Jose Manuel Delgado López

University of Granada | UGR · Department of Inorganic Chemistry

In the last years, biomimetic synthetic apatite nanoparticles (AP-NPs), having chemical similarity with the mineral phase of bone, have attracted a great interest in nanomedicine as potential drug carriers. To evaluate the therapeutic perspectives of AP-NPs through the mechanisms of action and organs they interact with, the non-invasive monitoring...

Monohydrocalcite (CaCO3·H2O) has been crystallized in silica-rich alkaline water solution. The crystallization proceeds by a counterdiffusion method without the presence of any other additive except dissolved silica. The crystallization has been followed in situ by optical microscopy and Raman microspectroscopy, while the time evolution of the pH a...

Newly-formed Fe terrace samples and corresponding water samples of Tinto and Odiel River, as well as, ancient terrace samples representing conditions of ancient Tinto River, were collected and studied by optical microscopy, Raman spectroscopy, X-ray diffraction, scanning electron microscopy, microprobe analysis, pseudo-total digestions, and by chem...

Multifunctional biomimetic nanoparticles (NPs) are acquiring increasing interest as carriers in medicine and basic research since they can efficiently combine labels for subsequent tracking, moieties for specific cell targeting, and bioactive molecules, e.g., drugs. In particular, because of their easy synthesis, low cost, good biocompatibility, hi...

BACKGROUND Viticulture has adapted foliar applications of biostimulants as a tool to improve crop quality. Recently, nanotechnology has been incorporated as a strategy to reduce the loss of biostimulants and treat nutrient deficiencies. Therefore, the present study aimed to investigate the effect of foliar applications of amorphous calcium phosphat...

Herein, a novel luminescent platform has been designed via in-situ mineralization of microfluidic paper-based analytical devices (µPAD) made of cellulose in the presence of Tb3+. Cellulose nanofibers were homogenously mineralized...

Background Elicitors induce defense mechanisms, triggering the synthesis of secondary metabolites. Irrigation has implications for a more sustainable viticulture and for grape composition. The aim was to investigate the influence on grape aroma composition during 2019 and 2020 of the foliar application of amorphous calcium phosphate (ACP) nanoparti...

Calcium phosphate nanoparticles were doped with zinc ions to produce multifunctional nanomaterials for efficient agronomic fortification and protection of plants. The resulting round-shaped nanoparticles (nanoZn) were composed of 20.3 wt % Ca, 14.8 wt % P, and 13.4 wt % Zn and showed a pH-controlled solubility. NanoZn were stable in aqueous solutio...

Introduction Pancreatic cancer (PC) shows a very poor response to current treatments. Development of drug resistance is one of the causes of the therapy failure, being PARP1 (poly ADP-ribose polymerase 1) a relevant protein in the resistance mechanism. In this work, we have functionalized calcium phosphate-based nanoparticles (NPs) with Olaparib (O...

In this work, Engineered Living Materials (ELMs), based on the combination of genetically-modified bacteria and mineral-reinforced organic matrices, and endowed with self-healing or regenerative properties and adaptation to specific biological environments were developed. Concretely, we produced ELMs combining human mesenchymal stem cells (hMSCs) a...

In recent years, foliar application of elicitors to the vineyard has been increasingly used, in particular, elicitation with methyl jasmonate (MeJ). However, due to the high cost of this compound, it is necessary to find a form of application in which the amount to be used is considerably reduced. Therefore, the aim of this work was study for the f...

Nanoparticles are emerging as a cutting-edge technology to improve crop agricultural input efficiency and reduce biotic and abiotic stresses. In viticulture, nanoparticles hold promise for the sustainable application of an elicitor (methyl jasmonate, MeJ), allowing a considerable dosage reduction. Herein, the influence of the foliar application of...

The structural composition of the cell wall of grape skins is related to the cell wall integrity and subsequent extraction of the different compounds that are contained inside vacuoles and also the cell wall breakdown products. Different reports have established that methyl jasmonate (MeJ) produces changes in the composition of the grape skin cell...

The effect produced by the application of methyl jasmonate (MeJA) in vineyards is clear, but this is a product that, despite its efficiency, is expensive, volatile and difficult to dissolve. Regarding increasing the MeJA use efficiency, new forms of application are proposed in this article, such as the use of calcium phosphate nanoparticles with tw...

Nanotechnology is emerging as a potential strategy to achieve sustainable agricultural productivity and global food security. Engineered nanoparticles (NPs) are endowed with the ability to deliver active ingredients in a...

Probiotic cellulose (PC), a living material (LM) consisting of probiotics integrated into bacterial cellulose, is the first example where life (probiotic proliferation) is the input to tune the viscoelasticity of the biomaterial. The gradual proliferation of probiotics within the matrix acts as a key modulator of the cellulose viscoelasticity, prov...

Due to the fast, emerging development of antibiotic-resistant bacteria, the need for novel, efficient routes to battle these pathogens is crucial; in this scenario, metal-organic frameworks (MOFs) are promising materials for combating them effectively. Herein, a novel Cu-MOF—namely 1—that displays the formula [Cu3L2(DMF)2]n (DMF = N,N-dimethylforma...

Amorphous calcium phosphate nanoparticles (ACP NPs) exhibit excellent biocompatibility and biodegradability properties. ACP NPs were functionalized with two coumarin compounds (esculetin and euphorbetin) extracted from Euphorbia lathyris seeds (BC-ACP NPs) showing high loading capacity (0.03% and 0.34% (w/w) for esculetin and euphorbetin, respectiv...

The phenolic, aromatic and nitrogen composition of a wine determines its organoleptic profile and quality. Elicitors have been used as a tool to stimulate the plant’s defense systems, favoring the synthesis of secondary metabolites. In this pioneering study, the elicitor methyl jasmonate in conventional form (MeJ) and in nanoparticle form (ACP-MeJ)...

Tools to address the mismatch between technological and phenolic maturity of grapes are needed. Application of elicitors could be an effective alternative. This work compares the effect of the application of methyl jasmonate (MeJ) in conventional form and, as a novelty, in the form of MeJ-doped nanoparticles (ACP-MeJ) on the phenolic composition of...

The application of methyl jasmonate (MeJ) as an elicitor to enhance secondary metabolites in grapes and wines has been studied, but there is little information about its use in conjunction with nanotechnology and no information about its effects on wine volatile compounds. This led us to study the impact of nanoparticles doped with MeJ (Nano-MeJ, 1...

In viticulture, the application of elicitors to the grapevines is increasing although their effect on the amino acids content is little studied. In this work, nanoparticles of methyl jasmonate (Ap-MeJ) were applied for the first time to Monastrell grapevines during two seasons (2019 and 2020) to increase its profitability and nitrogen plant uptake...

Probiotic bacteria were used as carriers of metallic nanoparticles to develop innovative oral agents for hyperthermia cancer therapy. Two synthetic strategies were used to produce the different therapeutic agents. First, the probiotic bacterium Lactobacillus fermentum was simultaneously loaded with magnetic (MNPs) and gold nanoparticles (AuNPs) of...

Self-assembled peptides and proteins have turned out to be excellent templates for the growth of inorganic minerals trying to emulate natural biomineralization processes. Doing this, researchers have developed complex sophisticate...

Organic-inorganic composite materials with tailoured properties can be designed in the lab through bio-inspired approaches. In this context, we exploited the particle-based crystallisation process of calcium sulfate, a technologically important...

Methyl jasmonate (MeJ), an elicitor able to trigger plant defence responses, is a natural and clean alternative to the use of hazardous pesticides. However, the efficient application of MeJ in fields is very limited due to its poor water solubility, thermal stability and phytotoxicity at the high dose required to produce beneficial effects in plant...

Nitrogen composition on grapevines has a direct effect on the quality of wines since it contributes to develop certain volatile compounds and assists in the correct kinetics of alcoholic fermentation. Several strategies can be used to ensure nitrogen content in grapes and one of them could be the use of elicitors such as methyl jasmonate. The use o...

In recent years, the application of nanotechnology for the development of new “smart fertilizers” is regarded as one of the most promising solutions for boosting a more sustainable and modern grapevine cultivation. Despite showing interesting potential benefits over conventional fertilization practices, the use of nanofertilizers in viticulture is...

The constant increase of antibiotic-resistant bacteria demands the design of novel antibiotic-free materials. The combination of antibacterials in a biocompatible biomaterial is a very promising strategy to treat infections caused by a broader spectrum of resistant pathogens. Here, we combined two antibacterials, silver nanoparticles (AgNPs) and li...

Two new coordination polymers (CPs) based on Zn(II) and Cd(II) and 1H-indazole-6-carboxylic acid (H2L) of general formulae [Zn(L)(H2O)]n (1) and [Cd2(HL)4]n (2) have been synthesized and fully characterized by elemental analyses, Fourier transformed infrared spectroscopy and single crystal X-ray diffraction. The results indicate that compound 1 pos...

Nanosized fertilizers are the new frontier of nanotechnology towards a sustainable agriculture. Here, an efficient N-nanofertilizer is obtained by post-synthetic modification (PSM) of nitrate-doped amorphous calcium phosphate (ACP) nanoparticles (NPs) with urea. The unwasteful PSM protocol leads to N-payloads as large as 8.1 w/w%, is well replicate...

In bone tissue engineering, the design of 3D systems capable of recreating composition, architecture and micromechanical environment of the native extracellular matrix (ECM) is still a challenge. While perfusion bioreactors have been proposed as potential tool to apply biomechanical stimuli, its use has been limited to a low number of biomaterials....

The alarming increase of antibiotic-resistant bacteria, causing conventional treatments of bacterial infections to become increasingly inefficient, is one of the biggest threats to global health. Here, we have developed probiotic cellulose, an antibiotic-free biomaterial for the treatment of severe skin infections and chronic wounds. This composite...

BACKGROUND The use of nanomaterials for the efficient delivery of active species in viticulture is still an unexplored opportunity. Nitrogen, an essential nutrient for grapevine development and wine quality, is commonly provided in the form of urea. However, the application of conventional fertilisers contributes to nitrate leaching and denitrifica...

The determination of creatinine levels is essential for the detection of renal and muscular dysfunction. Luminescent nanoparticles are emerging as fast, cheap and highly selective sensors for the detection and quantification of creatinine. Nevertheless, current nanosensors only have a short shelf life due to their poor chemical and colloidal stabil...

Bio-inspired synthetic calcium phosphate (CaP) nanoparticles (NPs), mimicking the mineral component of bone and teeth, are emergent materials for sustainable applications in agriculture. These sparingly soluble salts show self-inhibiting dissolution processes in undersaturated aqueous media, the control at the molecular and nanoscale levels of whic...

We report the formation of five novel multifunctional coordination polymers based on 1H-Indazole-4-carboxylic acid (HL). To the best of our knowledge, these complexes are the first examples of coordination compounds construct with this novel ligand. These materials were synthesized by soft solvothermal routes, possess different 2D-structures and sh...

Nanotechnology is emerging as a very promising tool towards more efficient and sustainable practices in agriculture. In this work, we propose the use of non-toxic calcium phosphate nanoparticles doped with urea (U-ACP) for the fertilization of Triticum durum plants. U-ACP nanoparticles present very similar morphology, structure, and composition tha...

A new concept of biomaterials for antibiotic‐free therapy of bacterial vaginosis (BV) is here proposed. These biomaterials are obtained by entrapping two probiotic biofilms, viz., Lactobacillus fermentum (Lf) and Lactobacillus acidophilus (La) into scaffolds of self‐assembled collagen fibers (col). An in‐depth characterization and viability assays...

We report on the formation of two novel multifunctional isomorphous (4,4) square-grid 2D coordination polymers based on 1H-indazole-5-carboxylic acid. To the best of our knowledge, these complexes are the first examples of 2D-coordination polymers constructed with this novel ligand. We have analysed in detail the structural, magnetic and anti-paras...

The occurrence of an amorphous calcium phosphate layer covering the crystalline apatite core has been suggested to be an intrinsic feature of both bone mineral and synthetic biomimetic analogs. However, an exahustive quantitative picture of the amorphous-crystalline relationship in these materials is still missing. Here, we present a multiple scale...

We report on the formation of two novel multifunctional isomorphous (4,4) square-grid 2D coordination polymers based on 1H-indazole-5-carboxylic acid. To the best of our knowledge, these complexes are the first examples of 2D-coordination polymers constructed with this novel ligand. We have analysed in detail the structural, magnetic and anti-paras...

Citrate and fluoride ions are two constituents of dental enamel hydroxyapatite (HA) nanocrystals. Their individual effect on HA crystallization was already studied, and it was proven that both citrate and fluoride ions regulate HA crystal growth. However, the combined effect of citrate and fluoride ions on HA nanocrystals has never been reported so...

https://pubs.acs.org/toc/aabmcb/3/3

Biomimetic calcium phosphate nanoparticles (CaP) have been actively used in biomedicine, due to their high biodegradability and biocompatibility. However, much less progress has been made regarding its application in precision agriculture, i.e., for the controlled delivery of active species to plants. Herein we report a straightforward and green sy...

Inside cover of the article: Atmospheric water triggers supramolecular gel formation of novel low molecular weight maslinic and oleanolic triterpenic derivatives

Pentacyclic triterpenes have a rigid lypophilic backbone decorated with polar functional groups such as hydroxyl, carbonyl and carboxyl, which make them attractive natural amphiphiles. The ability of this type of compounds to self-assemble into complex nanostructures has recently gained interest due in part to the abundant existing renewable feedst...

The formation of oriented enamel-like fluoride doped hydroxyapatite (HA) nanorods on amorphous calcium phosphate (ACP) substrates in a bare form and containing citrate is compared. It is found that the presence of citrate, delays the conversion into un-oriented HA that in turn affects the overgrowth of nanorods as well as their shape and surface fe...

The incidence of bone disorders and orthopedic surgeries are increasing worldwide representing a premier clinical need. The serious limitation in conventional therapies has led to a new discipline, the so-called bone tissue engineering (BTE), which aims to explore novel functional regeneration strategies via the synergistic combination of biomateri...

Novel reinforced cross‐linked lysozyme crystals containing homogeneous dispersions of single‐walled carbon nanotubes bundles (SWCNTs) are produced and characterized. The incorporation of SWCNTs inside lysozyme crystals gives rise to reinforced composite materials with tunable mechanical strength and electronic conductivity, while preserving the cry...

The fragility of protein crystals plays an important role in the final quality of the diffraction data and therefore that of the derived three-dimensional structural model. The growth of protein crystals in gels of various natures has been shown to overcome this problem, facilitating the manipulation of the crystals; this is probably owing, amongst...

Lysozyme crystals obtained in silica gel (dark part of the crystal schematized as linked spheres) regrown from fresh solution [Gavira et al. (2018), Acta Cryst. D74, 1200-1207]. A microscopic photo of the crystal (insert) is shown here with transmitted polarized light. Reinforced gel-grown protein crystals can be a good strategy for the production...

Abstract Demineralization of dental hard tissue is a widespread problem and the main responsible for dental caries and dentin hypersensitivity. The most promising strategies to induce the precipitation of new mineral phase are the application of materials releasing gradually Ca2+ and PO4 3− ions or mimicking the mineral phase of the host tissue. Ho...

Living organisms are able to induce and control the nucleation and crystallization of a wide variety of minerals. Vertebrates use calcium phosphates to build their mineral phases in hard tissues (i.e. bone, dentin and tooth enamel) and in pathological deposits (e.g. dental and urinary calculus and stones, atherosclerotic lesions). Understanding how...

The surface structure and hydrophilicity of synthetic nanocrystalline apatite with strongly bound citrates on their surface are here investigated at the molecular level, by combining advanced IR spectroscopy, microgravimetry and adsorption microcalorimetry. Citrate are found to form unidentate-like and ionic-like complexes with surface Ca²⁺ ions, w...

Here we report the synthesis and structural characterization of novel iron nanoparticles (FeNPs)-based short-peptide supramolecular hydrogels. These hybrid hydrogels composed of Fmoc-diphenylalanine (Fmoc-FF) peptide and FeNPs were prepared through the self-assembly of Fmoc-FF in a suspension containing FeNPs in the presence or absence of an extern...

Statement of significance: Citrate is an important component of the bone organic matrix but its specific role in bone mineralization is presently unclear. In this work, bioinspired in vitro collagen mineralization experiments in the presence of citrate have been carried out and the combined role of collagen and citrate in controlling mineral forma...

This work explores the mechanisms underlying the crystallization of citrate-functionalized amorphous calcium phosphate (cit-ACP) in two relevant media, combining in situ and ex situ characterization techniques. Results demonstrate that citrate desorption from cit-ACP triggers the surface-mediated transformation to nanocrystalline apatite (Ap). Our...

Understanding the mineralization mechanism of synthetic protein has recently aroused great interest especially in the development of advanced materials for bone regeneration. Herein, we propose the synthesis of composite materials through the mineralization of a recombinant collagen type I derived protein (RCP) enriched with RGD sequences in the pr...

Bioinspired citrate-carbonate-apatite (cAp) nanocrystals doped with divalent transition metal (M) ions, i.e., Mn2+, Co2+, and Ni2+, were prepared by batch thermal decomplexing of Ca2+/M/citrate/phosphate/carbonate solutions at 80 and 37°C, with initial Ca2+/M molar ratios of 9:1 and 5:5, and at different crystallization times ranging from 1 to 96 h...

Here we report that citrate plays a key dual role in the apatite crystallization: driving a growth pathway via an amorphous precursor and controlling the size of nanocrystals by the non-classical oriented aggregation mechanism. These results provide new insights in bone mineralization, where the role of citrate might be wider than has been thought...

Nanocrystalline apatites constitute the main inorganic part of human hard tissues (bone and teeth), and a growing focus is devoted to prepare synthetic analogs, so-called "biomimetic", able to precisely mimic the morphological and physical-chemical features of biological apatites. In fact, it is reasonable to hypothesize that by virtue of their hig...

Nanocrystalline nonstoichiometric apatites constitute the mineral part of bones, and synthetic approaches have been developed to prepare "biomimetic analogs" via "soft" chemical routes. These compounds exhibit many differences to stoichiometric hydroxyapatite, in that they are nanocrystalline, hydrated, nonstoichiometric, plate-like shaped, and the...

Nano-Sized drug carriers conjugated with moieties specifically targeting tumor cells are a promising tool in oncology, improving anticancer drug pharmacodynamic and pharmacokinetics, therapeutic index and reducing adverse side effects. Due to their high biocompatibility, physical properties, low cost and easy synthesis, nanocrystalline apatite appe...

A novel methodology for the assembly of collagen fibrils in microliter drops is proposed. It consists in the gradual increase of pH by means of vapour diffusion coming from the decomposition of NH4HCO3 solutions. The pH increase rate as well as the final steady pH of solutions containing collagen can be adjusted by varying the concentration of NH4H...

Bio-inspired apatite nanoparticles precipitated in the presence of citrate ions at increasing maturation times are characterized in terms of structure, size, morphology, and composition through advanced X-ray total scattering techniques. The origin of the platy crystal morphology, breaking the hexagonal symmetry, and the role of citrate ions is exp...

Nanocrystalline apatite platelets, the mineral component of bone, form from an amorphous precursor through a complex biomineralization process. Here, A. Guagliardi and co-workers use citrate-bio-inspired apatites as a system model and, by cross-coupling the results on crystal domains provided by X-ray total scattering modeling with atomic force mic...

Calcium carbonate precipitation at different values of the nominal ionic activity product (IAP) is studied in nanoliter and picoliter droplets at (20 +/- 2 degrees C). Experiments are carried out through direct mixing of equimolar reactant solutions using two different setups: first, droplet-based microfluidics using Teflon capillaries (nanoliter e...

Nanosized drug carriers functionalized with moieties specifically targeting tumor cells are promising tools in cancer therapy, due to their ability to circulate in the bloodstream for longer periods and their selectivity for tumor cells, enabling the sparing of healthy tissues. Because of its biocompatibility, high bioresorbability, and responsiven...

Superparamagnetic iron-substituted hydroxyapatite nanocrystals (FeHA) were used as a particulate emulsifier for the preparation of hybrid polymeric–inorganic materials by Pickering emulsion. As result, magnetic hollow micro-nanospheres (ranging from 2 μm to 500 nm) made of a polymeric shell of poly(l-lactic) acid coated with FeHA have been prepared...

Monohydrocalcite was crystallized in silica-rich alkaline solutions at room temperature using the counter diffusion method (CDM) in the absence of magnesium, by the reaction of calcium chloride and sodium carbonate. Field-emission scanning microscopy observations showed monohydrocalcite crystals with hundreds of micrometers in size exhibiting a uni...

In this work, the efficiency of bioinspired citrate-functionalized nanocrystalline apatites as nanocarriers for delivery of doxorubicin (DOXO) has been assessed. The nanoparticles were synthesized by thermal decomplexing of metastable Ca/citrate/phosphate/ solutions both in the absence (Ap) and in the presence (cAp) of carbonate ions. The presence...

In this paper the crystallization of a bioinspired citrate-functionalized apatite (cit-Ap) thin film (thickness about 2μm) on Ti-6Al-4V supports pre-coated with bioactive and corrosion resistant buffer layer of silicon nitride (Si3N4), silicon carbide (SiC) or titanium nitride (TiN) is reported. The apatitic coatings were produced by a new coating...

The time-evolution of calcium phosphate precipitation by vapor diffusion has been studied by in situ confocal Raman microspectroscopy. A hanging drop configuration within a device known as "crystallization mushroom" was employed in order to improve the Raman signal coming from growing crystals. This innovative methodology allowed to identify and fo...

This chapter describes some of the most important spectroscopic methods to study the materials surface. Special IR and Raman configurations providing information from the surface will be reviewed highlighting the main advantages and/or drawbacks for their applications in the study of biomaterials. Additionally, some examples are presented to demons...

In this paper, hybrid inorganic-organic core-shell hollow microspheres, made of poly(L: -lactic acid) (PLLA) and biomimetic nano apatites (HA), were prepared from biodegradable and biocompatible substances, suitable for bone tissue applications. Preparation is started from Pickering emulsification, i.e., solid particle-stabilized emulsions in the a...

Novel citrate-functionalized carbonate-apatite nanoparticles with mean lengths ranging from 20 to 100 nm were synthesized by a thermal-decomplexing batch method. Needle-like and plate-shaped morphologies were obtained in the absence and presence of sodium carbonate in the precipitation medium, respectively. The precipitation time and the presence o...

Calcium phosphate precipitation was carried out in the presence of l-aspartic acid (l-asp, iep = 2.77), l-alanine (l-ala, iep = 6.00), and l-arginine (l-arg, iep = 10.76) at different concentrations by using a vapor diffusion sitting drop method (VDSD) in microdroplets. Irrespective of the nature and the concentration of the amino acid used, the ea...

In this work we have used the sitting drop vapour diffusion technique, employing the “crystallization mushroom ” to analyze the evolution of calcium phosphate crystallization in micro-droplets containing high initial concentrations of Ca2+ and HPO42-. The decomposition of NH4HCO3 solution produces vapours of NH3 and CO2 which diffuse through the dr...