Exploring zinc oxide morphologies for aqueous solar cells by a photoelectrochemical, computational, and multivariate approach.

Dye-sensitized solar cells assembled with aqueous electrolytes are emerging as a sustainable photovoltaic technology suitable for safe indoor and portable electronics use. While the scientific community is exploring unconventional materials for preparing electrodes and electrolytes, this work presents the first study on zinc oxide as a semiconductor material to fabricate photoanodes for aqueous solar cells. Different morphologies (i.e., nanoparticles, multipods, and desert roses) are synthesized, characterized, and tested in laboratory-scale prototypes. This exploratory work, also integrated by a computational study and a multivariate investigation on the factors that influence electrode sensitization, confirms the possibility of using zinc oxide in the field of aqueous photovoltaics and opens the way to new morphologies and processes of functionalization or surface activation to boost the overall cell efficiency.

The Effect of Sulfur and Nitrogen Doping on the Oxygen Reduction Performance of Graphene/Iron Oxide Electrocatalysts Prepared by Using Microwave-Assisted Synthesis.

The synthesis of novel catalysts for the oxygen reduction reaction, by means of a fast one-pot microwave-assisted procedure, is reported herein and deeply explained. In particular, the important role of doping atoms, like sulfur and nitrogen, in Fe2O3-reduced graphene oxide nanocomposites is described to address the modification of catalytic performance. The presence of dopants is confirmed by X-ray Photoelectron Spectroscopy analysis, while the integration of iron oxide nanoparticles, by means of decoration of the graphene structure, is corroborated by electron microscopy, which also confirms that there is no damage to the graphene sheets induced by the synthesis procedure. The electrochemical characterizations put in evidence the synergistic catalysis effects of dopant atoms with Fe2O3 and, in particular, the importance of sulfur introduction into the graphene lattice. Catalytic performance of as-prepared materials toward oxygen reduction shows values close to the Pt/C reference material, commonly used for fuel cell and metal-air battery applications.

Reduced Graphene Oxide Embedded with ZnS Nanoparticles as Catalytic Cathodic Material for Li-S Batteries.

Lithium-sulfur technology is a strong candidate for the future generation of batteries due to its high specific capacity (1675 mAh g-1), low cost, and environmental impact. In this work, we propose a facile and solvent-free microwave synthesis for a composite material based on doped (sulfur and nitrogen) reduced graphene oxide embedded with zinc sulfide nanoparticles (SN-rGO/ZnS) to improve the battery performance. The chemical-physical characterization (XRD, XPS, FESEM, TGA) confirmed the effectiveness of the microwave approach in synthesizing the composite materials and their ability to be loaded with sulfur. The materials were then thoroughly characterized from an electrochemical point of view (cyclic voltammetry, galvanostatic cycling, Tafel plot, electrochemical impedance spectroscopy, and Li2S deposition test); the SN-rGO/ZnS/S8 cathode showed a strong affinity towards polysulfides, thus reducing their loss by diffusion and improving redox kinetics, allowing for faster LiPSs conversion. In terms of performance, the composite-based cathode increased the specific capacity at high rate (1 C) from 517 to 648 mAh g-1. At the same time, more stable behavior was observed at 0.5 C with capacity retention at the 750th cycle, where it was raised from 32.5% to 48.2%, thus confirming the beneficial effect of the heteroatomic doping process and the presence of zinc sulfide nanoparticles.

Iron-Doped ZnO Nanoparticles as Multifunctional Nanoplatforms for Theranostics.

Zinc oxide nanoparticles (ZnO NPs) are currently among the most promising nanomaterials for theranostics. However, they suffer from some drawbacks that could prevent their application in nanomedicine as theranostic agents. The doping of ZnO NPs can be effectively exploited to enhance the already-existing ZnO properties and introduce completely new functionalities in the doped material. Herein, we propose a novel synthetic approach for iron-doped ZnO (Fe:ZnO) NPs as a multifunctional theranostic nanoplatform aimed at cancer cell treatment. Pure ZnO and Fe:ZnO NPs, with two different levels of iron doping, were synthesized by a rapid wet-chemical method and analyzed in terms of morphology, crystal structure and chemical composition. Interestingly, Fe:ZnO NPs featured bioimaging potentialities thanks to superior optical properties and novel magnetic responsiveness. Moreover, iron doping provides a way to enhance the electromechanical behavior of the NPs, which are then expected to show enhanced therapeutic functionalities. Finally, the intrinsic therapeutic potentialities of the NPs were tested in terms of cytotoxicity and cellular uptake with both healthy B lymphocytes and cancerous Burkitt's lymphoma cells. Furthermore, their biocompatibility was tested with a pancreatic ductal adenocarcinoma cell line (BxPC-3), where the novel properties of the proposed iron-doped ZnO NPs can be potentially exploited for theranostics.

Microwave-Assisted Synthesis of Nitrogen and Sulphur Doped Graphene Decorated with Antimony Oxide: An Effective Catalyst for Oxygen Reduction Reaction.

In this study, we report on the facile synthesis of a novel electrocatalysts for the oxygen reduction reaction (ORR), based on reduced graphene oxide (RGO), functionalized with metallic and non-metallic elements. In particular, thanks to a fast one-pot microwave-assisted procedure, we induced, in the RGO graphene lattice, a combined doping with nitrogen and sulphur, and the simultaneous decoration with antimony oxide nanocrystals. The multi-doped-decorated material shows enhanced catalytic performance towards ORR, with respect to common nitrogen- or sulphur-doped carbon-based materials. The presence of co-doping is confirmed by transmission electron microscopy and X-ray photoelectron spectroscopy analysis. The detailed electrochemical characterization shows the simultaneous effects of dopant atoms on the catalytic behavior. In particular, the importance of nitrogen and sulphur atoms in driving the oxygen absorption, together with the role of antimony in enhancing the electrochemical performance toward the ORR, are discussed.

Polydopamine Nanoparticles as an Organic and Biodegradable Multitasking Tool for Neuroprotection and Remote Neuronal Stimulation.

Oxidative stress represents a common issue in most neurological diseases, causing severe impairments of neuronal cell physiological activity that ultimately lead to neuron loss of function and cellular death. In this work, lipid-coated polydopamine nanoparticles (L-PDNPs) are proposed both as antioxidant and neuroprotective agents, and as a photothermal conversion platform able to stimulate neuronal activity. L-PDNPs showed the ability to counteract reactive oxygen species (ROS) accumulation in differentiated SH-SY5Y, prevented mitochondrial ROS-induced dysfunctions and stimulated neurite outgrowth. Moreover, for the first time in the literature, the photothermal conversion capacity of L-PDNPs was used to increase the intracellular temperature of neuron-like cells through near-infrared (NIR) laser stimulation, and this phenomenon was thoroughly investigated using a fluorescent temperature-sensitive dye and modeled from a mathematical point of view. It was also demonstrated that the increment in temperature caused by the NIR stimulation of L-PDNPs was able to produce a Ca2+ influx in differentiated SH-SY5Y, being, to the best of our knowledge, the first example of organic nanostructures used in such an approach. This work could pave the way to new and exciting applications of polydopamine-based and of other NIR-responsive antioxidant nanomaterials in neuronal research.

Facile Chemical Synthesis of Doped ZnO Nanocrystals Exploiting Oleic Acid.

Zinc oxide nanocrystals (ZnO-NCs) doped with transition metal elements or rare earth elements can be probed for magnetic resonance imaging to be used as a molecular imaging technique for accurate diagnosis of various diseases. Herein, we use Mn as a candidate of transition metal elements and Gd as a presenter of rare earth elements. We report an easy and fast coprecipitation method exploiting oleic acid to synthesize spherical-shaped, small-sized doped ZnO-NCs. We show the improved colloidal stability of oleate-stabilized doped ZnO-NCs compared to the doped ZnO-NCs synthesized by conventional sol-gel synthesis method, i.e., without a stabilizing agent, especially for the Mn dopant. We also analyze their structural, morphological, optical, and magnetic properties. We are able to characterize the persistence of the crystalline properties (wurtzite structure) of ZnO in the doped structure and exclude the formation of undesired oxides by doping elements. Importantly, we determine the room-temperature ferromagnetism of the doped ZnO-NCs. This oleate-stabilized coprecipitation method can be subjected as a standard procedure to synthesize doped and also co-doped ZnO-NCs with any transition metal elements or rare earth elements. In the future, oleate-stabilized Gd/Mn-doped ZnO-NCs can be exploited as magnetic resonance imaging (MRI) contrast agents and possibly increase the signal intensity on T1-weighted images or reduce the signal intensity on T2-weighted images.

Zinc Oxide Nanocrystals and High-Energy Shock Waves: A New Synergy for the Treatment of Cancer Cells.

In the last years, different nanotools have been developed to fight cancer cells. They could be administered alone, exploiting their intrinsic toxicity, or remotely activated to achieve cell death. In the latter case, ultrasound (US) has been recently proposed to stimulate some nanomaterials because of the US outstanding property of deep tissue penetration and the possibility of focusing. In this study, for the first time, we report on the highly efficient killing capability of amino-propyl functionalized ZnO nanocrystals (ZnO NCs) in synergy with high-energy ultrasound shock waves (SW) for the treatment of cancer cells. The cytotoxicity and internalization of ZnO NCs were evaluated in cervical adenocarcinoma KB cells, as well as the safety of the SW treatment alone. Then, the remarkably high cytotoxic combination of ZnO NCs and SW was demonstrated, comparing the effect of multiple (3 times/day) SW treatments toward a single one, highlighting that multiple treatments are necessary to achieve efficient cell death. At last, preliminary tests to understand the mechanism of the observed synergistic effect were carried out, correlating the nanomaterial surface chemistry to the specific type of stimulus used. The obtained results can thus pave the way for a novel nanomedicine treatment, based on the synergistic effect of nanocrystals combined with highly intense mechanical pressure waves, offering high efficiency, deep and focused tissue penetration, and a reduction of side effects on healthy cells.

Piezo- and Photocatalytic Activity of Ferroelectric ZnO:Sb Thin Films for the Efficient Degradation of Rhodamine-ß dye Pollutant.

The discovery of novel catalytic materials showing unprecedented properties and improved functionalities represents a major challenge to design advanced oxidation processes for wastewater purification. In this work, antimony (Sb) doping is proposed as a powerful approach for enhancing the photo- and piezocatalytic performances of piezoelectric zinc oxide (ZnO) thin films. To investigate the role played by the dopant, the degradation of Rhodamine-ß (Rh-ß), a dye pollutant widely present in natural water sources, is studied when the catalyst is irradiated by ultraviolet (UV) light or ultrasound (US) waves. Depending on the doping level, the structural, optical, and ferroelectric properties of the catalyst can be properly set to maximize the dye degradation efficiency. Independently of the irradiation source, the fastest and complete dye degradation is observed in the presence of the doped catalyst and for an optimal amount of the inserted dopant. Among ZnO:Sb samples, the most doped one (5 at. %) shows improved UV light absorption and photocatalytic properties. Conversely, the piezocatalytic efficiency is maximized using the lowest Sb amount (1 at. %). The superior ferroelectric polarization observed in this case highly favors the adsorption of electrically charged species, in particular of the dye in the protonated form (Rh-ß+) and of OH-, to the catalyst surface and the production of hydroxyl radicals responsible for dye degradation.

Leveraging re-chargeable nanobubbles on amine-functionalized ZnO nanocrystals for sustained ultrasound cavitation towards echographic imaging.

Nanoparticles able to promote inertial cavitation when exposed to focused ultrasound have recently gained much attention due to their vast range of possible applications in the biomedical field, such as enhancing drug penetration in tumor or supporting ultrasound contrast imaging. Due to their nanometric size, these contrast agents could penetrate through the endothelial cells of the vasculature to target tissues, thus enabling higher imaging resolutions than commercial gas-filled microbubbles. Herein, Zinc Oxide NanoCrystals (ZnO NCs), opportunely functionalized with amino-propyl groups, are developed as novel nanoscale contrast agents that are able, for the first time, to induce a repeatedly and over-time sustained inertial cavitation as well as ultrasound contrast imaging. The mechanism behind this phenomenon is investigated, revealing that re-adsorption of air gas nanobubbles on the nanocrystal surface is the key factor for this re-chargeable cavitation. Moreover, inertial cavitation and significant echographic signals are obtained at physiologically relevant ultrasound conditions (MI < 1.9), showing great potential for low side-effects in in-vivo applications of the novel nanoscale agent from diagnostic imaging to gas-generating theranostic nanoplatforms and to drug delivery.

ZnO nanocrystals shuttled by extracellular vesicles as effective Trojan nano-horses against cancer cells.

Aim: The effective application of nanoparticles in cancer theranostics is jeopardized by their aggregation in biological media, rapid degradation and clearance. The design of biomimetic nanoconstructs with enhanced colloidal stability and non-immunogenicity is therefore essential. We propose naturally stable cell-derived extracellular vesicles to encapsulate zinc oxide (ZnO) nanocrystals as efficacious nanodrugs, to obtain highly biomimetic and stable Trojan nano-horses (TNHs). Materials & methods: Coupling efficiency, biostability, cellular cytotoxicity and internalization were tested. Results:In vitro studies showed a high internalization of TNHs into cancer cells and efficient cytotoxic activity thanks to ZnO intracellular release. Conclusion: TNHs represent an efficient biomimetic platform for future nanotheranostic applications, with biomimetic extracellular vesicle-lipid envelope, facilitated ZnO cellular uptake and potential therapeutic implications.

Zinc oxide nanocrystals as a nanoantibiotic and osteoinductive agent.

In this paper we aim to analyse the behaviour of ZnO nanocrystals (ZnO NCs), prepared with a new synthetic approach and not embedded in any composite matrix, for bone implant applications in vitro. In particular, we have developed a novel, fast and reproducible microwave-assisted synthesis, to obtain highly-crystalline, round-shaped ZnO NCs of 20 nm in diameter as an extremely-stable colloidal solution in ethanol. The nanocrystals were also partially chemically functionalized by anchoring amino-propyl groups to the ZnO surface (ZnO-NH2 NCs). Thus, the role of both ZnO NC concentration and surface chemistry were tested in terms of biocompatibility towards pre-osteoblast cells, promotion of cell proliferation and differentiation, and also in terms of antimicrobial activity against Gram positive and negative bacteria, such as Escherichia coli and Staphylococcus aureus, respectively. The results suggest that ZnO-NH2 NCs is the most promising candidate to solve infectious disease in bone implants and at the same time promote bone tissue proliferation, even at high concentrations. Although further investigations are needed to clarify the mechanism underlying the inhibition of biofilm formation and to investigate the role of the ZnO-NH2 NCs in in vivo assays, we demonstrated that fine and reproducible control over the chemical and structural parameters in ZnO nanomaterials can open up new horizons in the use of functionalized ZnO NCs as a highly biocompatible and osteoinductive nanoantibiotic agent for bone tissue engineering.

Sonophotocatalytic degradation mechanisms of Rhodamine B dye via radicals generation by micro- and nano-particles of ZnO.

In this work, it is proposed an environmental friendly sonophotocatalytic approach to efficiently treat polluted waters from industrial dyes exploiting ZnO micro- and nano-materials. For the first time, we deeply investigated the generation of reactive oxygen species (ROS) under ultrasound stimulation of different ZnO structures by Electron Paramagnetic Resonance Spectroscopy (EPR). Indeed, five zinc oxide (ZnO) micro- and nano-structures, i.e. Desert Roses (DRs), Multipods (MPs), Microwires (MWs), Nanoparticles (NPs) and Nanowires (NWs), were studied for the Rhodamine B (RhB) sonodegradation under ultrasonic irradiation. The DRs microparticles demonstrated the best sonocatalytic performance (100% degradation of RhB in 180 min) and the highest OH· radicals generation under ultrasonic irradiation. Strikingly, the coupling of ultrasound and sun-light irradiation in a sonophotodegradation approach led to 100% degradation efficiency, i.e. color reduction, of RhB in just 10 min, revealing a great positive synergy between the photocatalytic and sonocatalytic mechanisms. The RhB sonophotocatalytic degradation was also evaluated at different initial dye concentrations and with the presence of anions in solution. It was demonstrated a good stability over repeated cycles of dye treatment, which probe the applicability of this technique with industrial effluents. In conclusion, sonophotocatalytic degradation synergizing sunlight and ultrasound in the presence of DRs microparticles shows a great potential and a starting point to investigate further the efficient treatment of organic dyes in wastewater.

A Microwave-Assisted Synthesis of Zinc Oxide Nanocrystals Finely Tuned for Biological Applications.

Herein we report a novel, easy, fast and reliable microwave-assisted synthesis procedure for the preparation of colloidal zinc oxide nanocrystals (ZnO NCs) optimized for biological applications. ZnO NCs are also prepared by a conventional solvo-thermal approach and the properties of the two families of NCs are compared and discussed. All of the NCs are fully characterized in terms of morphological analysis, crystalline structure, chemical composition and optical properties, both as pristine nanomaterials or after amino-propyl group functionalization. Compared to the conventional approach, the novel microwave-derived ZnO NCs demonstrate outstanding colloidal stability in ethanol and water with long shelf-life. Furthermore, together with their more uniform size, shape and chemical surface properties, this long-term colloidal stability also contributes to the highly reproducible data in terms of biocompatibility. Actually, a significantly different biological behavior of the microwave-synthesized ZnO NCs is reported with respect to NCs prepared by the conventional synthesis procedure. In particular, consistent cytotoxicity and highly reproducible cell uptake toward KB cancer cells are measured with the use of microwave-synthesized ZnO NCs, in contrast to the non-reproducible and scattered data obtained with the conventionally-synthesized ones. Thus, we demonstrate how the synthetic route and, as a consequence, the control over all the nanomaterial properties are prominent points to be considered when dealing with the biological world for the achievement of reproducible and reliable results, and how the use of commercially-available and under-characterized nanomaterials should be discouraged in this view.

Design, Fabrication, and In Vitro Evaluation of Nanoceria-Loaded Nanostructured Lipid Carriers for the Treatment of Neurological Diseases.

Neurodegenerative diseases comprise a large group of disorders characterized by a dramatic synaptic connections loss, occurring as a result of neurodegeneration, which is closely related to the overproduction of reactive oxygen and nitrogen species. Currently, the treatment of neurodegenerative diseases has been limited mainly because of the inability of the synthesized delivery systems to cross the blood-brain barrier and to successfully deliver their therapeutic cargo to the diseased tissue. Taking into consideration the aforementioned limitations, we designed a lipid-based nanotherapeutic vector composed of biomimetic lipids and CeO2 nanoparticles (nanoceria, NC). NC have shown to be a promising tool for the treatment of several pathological conditions ranging from cancer to neurological diseases, mainly because of their antioxidant properties, while lipid-based structures have been shown to have an inherent ability to cross the blood-brain barrier. The lipid-based nanotherapeutics were successfully fabricated using a combination of ultrasonication and high-pressure homogenization techniques, and they were fully characterized morphologically and physicochemically. Their antioxidant ability was demonstrated using electron paramagnetic resonance spectroscopy and antioxidant assays. These innovative nanotherapeutics demonstrated a higher colloidal stability with respect to free NC, preserving at the same time their antioxidant properties. Finally, the ability of the lipid carriers to cross a model of the blood-brain barrier and to be internalized by neurons, acting both as neuroprotective and pro-neurogenic agents, was demonstrated using single- and triple-culture systems.

Lipid-Coated Zinc Oxide Nanoparticles as Innovative ROS-Generators for Photodynamic Therapy in Cancer Cells.

In the present paper, we use zinc oxide nanoparticles under the excitation of ultraviolet (UV) light for the generation of Reactive Oxygen Species (ROS), with the aim of further using these species for fighting cancer cells in vitro. Owing to the difficulties in obtaining highly dispersed nanoparticles (NPs) in biological media, we propose their coating with a double-lipidic layer and we evaluate their colloidal stability in comparison to the pristine zinc oxide NPs. Then, using Electron Paramagnetic Resonance (EPR) coupled with the spin-trapping technique, we demonstrate and characterize the ability of bare and lipid-coated ZnO NPs to generate ROS in water only when remotely actuated via UV light irradiation. Interestingly, our results reveal that the surface chemistry of the NPs greatly influences the type of photo-generated ROS. Finally, we show that lipid-coated ZnO NPs are effectively internalized inside human epithelial carcinoma cells (HeLa) via a lysosomal pathway and that they can generate ROS inside cancer cells, leading to enhanced cell death. The results are promising for the development of ZnO-based therapeutic systems.

Toward Plastic Smart Windows: Optimization of Indium Tin Oxide Electrodes for the Synthesis of Electrochromic Devices on Polycarbonate Substrates.

Plastic smart windows are becoming one of the key elements in view of the fabrication of inexpensive, lightweight electrochromic (EC) devices to be integrated in the new generation of high-energy-efficiency buildings and automotive applications. However, fabricating electrochromic devices on polymer substrates requires a reduction of process temperature, so in this work we focus on the development of a completely room-temperature deposition process aimed at the preparation of ITO-coated polycarbonate (PC) structures acting as transparent and conductive plastic supports. Without providing any substrate heating or surface activation pretreatments of the polymer, different deposition conditions are used for growing indium tin oxide (ITO) thin films by the radiofrequency magnetron sputtering technique. According to the characterization results, the set of optimal deposition parameters is selected to deposit ITO electrodes having high optical transmittance in the visible range (∼90%) together with low sheet resistance (∼8 ohm/sq). The as-prepared ITO/PC structures are then successfully tested as conductive supports for the fabrication of plastic smart windows. To this purpose, tungsten trioxide thin films are deposited by the reactive sputtering technique on the ITO/PC structures, and the resulting single electrode EC devices are characterized by chronoamperometric experiments and cyclic voltammetry. The fast switching response between colored and bleached states, together with the stability and reversibility of their electrochromic behavior after several cycling tests, are considered to be representative of the high quality of the EC film but especially of the ITO electrode. Indeed, even if no adhesion promoters, additional surface activation pretreatments, or substrate heating were used to promote the mechanical adhesion among the electrode and the PC surface, the observed EC response confirmed that the developed materials can be successfully employed for the fabrication of lightweight and inexpensive plastic EC devices.

Microwave-Assisted Synthesis of Reduced Graphene Oxide/SnO2 Nanocomposite for Oxygen Reduction Reaction in Microbial Fuel Cells.

We report on an easy, fast, eco-friendly, and reliable method for the synthesis of reduced graphene oxide/SnO2 nanocomposite as cathode material for application in microbial fuel cells (MFCs). The material was prepared starting from graphene oxide that has been reduced to graphene during the hydrothermal synthesis of the nanocomposite, carried out in a microwave system. Structural and morphological characterizations evidenced the formation of nanocomposite sheets, with SnO2 crystals of few nanometers integrated in the graphene matrix. Physico-chemical analysis revealed the formation of SnO2 nanoparticles, as well as the functionalization of the graphene by the presence of nitrogen atoms. Electrochemical characterizations put in evidence the ability of such composite to exploit a cocatalysis mechanism for the oxygen reduction reaction, provided by the presence of both SnO2 and nitrogen. In addition, the novel composite catalyst was successfully employed as cathode in seawater-based MFCs, giving electrical performances comparable to those of reference devices employing Pt as catalyst.

UV-Induced Radical Photo-Polymerization: A Smart Tool for Preparing Polymer Electrolyte Membranes for Energy Storage Devices.

In the present work, the preparation and characterization of quasi-solid polymer electrolyte membranes based on methacrylic monomers and oligomers, with the addition of organic plasticizers and lithium salt, are described. Noticeable improvements in the mechanical properties by reinforcement with natural cellulose hand-sheets or nanoscale microfibrillated cellulose fibers are also demonstrated. The ionic conductivity of the various prepared membranes is very high, with average values approaching 10-3 S cm-1 at ambient temperature. The electrochemical stability window is wide (anodic breakdown voltages > 4.5 V vs. Li in all the cases) along with good cyclability in lithium cells at ambient temperature. The galvanostatic cycling tests are conducted by constructing laboratory-scale lithium cells using LiFePO4 as cathode and lithium metal as anode with the selected polymer electrolyte membrane as the electrolyte separator. The results obtained demonstrate that UV induced radical photo-polymerization is a well suited method for an easy and rapid preparation of easy tunable quasi-solid polymer electrolyte membranes for energy storage devices.

The richest collection of tautomeric polymorphs: the case of 2-thiobarbituric acid.

Five new polymorphs and one hydrated form of 2-thiobarbituric acid have been isolated and characterised by solid-state methods. In both the crystalline form II and in the hydrate form, the 2-thiobarbituric molecules are present in the enol form, whereas only the keto isomer is present in crystalline forms I (reported in 1967 by Calas and Martinex), III, V and VI. In form IV, on the other hand, a 50:50 ordered mixture of enol/keto molecules is present. All new forms have been characterised by single-crystal X-ray diffraction, 1D and 2D ((1)H, (13)C, and (15)N) solid-state NMR spectroscopy, Raman spectroscopy and X-ray powder diffraction at variable temperature. It has been possible to induce keto-enol conversion between the forms by mechanical methods. The role of hydrogen-bond interactions in determining the relative stability of the polymorphs and as a driving force in the conversions has been ascertained. To the best of the authors' knowledge, the 2-thiobarbituric family of crystal forms represents the richest collection of examples of tautomeric polymorphism so far reported in the literature.