Charge carrier recombination processes, intragap defect states, and photoluminescence mechanisms in stoichiometric and reduced TiO2 brookite nanorods: an interpretation scheme through in situ photoluminescence excitation spectroscopy in controlled environment.

The study of titanium dioxide (TiO2) in the brookite phase is gaining popularity as evidence has shown the efficient photocatalytic performance of this less investigated polymorph. It has been recently reported that defective anisotropic brookite TiO2 nanorods display remarkable substrate-specific reactivity towards alcohol photoreforming, with rates of hydrogen production significantly (18-fold) higher than those exhibited by anatase TiO2 nanoparticles. To elucidate the basic photo-physical mechanisms and peculiarities leading to such an improvement in the photoactive efficiency, we investigated the recombination processes of photoexcited charge carriers in both stoichiometric and reduced brookite nanorods via photoluminescence excitation spectroscopy in controlled environment. Through an investigation procedure employing both supragap and subgap excitation during successive exposure to oxidizing and reducing gaseous agents, we firstly obtained an interpretation scheme describing the main photoluminescence and charge recombination pathways in stoichiometric and reduced brookite, which includes information about the spatial and energetic position of the intragap states involved in photoluminescence mechanisms, and secondly identified a specific photoluminescence enhancement process occurring in only reduced brookite nanorods, which indicates the injection of a conduction band electron during ethanol photo-oxidation. The latter finding may shed light on the empirical evidence about the exceptional reactivity of reduced brookite nanorods toward the photo-oxidation of alcohols and the concomitant efficiency of photocatalytic hydrogen generation.

Diffractive Refractometer Based on Scalar Theory.

The measurement of the refractive index typically requires the use of optical ellipsometry which, although potentially very accurate, is extremely sensitive to the structural properties of the sample and its theoretical modeling, and typically requires specialized expertise to obtain reliable output data. Here, we propose a simple diffractive method for the measurement of the refractive index of homogenous solid thin films, which requires only the structuring of the surface of the material to be measured with the profile of a diffraction grating. The refractive index of an exemplary soft-moldable material is successfully estimated over a wide wavelength range by simply incorporating the measured topography and diffraction efficiency of the grating into a convenient scalar theory-based diffraction model. Without the need for specialized expertise and equipment, the method can serve as a simple and widely accessible optical characterization of materials useful in material science and photonics applications.

Over-Expressed GATA-1S, the Short Isoform of the Hematopoietic Transcriptional Factor GATA-1, Inhibits Ferroptosis in K562 Myeloid Leukemia Cells by Preventing Lipid Peroxidation.

Ferroptosis is a recently recognized form of regulated cell death involving lipid peroxidation. Glutathione peroxidase 4 (GPX4) plays a central role in the regulation of ferroptosis through the suppression of lipid peroxidation generation. Connections have been reported between ferroptosis, lipid metabolism, cancer onset, and drug resistance. Recently, interest has grown in ferroptosis induction as a potential strategy to overcome drug resistance in hematological malignancies. GATA-1 is a key transcriptional factor controlling hematopoiesis-related gene expression. Two GATA-1 isoforms, the full-length protein (GATA-1FL) and a shorter isoform (GATA-1S), are described. A balanced GATA-1FL/GATA-1S ratio helps to control hematopoiesis, with GATA-1S overexpression being associated with hematological malignancies by promoting proliferation and survival pathways in hematopoietic precursors. Recently, optical techniques allowed us to highlight different lipid profiles associated with the expression of GATA-1 isoforms, thus raising the hypothesis that ferroptosis-regulated processes could be involved. Lipidomic and functional analysis were conducted to elucidate these mechanisms. Studies on lipid peroxidation production, cell viability, cell death, and gene expression were used to evaluate the impact of GPX4 inhibition. Here, we provide the first evidence that over-expressed GATA-1S prevents K562 myeloid leukemia cells from lipid peroxidation-induced ferroptosis. Targeting ferroptosis is a promising strategy to overcome chemoresistance. Therefore, our results could provide novel potential therapeutic approaches and targets to overcome drug resistance in hematological malignancies.

First-Principles Study of Cu-Based Inorganic Hole Transport Materials for Solar Cell Applications.

Perovskite solar cells (PSCs) and dye-sensitized solar cells (DSCs) both represent promising strategies for the sustainable conversion of sunlight into electricity and fuels. However, a few flaws of current devices hinder the large-scale establishment of such technologies. On one hand, PSCs suffer from instabilities and undesired phenomena mostly linked to the perovskite/hole transport layer (HTL) interface. Most of the currently employed organic HTL (e.g., Spiro-OMeTAD) are supposed to contribute to the perovskite decomposition and to be responsible for charge recombination processes and polarization barriers. On the other hand, power conversion efficiencies (PCEs) of DSCs are still too low to compete with other conversion technologies. Tandem cells are built by assembling p-type and n-type DSCs in a cascade architecture and, since each dye absorbs on a different portion of the solar spectrum, the harvesting window is increased and the theoretical efficiency limit for a single chromophore (i.e., the Shockley-Queisser limit) is overcome. However, such a strategy is hindered by the lack of a p-type semiconductor with optimal photocathode features. Nickel oxide has been, by far, the first-choice inorganic p-type semiconductor for both PV technologies, but its toxicity and non-optimal features (e.g., too low open circuit voltage and the presence of trap states) call for alternatives. Herein, we study of three p-type semiconductors as possible alternative to NiO, namely CuI, CuSCN and Cu2O. To this aim, we compare the structural and electronic features of the three materials by means of a unified theoretical approach based on the state-of-the art density functional theory (DFT). We focus on the calculation of their valence band edge energies and compare such values with those of two widely employed photo-absorbers, i.e., methylammonium lead iodide (MAPI) and the triple cation MAFACsPbBrI in PSCs and P1 and Y123 dyes in DSCs, given that the band alignment and the energy offset are crucial for the charge transport at the interfaces and have direct implications on the final efficiency. We dissect the effect a copper vacancy (i.e., intrinsic p-type doping) on the alignment pattern and rationalize it from both a structural and an electronic perspective. Our data show how defects can represent a crucial degree of freedom to control the driving force for hole injection in these devices.

Varifocal diffractive lenses for multi-depth microscope imaging.

Flat optical elements enable the realization of ultra-thin devices able to either reproduce or overcome the functionalities of standard bulky components. The fabrication of these elements involves the structuration of material surfaces on the light wavelength scale, whose geometry has to be carefully designed to achieve the desired optical functionality. In addition to the limits imposed by lithographic design-performance compromises, their optical behavior cannot be accurately tuned afterward, making them difficult to integrate in dynamic optical systems. Here we show the realization of fully reconfigurable flat varifocal diffractive lens, which can be in-place realized, erased and reshaped directly on the surface of an azopolymer film by an all-optical holographic process. Integrating the lens in the same optical system used as standard refractive microscope, results in a hybrid microscope capable of multi-depth object imaging. Our approach demonstrates that reshapable flat optics can be a valid choice to integrate, or even substitute, modern optical systems for advanced functionalities.

An Instantaneous Recombination Rate Method for the Analysis of Interband Recombination Processes in ZnO Crystals.

Time-resolved photoluminescence (TRPL) analysis is often performed to assess the qualitative features of semiconductor crystals using predetermined functions (e.g., double- or multi-exponentials) to fit the decays of PL intensity. However, in many cases-including the notable case of interband PL in direct gap semiconductors-this approach just provides phenomenological parameters and not fundamental physical quantities. In the present work, we highlight that within a properly chosen range of laser excitation, the TRPL of zinc oxide (ZnO) bulk crystals can be described with excellent precision with second-order kinetics for the total recombination rate. We show that this allows us to define an original method for data analysis, based on evaluating the "instantaneous" recombination rate that drives the initial slope of the decay curves, acquired as a function of the excitation laser fluence. The method is used to fit experimental data, determining useful information on fundamental quantities that appear in the second-order recombination rate, namely the PL (unimolecular) lifetime, the bimolecular recombination coefficient, the non-radiative lifetime and the equilibrium free-carrier concentration. Results reasonably close to those typically obtained in direct gap semiconductors are extracted. The method may represent a useful tool for gaining insight into the recombination processes of a charge carrier in ZnO, and for obtaining quantitative information on ZnO excitonic dynamics.

Enhanced photoinduced mass migration in supramolecular azopolymers by H-bond driven positional constraint.

Here we investigated the role of hydrogen bonding in the design of supramolecular azopolymers with a highly directional and constrained azobenzene-chain interaction involving the aromatic ring of the photoactive molecule, by exploiting the 2-aminopyrimidine/carboxylic acid supramolecular synthon as the tool for molecular recognition. We have shown that this approach is advantageous for producing affordable and versatile photopatternable azomaterials by complexation with polyacrylic acid (PAA). Molecular model complexes were successfully prepared and characterized by X-ray diffraction analysis and FTIR spectroscopy to reveal the multiple, non-ionic interaction occurring between the azobenzene units and the polymer chains. Surface photopatterning of thin films, driven by the typical mass migration phenomenon occurring in azopolymers, resulted strongly enhanced with increasing azobenzene content until equimolar composition. Results show that polymers with synthon-based azobenzenes markedly outperform single H-bonded systems bearing azomolecules with similar structure and electronic properties. We finally demonstrated that the azobenzene units can be easily extracted from a photopatterned film by a simple solvent rinse and without any chemical pre-treatment, leaving the periodicity of the inscribed surface relief gratings unaltered. This result was enabled by the orthogonal solubility of the components in the supramolecular system.

Charge Carrier Processes and Optical Properties in TiO2 and TiO2-Based Heterojunction Photocatalysts: A Review.

Photocatalysis based technologies have a key role in addressing important challenges of the ecological transition, such as environment remediation and conversion of renewable energies. Photocatalysts can in fact be used in hydrogen (H2) production (e.g., via water splitting or photo-reforming of organic substrates), CO2 reduction, pollution mitigation and water or air remediation via oxidation (photodegradation) of pollutants. Titanium dioxide (TiO2) is a "benchmark" photocatalyst, thanks to many favorable characteristics. We here review the basic knowledge on the charge carrier processes that define the optical and photophysical properties of intrinsic TiO2. We describe the main characteristics and advantages of TiO2 as photocatalyst, followed by a summary of historical facts about its application. Next, the dynamics of photogenerated electrons and holes is reviewed, including energy levels and trapping states, charge separation and charge recombination. A section on optical absorption and optical properties follows, including a discussion on TiO2 photoluminescence and on the effect of molecular oxygen (O2) on radiative recombination. We next summarize the elementary photocatalytic processes in aqueous solution, including the photogeneration of reactive oxygen species (ROS) and the hydrogen evolution reaction. We pinpoint the TiO2 limitations and possible ways to overcome them by discussing some of the "hottest" research trends toward solar hydrogen production, which are classified in two categories: (1) approaches based on the use of engineered TiO2 without any cocatalysts. Discussed topics are highly-reduced "black TiO2", grey and colored TiO2, surface-engineered anatase nanocrystals; (2) strategies based on heterojunction photocatalysts, where TiO2 is electronically coupled with a different material acting as cocatalyst or as sensitizer. Examples discussed include TiO2 composites or heterostructures with metals (e.g., Pt-TiO2, Au-TiO2), with other metal oxides (e.g., Cu2O, NiO, etc.), direct Z-scheme heterojunctions with g-C3N4 (graphitic carbon nitride) and dye-sensitized TiO2.

Time-gated luminescence imaging of positively charged poly-l-lysine-coated highly microporous silicon nanoparticles in living Hydra polyp.

The development of non-toxic fluorescent agents alternative to heavy metal-based semiconductor quantum dots represents a relevant topic in biomedical research and in particular in the bioimaging field. Herein, highly luminescent Si─H terminal microporous silicon nanoparticles with µs-lived photoemission are chemically modified with a two step process and successfully used as label-free probes for in vivo time-gated luminescence imaging. In this context, Hydra vulgaris is used as model organism for in vivo study and validity assessment. The application of time gating allows to pursue an effective sorting of the signals, getting rid of the most common sources of noise that are fast-decay tissue autofluorescence and excitation scattering within the tissue. Indeed, an enhancement by a factor ~ 20 in the image signal-to-noise ratio can be estimated.

Structural and electronic properties of defective 2D transition metal dichalcogenide heterostructures.

We present a first-principles study on the structure-property relationships in MoS2 and WS2 monolayers and their vertically stacked hetero-bilayer, with and without Sulfur vacancies, in order to dissect the electronic features behind their photocatalytic water splitting capabilities. We also benchmark the accuracy of three different exchange-correlation density functionals for both minimum-energy geometries and electronic structure. The best compromise between computational cost and qualitative accuracy is achieved with the HSE06 density functional on top of Perdew-Burke-Ernzerhof minima, including dispersion with Grimme's D3 scheme. This computational approach predicts the presence of mid-gap states for defective monolayers, in accordance with the present literature. For the heterojunction, we find unexpected vacancy-position dependent electronic features: the location of the defects leads either to mid-gap trap states, detrimental for photocatalyst or to a modification of characteristic type II band alignment behavior, responsible for interlayer charge separation and low recombination rates.

Quantitative Study of Morphological Features of Stem Cells onto Photopatterned Azopolymer Films.

In the last decade, the use of photolithography for the fabrication of structured substrates with controlled morphological patterns that are able to interact with cells at micrometric and nanometric size scales is strongly growing. A promising simple and versatile microfabrication method is based on the physical mass transport induced by visible light in photosensitive azobenzene-containing polymers (or azopolymers). Such light-driven material transport produces a modulation of the surface of the azopolymer film, whose geometry is controlled by the intensity and the polarization distributions of the irradiated light. Herein, two anisotropic structured azopolymer films have been used as substrates to evaluate the effects of topological signals on the in vitro response of human mesenchymal stem cells (hMSCs). The light-induced substrate patterns consist of parallel microgrooves, which are produced in a spatially confined or over large-scale areas of the samples, respectively. The analysis of confocal optical images of the in vitro hMSC cells grown on the patterned films offered relevant information about cell morphology-i.e., nuclei deformation and actin filaments elongation-in relation to the geometry and the spatial extent of the structured area of substrates. The results, together with the possibility of simple, versatile, and cost-effective light-induced structuration of azopolymers, promise the successful use of these materials as anisotropic platforms to study the cell guidance mechanisms governing in vitro tissue formation.

First-principles study of Na insertion at TiO2 anatase surfaces: new hints for Na-ion battery design.

Na-ion batteries (NIBs) are attracting widespread interest as a potentially more convenient alternative to current state-of-the-art Li-ion batteries (LIBs), chiefly for large-scale energy storage from renewables. Developing novel active materials is essential for the deployment of NIBs, especially in terms of negative electrodes that can accommodate the larger sodium ions. We focus on TiO2 anatase, which has been proposed as a promising anode material for the overall balance of performance, stability and cost. As the exposed crystal facets in different morphologies of nanostructured anatase can affect the electrochemical performances, here we report a theoretical investigation of Na+ adsorption and migration through (101), (100) and (001) surface terminations, thus explaining the different activities toward sodiation reported in the literature. Energy barriers computed by means of the CI-NEB method at the DFT+U level of theory show that the (001) surface is the most effective termination for Na+ insertion. We also provide a detailed analysis to elucidate that the energy barriers are due to structural modifications of the lattice upon sodiation. From these results we derive new design directions for the development of cheap and effective oxide-based nanostructured electrode materials for advanced NIBs.

Spontaneous wrinkle emergence in nascent eumelanin thin films.

Self-patterning processes originated by physical stimuli have been extensively documented in thin films, whereas spontaneous wrinkling phenomena due to chemical transformation processes are, to the best of our knowledge, unprecedented. Herein we report a case of spontaneous polymerization-driven surface nano-patterning (∼500 nm) that develops in smooth thin solid films of 5,6-dihydroxyindole (DHI), a major precursor of eumelanin polymers, over a time scale of 30 to 60 days in air at room temperature. The phenomenon can be observed only above a critical film thickness of ∼250 nm and it is affected by exposure to ammonia vapors causing acceleration of the oxidation process. The thickness-dependent onset of wrinkling can be attributed to non-homogeneous rates of oxidation through the film causing slow swelling/expansion of the inner layers followed by fast stiffening and cross-linking in the outer layer exposed to higher oxygen levels.

Luminescent cis-Iridium(III) Complex Based on a Bis(6,7-dimethoxy-3,4-dihydroisoquinoline) Platform Featuring an Unusual cis Orientation of the C∧N Ligands: From a Theoretical Approach to a Deep Red LEEC Device.

By pursuing the strategy of manipulating natural compounds to obtain functional materials, in this work, we report on the synthesis and characterization of a luminescent cationic iridium complex (cis-1), designed starting from the catecholic neurotransmitter dopamine, exhibiting the unusual cis arrangement of the C∧N ligands. Through an integrated experimental and theoretical approach, it was possible to delineate the optoelectronic properties of cis-1. In detail, (a) a series of absorption maxima in the range 300-400 nm was assigned to metal-to-ligand charge transfer and weak and broad absorption maxima at longer wavelengths (400-500 nm) were ascribable to spin-forbidden transitions with a mixed character; (b) there was an intense red phosphorescence with emission set in the range 580-710 nm; and (c) a highest occupied molecular orbital was mainly localized on the metal and the 2-phenylpiridine ligand and a lowest unoccupied molecular orbital was localized on the N∧N ligand, with a ΔH-L set at 2.20 eV. This investigation allowed the design of light-emitting electrochemical cell (LEEC) devices endowed with good performance. The poor literature reporting on the use of cis-iridium(III) complexes in LEECs prompted us to investigate the role played by the selected cathode and the thickness of the emitting layer, as well as the doping effect exerted by ionic liquids on the performance of the devices. All the devices exhibited a deep red emission, in some cases, quite near the pure color (devices #1, #4, and #8), expanding the panorama of the iridium-based red-to-near-infrared LEEC devices. The characteristics of the devices, such as the brightness reaching values of 162 cd/m2 for device #7, suggested that the performances of cis-1 are comparable to those of trans isomers, opening new perspective toward designing a new set of luminescent materials for optoelectronic devices.

Hexamethylenediamine-Mediated Polydopamine Film Deposition: Inhibition by Resorcinol as a Strategy for Mapping Quinone Targeting Mechanisms.

Hexamethylenediamine (HMDA) and other long chain aliphatic diamines can induce substrate-independent polymer film deposition from dopamine and several other catechols substrates at relatively low concentrations, however the mechanism of the diamine-promoted effect has remained little understood. Herein, we report data indicating that: (a) film deposition from 1 mM HMDA and dopamine is not affected by chemical oxidation with periodate but is markedly inhibited by resorcinol, which also prevents PDA film formation at 10 mM monomer concentration in the absence of HMDA; (b) N-acetylation of HMDA completely inhibits the effect on PDA film formation; (c) HMDA enables surface functionalization with 1 mM 5,6-dihydroxyindole (DHI) polymerization at pH 9.0 in a resorcinol-inhibitable manner. Structural investigation of the polymers produced from dopamine and DHI in the presence of HMDA using solid state 13C and 15N NMR and MALDI-MS suggested formation of covalent cross linked structures. It is concluded that HMDA enhances polydopamine adhesion by acting both on dopamine quinone and downstream, e.g., via covalent coupling with DHI. These results provide new insights into the mechanisms of PDA adhesion and disclose resorcinol as a new potent tool for targeting/mapping quinone intermediates and for controlling polymer growth.

Computer-generated holograms for complex surface reliefs on azopolymer films.

The light-driven superficial structuration observed on the surface of films of azobenzene-containing polymers follows the optical field distribution of the illuminating light pattern, i.e. the light polarization state and the intensity distribution. The ability to precisely manipulate the illuminating intensity pattern can hence provide a new level in the range of complex light-induced superficial textures accessible onto azopolymer film surfaces. In this respect, digital holography, based on the principles of the Computer-Generated Holograms (CGHs), and actually implemented by means of a versatile liquid crystal spatial light modulator, can represent a unique experimental tool in the field of the light-induced mass migration in azo-materials. In the present work, we demonstrate the possibility to precisely control the features and the quality of complex light patterns generated through CGHs in order to induce arbitrarily complex surface reliefs onto the surface of an azopolymer. The results shown here can potentially broaden the range of possible applications of photo-responsive azopolymer films in the fields of surface engineering, biology and photonics.

Ab initio Study of Anchoring Groups for CuGaO2 Delafossite-Based p-Type Dye Sensitized Solar Cells.

Here we report the first theoretical characterization of the interface between the CuGaO2 delafossite oxide and the carboxylic (-COOH) and phosphonic acid (-PO3H2) anchoring groups. The promising use of delafossites as effective alternative to nickel oxide in p-type DSSC is still limited by practical difficulties in sensitizing the delafossite surface. Thus, this work provides atomistic insights on the structure and energetics of all the possible interactions between the anchoring functional groups and the CuGaO2 surface species, including the effects of the Mg doping and of the solvent medium. Our results highlight the presence of a strong selectivity toward the monodentate binding mode on surface Ga atoms for both the carboxylic and phosphonic acid groups. Since the binding modes have a strong influence on the hole injection thermodynamics, these findings have direct implications for further development of delafossite based p-type DSSCs.

Analysis of nascent silicon phase-change gratings induced by femtosecond laser irradiation in vacuum.

The formation of periodic surface structures is a general effect of femtosecond laser irradiation of solid targets showing promising interest in material science and technology. However, the experiments are typically carried out in air, a condition in which the target surface becomes densely decorated with nanoparticles that can influence the formation of the surface structures in the early stage of the irradiation process. Here we report an investigation of structures generation on a silicon surface irradiated in vacuum (10-5 mbar) with a low number of laser pulses (N ≤ 10) that exploits several microscopy techniques (optical, atomic force, electron and Raman). Our analyses allow identifying the creation of silicon phase-change gratings consisting of alternating amorphous and crystalline periodic lines, with almost no material removal, located at the periphery of a shallow ablation crater. These gratings originate from two different kinds of defects: (i) the first is characterized by a peculiar lobed shape that is produced by the first few laser pulses; (ii) the second is provided by the one-dimensional, linear singularity defined by the ablation edge of the nascent crater. Both kind of defects lead to grating structures extending outwards the amorphous central area of the crater along the direction of the laser polarization. Comparative analysis with the surface formed in air, in the same experimental conditions, evidences the important role played by nanoparticles densely decorating the target in air and the striking variation occurring in vacuum.

Structural Basis of Polydopamine Film Formation: Probing 5,6-Dihydroxyindole-Based Eumelanin Type Units and the Porphyrin Issue.

The role of 5,6-dihydroxyindole (DHI)-based oligomers, including porphyrin-like tetramers, in polydopamine (PDA) film formation was addressed by a comparative structural investigation against model polymers from DHI and its 2,7'-dimer. MALDI-MS data showed that (a) PDA is structurally different from DHI melanin and does not contain species compatible with DHI-based oligomers as primary building blocks; (b) PDA films and precipitate display a single main peak at m/ z 402 in common; (c) no species matching the range of m/ z values expected for cyclic porphyrin-type tetramers was detected in DHI melanin produced in the presence or in the absence of folic acid (FA) as templating agent, nor by oxidation of the 2,7'-dimer of DHI as putative precursor. 15N NMR resonances and Raman spectra predicted by extensive DFT calculations on porphyrin-type structures at various oxidation levels did not match spectral data for PDA or DHI melanin. Notably, unlike PDA, which gave structurally homogeneous films on quartz on atomic force microscopy (AFM) and micro-Raman spectroscopy, DHI melanin did not form any adhesive deposit after as long as 24 h. It is concluded that PDA film deposition involves structural components unrelated to DHI-based oligomers or porphyrin-type tetramers, which, on mechanism-based analysis, may arise by quinone-amine conjugation leading to polycyclic systems with extensive chain breakdown.

The Chemistry of Polydopamine Film Formation: The Amine-Quinone Interplay.

Despite extensive investigations over the past decade, the chemical basis of the extraordinary underwater adhesion properties of polydopamine (PDA) has remained not entirely understood. The bulk of evidence points to PDA wet adhesion as a complex process based on film deposition, and growth in which primary amine groups, besides catechol moieties, play a central role. However, the detailed interplay of chemical interactions underlying the dynamics of film formation has not yet been elucidated. Herein, we report the results of a series of experiments showing that coating formation from dopamine at pH 9.0 in carbonate buffer: (a) Requires high dopamine concentrations (>1 mM); (b) is due to species produced in the early stages of dopamine autoxidation; (c) is accelerated by equimolar amounts of periodate causing fast conversion to the o-quinone; and (d) is enhanced by the addition of hexamethylenediamine (HMDA) and other long chain aliphatic amines even at low dopamine concentrations (<1 mM). It is proposed that concentration-dependent PDA film formation reflects the competition between intermolecular amine-quinone condensation processes, leading to adhesive cross-linked oligomer structures, and the intramolecular cyclization route forming little adhesive 5,6-dihydroxyindole (DHI) units. Film growth would then be sustained by dopamine and other soluble species that can be adsorbed on the surface.