activation mechanisms. A first step is usually to rationalize their UV-vis spectra for which time-dependent density functional theory (TD-DFT) is an indispensable tool. We carried out TD-DFT calculations with a systematic series of non-relativistic (NR), scalar-relativistic (SR), and four-component (4c) Hamiltonians. As expected, large differences are found between spectra calculated within 4c and NR frameworks, while the most intense features (found at higher energies below 300 nm) can be reasonably well reproduced within a SR framework. It is also shown that effective core potentials (ECPs) yield essentially similar results as all-electron SR calculations. Yet the underlying transitions can be strongly influenced by spin-orbit coupling, which is only present in the 4c framework: while this can affect both intense and less intense transitions in the spectra, the effect is most pronounced for weaker transitions at lower energies, above 300 nm. Since the investigated complexes are activated with light of wavelengths above 300 nm, employing a method with explicit inclusion of spin-orbit coupling may be crucial to rationalize the activation mechanism.

Tetraphenylethene-Based Supramolecular Coordination Frameworks with Aggregation-Induced Emission for an Artificial Light-Harvesting System.

Supramolecular coordination is an efficient strategy to construct supramolecular coordination frameworks with predesigned structures, assembled shapes, and specific function. In this work, we report the synthesis, structural characterization, and photophysical property of two tetraphenylethene-based supramolecular coordination frameworks 1a and 1b formed from 1,1,2,2-tetrakis(4-(pyridin-4-yl)phenyl)ethene (2a) or 1,1,2,2-tetrakis(4-((E)-2-(pyridin-4-yl)vinyl)phenyl)ethene (2b) and a linear difunctional platinum(II) ligand (3a) via coordination-driven self-assembly. Controlled by the specific angularity and geometry of tetraphenylethene (with 60° and 120°) and difunctional Pt(II) linker (with 180°), these supramolecular coordination frameworks possess a well-defined and two-dimensional (2D) rhombic network-type topology with good periodicity and porosity. Given the aggregation-induced emission (AIE) property of tetraphenylethene units and the porosity of frameworks, 1a and 1b have been successfully used as fluorescent platforms and energy donors to fabricate efficient artificial light-harvesting materials with two fluorescent acceptors (Nile Red and Sulforhodamine 101) via noncovalent interactions in aqueous solution. Furthermore, these light-harvesting materials have been applied for promoting cancer cell imaging with a full shift of imaging channels from blue/green channels to the red channel. Thus, this study provides an effective approach to fabricate functional frameworks as fluorescent platforms for developing more fluorescent materials.

Combinatorial photochemotherapy on liver cancer stem cells with organoplatinum(ii) metallacage-based nanoparticles.

Liver cancer is a kind of lethal and aggressive malignant neoplasm with a high rate of relapse and metastasis after therapy. An important cause for the relapse and metastasis is the existence of liver cancer stem cells (CSCs), which have high resistance to chemotherapy and high tumorigenic potential. Therefore, it is crucial to develop new methods to eradicate CSCs in tumors. Herein, we develop a photodynamic therapy (PDT) that features bimodal metallacage-loaded nanoparticles (MNPs) for integrated chemotherapy. This platform achieves chemo-photodynamic combinational therapy. Organoplatinum(ii) metallacage-loaded nanoparticles show excellent ability to kill liver CSCs, decreasing their mobility and sphenoid formation ability under near-infrared laser irradiation. Importantly, MNPs can successfully penetrate into 3D tumor spheroids, which display higher drug resistance compared to traditional 2D cultured cells. This destroys CSCs and prevents subsequent tumor formation in vivo. With the excellent combinational therapeutic results in hand, the working mechanisms of MNPs were then studied. MNPs under NIR light irradiation can generate reactive oxygen species (ROS), resulting in damage of mitochondrial membrane and subsequent cell apoptosis with chemotherapeutic platinum. This study proves the great potential of MNPs for combinational cancer therapy, providing a new insight for the next generation of nanomedicines.

Photoactive platinum(ii) ß-diketonates as dual action anticancer agents.

Platinum(ii) complexes, viz. [Pt(L)(cur)] (1), [Pt(L)(py-acac)] (2) and [Pt(L)(an-acac)] (3), where HL is 4,4'-bis-dimethoxyazobenzene, Hcur is curcumin, Hpy-acac and Han-acac are pyrenyl and anthracenyl appended acetylacetone, were prepared, characterized and their anticancer activities were studied. Complex [Pt(L)(acac)] (4) was used as a control. Complex 1 showed an absorption band at 430 nm (ε = 8.8 × 10(4) M(-1) cm(-1)). The anthracenyl and pyrenyl complexes displayed bands near 390 nm (ε = 3.7 × 10(4) for 3 and 4.4 × 10(4) M(-1) cm(-1) for 2). Complex 1 showed an emission band at 525 nm (Φ = 0.017) in 10% DMSO-DPBS (pH, 7.2), while 2 and 3 were blue emissive (λem = 440 and 435, Φ = 0.058 and 0.045). There was an enhancement in emission intensity on glutathione (GSH) addition indicating diketonate release. The platinum(ii) species thus formed acted as a transcription inhibitor. The released ß-diketonate base showed photo-chemotherapeutic activity. The complexes photocleaved plasmid DNA under blue light of 457 nm forming ∼75% nicked circular (NC) DNA with hydroxyl radicals and singlet oxygen as the ROS. Complexes 1-3 were photocytotoxic in skin keratinocyte HaCaT cells giving IC50 of 8-14 µM under visible light (400-700 nm, 10 J cm(-2)), while being non-toxic in the dark (IC50: ∼60 µM). Complex 4 was inactive. Complexes 1-3 generating cellular ROS caused apoptotic cell death under visible light as evidenced from DCFDA and annexin-V/FITC-PI assays. This work presents a novel way to deliver an active platinum(ii) species and a phototoxic ß-diketone species to the cancer cells.

Laser patterning of platinum electrodes for safe neurostimulation.

OBJECTIVE: Laser surface modification of platinum (Pt) electrodes was investigated for use in neuroprosthetics. Surface modification was applied to increase the surface area of the electrode and improve its ability to transfer charge within safe electrochemical stimulation limits. APPROACH: Electrode arrays were laser micromachined to produce Pt electrodes with smooth surfaces, which were then modified with four laser patterning techniques to produce surface structures which were nanosecond patterned, square profile, triangular profile and roughened on the micron scale through structured laser interference patterning (SLIP). Improvements in charge transfer were shown through electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV) and biphasic stimulation at clinically relevant levels. A new method was investigated and validated which enabled the assessment of in vivo electrochemically safe charge injection limits. MAIN RESULTS: All of the modified surfaces provided electrical advantage over the smooth Pt. The SLIP surface provided the greatest benefit both in vitro and in vivo, and this surface was the only type which had injection limits above the threshold for neural stimulation, at a level shown to produce a response in the feline visual cortex when using an electrode array implanted in the suprachoroidal space of the eye. This surface was found to be stable when stimulated with more than 150 million clinically relevant pulses in physiological saline. SIGNIFICANCE: Critical to the assessment of implant devices is accurate determination of safe usage limits in an in vivo environment. Laser patterning, in particular SLIP, is a superior technique for improving the performance of implant electrodes without altering the interfacial electrode chemistry through coating. Future work will require chronic in vivo assessment of these electrode patterns.

Pt nanoparticles/TiO2 for photocatalytic degradation of phenols in wastewater.

Pt nanoparticles/TiO2 catalysts were prepared and evaluated for UV-photocatalytic degradation ofphenol and 2-chlorophenol (2-CP) in synthetic wastewater solutions. The catalysts were synthesized by immobilizing colloidal Pt nanoparticles onto titanium dioxide (rutile TiO2). Analytical techniques, such as standard Brunauer-Emmett-Teller isotherms, X-ray diffraction, transmission electron microscope, were utillized for investigating the specific surface area, structure, and particle size distribution of the catalysts and its components. The photocatalytic activities of both phenol and 2-CP solutions were studied in a 1L batch photoreactor independently, under 450 W UV irradiation. Samples were drawn at regular intervals and residual concentration of phenol and 2-CP in the samples was analysed using an UV-visible spectrophotometer. Parameters controlling the photocatalytic process, including catalyst concentration, solution pH, and initial phenol (2-CP) concentration, were investigated. The obtained results revealed that Pt/TiO2 showed higher photocatalytic degradation for both phenol and 2-CP pollutants in solution (as compared to the rutile TiO2). The degradation efficiencies of 87.7% and 100% were obtained for phenol and 2-CP, respectively, under optimized conditions (0.5 g/L catalyst with a pollutant concentration of 50 mg/L after irradiation time of 180 min).

Schottky or Ohmic metal-semiconductor contact: influence on photocatalytic efficiency of Ag/ZnO and Pt/ZnO model systems.

The relationship between the contact type in metal-semiconductor junctions and their photocatalytic efficiencies is investigated. Two metal-semiconductor junctions, silver on zinc oxide (Ag/ZnO) and platinum on zinc oxide (Pt/ZnO) serve as model system for Ohmic and Schottky metal-semiconductor contact, respectively. Ag/ZnO, with Ohmic contact, exhibits a higher photocatalytic efficiency than Pt/ZnO, with Schottky contact. The direction of electric fields within the semiconductor is found to play a crucial role in the separation of photogenerated charges, and thus strongly influences the photocatalytic efficiency.

A full-sunlight-driven photocatalyst with super long-persistent energy storage ability.

A major drawback of traditional photocatalysts like TiO2 is that they can only work under illumination, and the light has to be UV. As a solution for this limitation, visible-light-driven energy storage photocatalysts have been developed in recent years. However, energy storage photocatalysts that are full-sunlight-driven (UV-visible-NIR) and possess long-lasting energy storage ability are lacking. Here we report, a Pt-loaded and hydrogen-treated WO3 that exhibits a strong absorption at full-sunlight spectrum (300-1,000 nm), and with a super-long energy storage time of more than 300 h to have formaldehyde degraded in dark. In this new material system, the hydrogen treated WO3 functions as the light harvesting material and energy storage material simultaneously, while Pt mainly acts as the cocatalyst to have the energy storage effect displayed. The extraordinary full-spectrum absorption effect and long persistent energy storage ability make the material a potential solar-energy storage and an effective photocatalyst in practice.

Platinum monolayer electrocatalyst on gold nanostructures on silicon for photoelectrochemical hydrogen evolution.

Pt monolayer decorated gold nanostructured film on planar p-type silicon is utilized for photoelectrochemical H2 generation in this work. First, gold nanostructured film on silicon was spontaneously produced by galvanic displacement of the reduction of gold ion and the oxidation of silicon in the presence of fluoride anion. Second, underpotential deposition (UPD) of copper under illumination produced Cu monolayer on gold nanostructured film followed by galvanic exchange of less-noble Cu monolayer with more-noble PtCl6(2-). Pt(shell)/Au(core) on p-type silicon showed the similar activity with platinum nanoparticle on silicon for photoelectrochemical hydrogen evolution reaction in spite of low platinum loading. From Tafel analysis, Pt(shell)/Au(core) electrocatalyst shows the higher area-specific activity than platinum nanoparticle on silicon demonstrating the significant role of underlying gold for charge transfer reaction from silicon to H(+) through platinum catalyst.

Light-induced catalytic and cytotoxic properties of phosphorescent transition metal compounds with a d8 electronic configuration.

Transition metal compounds are well documented to have diverse applications such as in catalysis, light-emitting materials and therapeutics. In the areas of photocatalysis and photodynamic therapy, metal compounds of heavy transition metals are highly sought after because they can give rise to triplet excited states upon photoexcitation. The long lifetimes (more than 1 µs) of the triplet states of transition metal compounds allow for bimolecular reactions/processes such as energy transfer and/or electron transfer to occur. Reactions of triplet excited states of luminescent metal compounds with oxygen in cells may generate reactive oxygen species and/or induce damage to DNA, leading to cell death. This article recaps the recent findings on photochemical and phototoxic properties of luminescent platinum(II) and gold(III) compounds both from the literature and experimental results from our group.

In situ study of atomic structure transformations of Pt-Ni nanoparticle catalysts during electrochemical potential cycling.

When exposed to corrosive anodic electrochemical environments, Pt alloy nanoparticles (NPs) undergo selective dissolution of the less noble component, resulting in catalytically active bimetallic Pt-rich core-shell structures. Structural evolution of PtNi6 and PtNi3 NP catalysts during their electrochemical activation and catalysis was studied by in situ anomalous small-angle X-ray scattering to obtain insight in element-specific particle size evolution and time-resolved insight in the intraparticle structure evolution. Ex situ high-energy X-ray diffraction coupled with pair distribution function analysis was employed to obtain detailed information on the atomic-scale ordering, particle phases, structural coherence lengths, and particle segregation. Our studies reveal a spontaneous electrochemically induced formation of PtNi particles of ordered Au3Cu-type alloy structures from disordered alloy phases (solid solutions) concomitant with surface Ni dissolution, which is coupled to spontaneous residual Ni metal segregation during the activation of PtNi6. Pt-enriched core-shell structures were not formed using the studied Ni-rich nanoparticle precursors. In contrast, disordered PtNi3 alloy nanoparticles lose Ni more rapidly, forming Pt-enriched core-shell structures with superior catalytic activity. Our X-ray scattering results are confirmed by STEM/EELS results on similar nanoparticles.

A high efficiency microreactor with Pt/ZnO nanorod arrays on the inner wall for photodegradation of phenol.

A high efficiency microreactor with Pt coated ZnO (Pt/ZnO) nanorod arrays on the inner wall was successfully fabricated by pumping a Pt sol into the microchannel containing preformed ZnO nanorod arrays. Phenol was selected as a persistent organic pollutant to evaluate the photocatalytic performance of the microreactors. The microreactor which was coated by Pt sol for 5 min showed the best photocatalytic performance compared with other Pt/ZnO nanorod array-modified microreactors. The presence of Pt nanoparticles on the surfaces of ZnO nanorods promoted the separation of photoinduced electron-hole pairs and thus enhanced the photocatalytic activity. In addition, the recyclable property of the microcreator was investigated. It was found that the microreactor displayed higher durability during the continuous photocatalytic process.

Optical property study of FePt-C nanocomposite thin film for heat-assisted magnetic recording.

Optical properties of the FePt-C nanocomposite thin film that was synthesized by sputtering with MgO/NiTa underlayer on glass substrate have been determined by an approach combining spectroscopic ellipsometry and transmission over the wavelength range of 380 - 1700 nm. It was observed that the refractive index is larger than the extinction coefficient, indicating that free electron absorption is not the dominant optical transition in the FePt-C thin film. Compared with FePt thin film, the FePt-C thin film has smaller optical constants, which lead to better optical performance including smaller optical spot on recording media and higher transducer efficiency for heat assisted magnetic recording.

Templated assembly of Co-Pt nanoparticles via thermal and laser-induced dewetting of bilayer metal films.

Templated dewetting of a Co/Pt metal bilayer film on a topographic substrate was used to assemble arrays of Co-Pt alloy nanoparticles, with highly uniform particle size, shape and notably composition compared to nanoparticles formed on an untemplated substrate. Solid-state and liquid-state dewetting processes, using furnace annealing and laser irradiation respectively, were compared. Liquid state dewetting produced more uniform, conformal nanoparticles but they had a polycrystalline disordered fcc structure and relatively low magnetic coercivity. In contrast, solid state dewetting enabled formation of magnetically hard, ordered L1(0) Co-Pt single-crystal particles with coercivity >12 kOe. Furnace annealing converted the nanoparticles formed by liquid state dewetting into the L1(0) phase.

Enhanced material purity and resolution via synchronized laser assisted electron beam induced deposition of platinum.

We introduce a laser assisted electron beam induced deposition (LAEBID) process which is a nanoscale direct write synthesis method that integrates an electron beam induced deposition process with a synchronized pulsed laser step to induce thermal desorption of reaction by-products. Localized, spatially overlapping electron and photon pulses enable the thermal desorption of the reaction by-product while mitigating issues associated with bulk substrate heating, which can shorten the precursor residence time and distort pattern fidelity due to thermal drift. Current results demonstrate purification of platinum deposits (reduced carbon content by ~50%) with the addition of synchronized laser pulses as well as a significant reduction in deposit resistivity. Measured resistivities from platinum LAEBID structures (4 × 10(3)µΩ cm) are nearly 4 orders of magnitude lower than standard EBID platinum structures (2.2 × 10(7)µΩ cm) from the same precursor and are lower than the lowest reported EBID platinum resistivity with post-deposition annealing (1.4 × 10(4)µΩ cm). Finally the LAEBID process demonstrates improved deposit resolution by ~25% compared to EBID structures under the conditions investigated in this work.