Amidst an ever-increasing demand for the enhancement of the lifestyle and the modulation of modern diseases, the functionalization of biomaterials is of utmost importance. One of the leading materials for the aforementioned purpose have been calcium phosphates (CaPs). They have been widely used in bone regeneration displaying favourable regenerative potential and biological properties. Many studies have placed their entire focus on facilitating the osteogenic differentiation of stem cells and bone progenitor cells, while the aspect of antibacterial properties has been surmounted. Nevertheless, increasing antibiotic resistance of bacteria requires the development of new materials and the usage of alternative approaches such as ion doping. Gallium (Ga) has been the potential star on the rise among the ions. However, the obstacle that accompanies gallium is the scarcity of research performed and the variety of amalgamations. The question that imposes itself is how a growing field of therapeutics can be further entwined with advances in material science, and how will the incorporation of gallium bring a new outlook. The present study offers a comprehensive overview of state-of-the-art gallium containing calcium phosphates (GaCaPs), their synthesis methods, antibacterial properties, and biocompatibility. Considering their vast potential as antibacterial agents, the need for a methodical perspective is highly necessary to determine if it is a direction on the brink of recognition or a fruitless endeavour. STATEMENT OF SIGNIFICANCE: Although several studies have been published on various metal ions-containing calcium phosphates, to this date there is no systematic overview pointing out the properties and benefits of gallium containing calcium phosphates. Here we offer a critical overview, including synthesis, structure and biological properties of gallium containing calcium phosphates.

Calcium phosphates (CaPs) have been used in bone regeneration for decades. Among the described CaPs, synthetic hydroxyapatite (HAp) has a chemical composition similar to that of natural bone. Gallium-containing compounds have been studied since the 1970s for the treatment of autoimmune diseases and have shown beneficial properties, such as antibacterial activity and inhibition of osteoclast activity. In this study, we synthesized hydroxyapatite (HAp) powder with Ga doping ratios up to 6.9 ± 0.5 wt% using the wet chemical precipitation method. The obtained products were characterized using XRD, BET, FTIR, and ICP-MS. Ga³⁺ ion release was determined in the cell culture media for up to 30 days. Antibacterial activity was assessed against five bacterial species: Pseudomonas aeruginosa, Escherichia coli, Staphylococcus aureus, Staphylococcus epidermidis, and Streptococcus pyogenes. The biocompatibility of the GaHAp samples was determined in human fibroblasts (hTERT-BJ1) through direct and indirect tests. The structure of the synthesized products was characteristic of HAp, as revealed with XRD and FTIR, although the addition of Ga caused a decrease in the crystallite size. Ga³⁺ was released from GaHAp paste in a steady manner, with approximately 40% being released within 21 days. GaHAp with the highest gallium contents, 5.5 ± 0.1 wt% and 6.9 ± 0.5 wt%, inhibited the growth of all five bacterial species, with the greatest activity being against Pseudomonas aeruginosa. Biocompatibility assays showed maintained cell viability (~80%) after seven days of indirect exposure to GaHAp. However, when GaHAp with Ga content above 3.3 ± 0.4 wt% was directly applied on the cells, a decrease in metabolic activity was observed on the seventh day. Overall, these results show that GaHAp with Ga content below 3.3 ± 0.4 wt% has attractive antimicrobial properties, without affecting the cell metabolic activity, creating a material that could be used for bone regeneration and prevention of infection.

Among the various methods for collecting oil spills and oil products, including from the water surface, one of the most effective is the use of sorbents. In this work, three-component bio-based composite granular adsorbents were produced and studied for oil products’ pollution collection. A bio-based binder made of peat, devulcanised crumb rubber from used tyres, and part fly ash as cenospheres were used for absorbent production. The structure, surface morphology, porosity, mechanical properties, and sorption kinetics of the obtained samples were studied. Composite hydrophobicity and sorption capacity to oil products, such as diesel fuel (DF) and motor oil (MO), were determined. The obtained pellets are characterised by a sufficiently pronounced ability to absorb oil products such as DF. As the amount of CR in the granules increases, the diesel absorption capacity increases significantly. The case of 30-70-0 is almost three times higher than the granules from homogenised peat. The increase in q is due to two factors: the pronounced surface hydrophobicity of the samples (Θ = 152°) and a heterogeneous porous granule structure. The presence of the cenosphere in the biocomposite reduces its surface hydrophobicity while increasing the diesel absorption capacity. Relatively rapid realisation of the maximum saturation by the MO was noted. In common, the designed absorbent shows up to 0.7 g·g⁻¹ sorption capacity for MO and up to 1.55 g·g⁻¹ sorption capacity for diesel. A possible mechanism of DF absorption and the limiting stages of the process approximated for different kinetic models are discussed. The Weber–Morris diffusion model is used to primarily distinguish the limiting effect of the external and internal diffusion of the adsorbate on the absorption process.

Among the various methods for collecting oil spills and oil products, including from the water surface, one of the most effective is the use of sorbents. In this work, three-component bio-based composite granular adsorbents were produced and studied for oil products pollution collection. A bio-based binder made of peat, devulcanised crumb rubber from used tyres, and part fly ash as cenospheres were used for absorbent production. The structure, surface morphology, porosity, mechanical properties, and sorption kinetics of the obtained samples were studied. Composite hydrophobicity and sorption capacity to oil products such as diesel fuel (DF) and motor oil (MO) were determined. The obtained pellets are characterised by a sufficiently pronounced ability to absorb oil products such as DF. As the amount of CR in the granules increases, the diesel absorption capacity increases significantly. The case of 30-70-0 is almost 3 times higher than the granules from homogenised peat. The increase in q is due to two factors: pronounced surface hydrophobicity of the samples (Θ = 152°) and a heterogeneous porous granule structure. The presence of the cenosphere in the biocomposite reduces its surface hydrophobicity while increasing the diesel absorption capacity. Relatively rapid realisation of the maximum saturation by the MO was noted. In common, the designed absorbent shows up to 0.7 g·g^-1 sorption capacity for MO and up to 1.55 g·g^-1 sorption capacity for diesel. A possible mechanism of DF absorption and the limiting stages of the process approximated for different kinetic models are discussed. The Weber-Morris diffusion model is used to primarily distinguish the limiting effect of external and internal diffusion of adsorbate on the absorption process

Promocijas darbā sintezēti galliju saturoši hidroksilapatīta (HAp) un amorfā kalcija fosfāta (ACP) materiāli, raksturotas abu materiālu fizikāli ķīmiskās īpašības un novērtēta to antibakteriālā aktivitāte pret Staphylococcus aureus un Escherichia coli baktērijām. Papildus analizēta gallija ietekme uz ACP termisko stabilitāti un stabilitāti dažāda sastāva ūdens vidē. Darba izstrādes gaitā pētīta arī GaHAp keramika, kas iegūta augsttemperatūras saķepināšanas rezultātā. Augsttemperatūrā apstrādātiem paraugiem izvērtēta gallija ietekme uz hidroksilapatīta struktūru un analizētas teorētiski iespējamās gallija aizvietošanās vietas kristālrežģī, izmantojot Profex programmatūru.