From Classical to Advanced Use of Polymers in Food and Beverage Applications

Polymers are extensively used in food and beverage packaging to shield against contaminants and external damage due to their barrier properties, protecting the goods inside and reducing waste. However, current trends in polymers for food, water, and beverage applications are moving forward into the design and preparation of advanced polymers, which can act as active packaging, bearing active ingredients in their formulation, or controlling the head-space composition to extend the shelf-life of the goods inside. In addition, polymers can serve as sensory polymers to detect and indicate the presence of target species, including contaminants of food quality indicators, or even to remove or separate target species for later quantification. Polymers are nowadays essential materials for both food safety and the extension of food shelf-life, which are key goals of the food industry, and the irruption of smart materials is opening new opportunities for going even further in these goals. This review describes the state of the art following the last 10 years of research within the field of food and beverage polymer’s applications, covering present applications, perspectives, and concerns related to waste generation and the circular economy.This work was supported by the Regional Government of Castilla y León (Junta de Castilla y León) and by the Ministry of Science and Innovation MICIN and the European Union NextGeneration EU PRTR. The project leading to these results has received funding from “La Caixa” Foundation, under the agreement LCF/PR/PR18/51130007. We also gratefully acknowledge the grant PID2020-113264RB-I00 funded by MCIN/AEI/10.13039/501100011033 and by “ERDF A way of making Europe”. Finally, we want to acknowledge the funding from Ministerio de UniversidadesEuropean Union in the frame of NextGenerationEU RD 289/2021 (Universidad Politécnica de Madrid and Universidad Autónoma de Madrid-CA1/RSUE/2021-00409)

Polymer films containing chemically anchored diazonium salts with long-term stability as colorimetric sensors

We have prepared polymeric films as easy-to-handle sensory materials for the colorimetric detection and quantification of phenol derivatives (phenols) in water. Phenols in water resources result from their presence in pesticides and fungicides, among other goods, and are harmful ecotoxins. Colorless polymeric films with pendant diazonium groups attached to the acrylic polymer structure were designed and prepared for use as sensory matrices to detect phenol-derived species in water. Upon dipping the sensory films into aqueous media, the material swells, and if phenols are present, they react with the diazonium groups of the polymer to render a highly colored azo group, giving rise to the recognition phenomenon. The color development can be visually followed for a qualitative determination of phenols. Additionally, quantitative analysis can be performed by two different techniques: a) by using a UV–vis spectrophotometer (limit of detection of 0.12 ppm for 2-phenylphenol) and/or b) by using a smartphone with subsequent RGB analysis (limit of detection of 30 ppb for 2-phenylphenol)Fondo Europeo de Desarrollo Regional (FEDER) and the Spanish Agencia Estatal de Investigación (AEI) (MAT2017-84501-R

Segmented-block poly(ether amide)s containing flexible polydisperse polyethyleneoxide sequences and rigid aromatic amide moieties

We describe the synthesis and characterization of three novel aromatic diamines containing oxyethylene sequences of different lengths. These diamines were polymerized using the low-temperature solution polycondensation method with isophthaloyl chloride (IPC), terepthaloyl chloride (TPC), [1,1’-biphenyl]-4,4’-dicarbonyl dichloride (BDC), and 4,4′-oxybis(benzoyl chloride) (OBE), obtaining twelve poly(ether amide)s with short segments of polydisperse polyethyleneoxide (PEO) sequences in the polymer backbone. These polymers show reasonably high molecular mass materials (Mw > 12,000), and the relationship between their structure and properties has been carefully studied. Compared with conventional polyamides containing monodisperse PEO sequences, the polydispersity of the PEO segments within the structural units exerts a significant influence on the crystallinity, flexibility, solubility, and the thermal properties of the polymers. For instance, the all-para oriented polyamides (TPCP-A), with an average number of 8.2 ethylenoxide units per structural unit can be transformed conventionally (Tm = 259 °C) in comparison with thermally untransformable polymer with 2 ethylenoxide units (Tm = 425 °C)FEDER (Fondo Europeo de Desarrollo Regional), the Spanish Agencia Estatal de Investigación (PID2020-113264RB-I00/AEI/10.13039/501100011033) and (PID2019-108583RJ-I00/AEI/ 10.13039/501100011033), and the Consejería de Educación—Junta de Castilla y León (BU306P1

Why is the Sensory Response of Organic Probes within a Polymer Film Different in Solution and in the Solid-State? Evidence and Application to the Detection of Amino Acids in Human Chronic Wounds

We anchored a colourimetric probe, comprising a complex containing copper (Cu(II)) and a dye, to a polymer matrix obtaining film‐shaped chemosensors with induced selectivity toward glycine. This sensory material is exploited in the selectivity detection of glycine in complex mixtures of amino acids mimicking elastin, collagen and epidermis, and also in following the protease activity in a beefsteak and chronic human wounds. We use the term inducing because the probe in solution is not selective toward any amino acid and we get selectivity toward glycine using the solid‐state. Overall, we found that the chemical behaviour of a chemical probe can be entirely changed by changing its chemical environment. Regarding its behaviour in solution, this change has been achieved by isolating the probe by anchoring the motifs in a polymer matrix, in an amorphous state, avoiding the interaction of one sensory motif with another. Moreover, this selectivity change can be further tuned because of the effectiveness of the transport of targets both by the physical nature of the interface of the polymer matrix/solution, where the target chemicals are dissolved, for instance, and inside the matrix where the recognition takes place. The interest in chronic human wounds is related to the fact that our methods are rapid and inexpensive, and also considering that the protease activity can correlate with the evolution of chronic wounds.FEDER (Fondo Europeo de Desarrollo Regional), and both the Spanish Ministerio de Economía, Industria y Competitividad (MAT2017‐84501‐R) and the Consejería de Educación—Junta de Castilla y León (BU061U16

Del aprendizaje por competencias a la evaluación formativa de su adquisición: metodología y materiales

Ponencia presentada en: VI Jornadas de Innovación Docente de la UBU, Burgos, 23 y 24 de febrero de 2012, organizadas por el Instituto de Formación e Innovación Educativa-IFIE de la Universidad de Burgo

Versatile applications of water soluble Gold complexes

Resumen del trabajo presentado a la II Conferencia Internacional sobre Complejos Metálicos Solubles en Agua: Metales y Agua, celebrada en Jaca, Huesca (España) del 13 al 15 de junio de 2017.The ability of the different water soluble phosphanes, as 1,3,5-triaza-7-phosphadaamante (PTA), some of its derivatives as DAPTA, and mono- di- and tri-sulfonate triphenylphospane (TPPMS, TPPDS, and TPPTS) to trasmit their water solubility to the corresponding gold complexes has permited the synthesis of compounds that found applications in a wide of different areas: new pigments in designed tiles, as new drugs on different molecular therapy and recyclable catalyst precursor to operate in water. In this commmunication we present results of our group. The use of ploter for the new type of ceramics requires the shynthesis of new inks able to develop the colors in the oven at high temperature. The gold complexes are selected for the formation of magenta red color. The new ink should be soluble in water of at least in alcholic media for enviromental aspects. The water solubility of the new gold complexes made them suitable to dissolve in the blood serum and, therefore, be effective as new agents of molecular therapy eg as anticancer drugs. We present results against different types of cancer cells, both in vitro and in vivo. Among the new non platinum complexes as potential anticancer drug, gold(I) derivatives have gained increasing attention due to the observation that the action mechanism is different to the cis-platinum and non interaction with DNA occurs, and inhibit the enzyme thioredoxin reductasa, (TrxR), making these complexes very appropriate for a second treatment against cis-platinum resistance cancer. Some synergic effect with other cancer drug as 5-flluorouracile is presented. Again the water solubility of some of these complexes or palladium derivatives could be of interest as catalyst precursors for different C-C coupling reactions in water. Apart of the interest for using water as solvent, they permits in many case one important recovery and recycle of the catalyst. The use of other water soluble phosphanes and new thiolate funtionalized to improve their solubility in this media is presented.Peer reviewe

Pyridine-2-thionate as a versatile ligand in Pd(II) and Pt(II) chemistry: the presence of three different co-ordination modes in [Pd2(µ2-S,N-C5H4SN)(µ2-2S-C5H4SN)(µ2-dppm)(S-C5H4SN)2]

8 pages, 5 tables, 4 figures, 1 scheme.-- First published as an Advance Article on the web 28th Oct. 2005.Reactions of [MCl2(L–L)], M = Pt, Pd; L–L = bis(diphenylphosphino)methane (dppm) or bis(diphenylphosphino)ethane (dppe), with NaC5H4SN in a 1 : 2 molar ratio lead to mononuclear species [M(S-C5H4SN)2(P–P)], M = Pt; L–L = dppm ( 1) or dppe ( 2) and M = Pd; L–L = dppe ( 3), as well as to the dinuclear [Pd2(µ2-S,N-C5H4SN)(µ2-2S-C5H4SN)(µ2-dppm)(S-C5H4SN)2] ( 4). In contrast, reaction of [MCl2(dppm)] with NaC5H4SN in a 1 : 1 molar ratio leads to [Pd2(µ2-S,N-C5H4SN)3(µ2-dppm)]Cl ( 5) and trans-[Pt(S-C5H4SN)2(PPh2Me)2] ( 6) respectively. The latter is formed in low yield by cleavage of the dppm ligand. The dinuclear derivatives 4 and 5 present an A-frame and lantern structure, respectively. The former showing three different co-ordination modes in the same molecule with a short Pd–Pd distance of 2.9583 (9) Å and the latter with three bridging S,N thionate ligands showing a shorter Pd–Pd distance of 2.7291 (13) Å. Both distances could be imposed by the bridging ligands or point to some sort of metal–metal interaction.Financial support from MCyT-Spain-(BQU2002-04090-CO2-01 and BQU2002-00435) and JCyL-Spain-(BU15/03) is gratefully acknowledged.Peer reviewe

Trans-thionate derivatives of Pt(II) and Pd(II) with water-soluble phosphane PTA and DAPTA ligands: Antiproliferative activity against human ovarian cancer cell lines

A series of PTA and DAPTA platinum(II) and palladium(II) thionate complexes of the type trans-[M(SN)2P2] were prepared from the reaction of cis-[MCl2P2] [M = Pt, Pd; P = PTA (1,3,5-triaza-7-phosphaadamantane), DAPTA (3,7-diacetyl-1,3,7-triaza-5- phosphabicyclo[3.3.1]nonane)] with the in situ generated sodium salts of the heterocyclic thiones S-m-methylpyrimidine-2-thione, S-4,6-dimethylpyrimidine-2- thione, S-4,6-dihydroxypyrimidine-2-thione, benzothiazole-2-thione, benzoxazole-2-thione, S-1,3,4,-thiadiazole-2-thione, S-4,5-H-thiazolan-2-thione, and S-pyrimidine-4(1H)-one-2-thione. The X-ray structures of six of the compounds confirm the trans disposition and, only in the case of [Pd 2Cl2(S-pyrimidine-4(1H)-one-2-thionate) 2(PTA)2], a dinuclear structure with a Pd-Pd distance of 3.0265(14)Å was observed. In vitro cytotoxicities against human ovarian cancer cell lines A2780 and A2780cisR were evaluated for ten complexes showing a high inhibition of cellular growth with a comparable inhibitory potency (IC50) against A2780 cells to that of cisplatin. Notably, the compounds also show significant (up to 7-fold higher) activity in cisplatin-resistant A2780cisR cell lines. © 2013 American Chemical Society.We thank the Spanish Ministry for Education, Junta de Castilla y León, as well as the University of Burgos for generous financial support (Grants CTQ2008-06716-CO3-01, BU033A06, and 112-541A-487.01).Peer Reviewe

In vitro antiproliferative activity of thionate platinum(II) and palladium (II) complexes with PTA and DAPTA

Trabajo presentado al International Symposium on Metal Complexes celebrado en Burgos (España) del 16 al 20 de junio de 2013.Some studies have been focused on the preparation of water-soluble gold, platinum and palladium complexes with satisfactory cytotoxicity results. We have previously reported water-soluble gold(I) and platinum(II) complexes containing heterocyclic thionates [Au(SN)(P)] and trans-[Pt(SN)2(P)2] [SN = C5H4NS (pyridine-2-thionate), C4H3N2S (pyrimidine-2-thionate); P = PTA, PTA], which showed interesting in vitro antitumor properties in a series of tested cancer cell lines [1]. Therefore, we have been interested in synthesizing new water-soluble thionate palladium(II) and platinum(II) derivatives with PTA (1,3,5-triaza-7-phosphaadamantane) and DAPTA (3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo-[3.3.1] nonane). Here we present the preparation and characterization of a series of slightly water-soluble mononuclear thionate Pd(II) and Pt(II) complexes of the type trans-[M(SN)2(P)2] as evidenced by the X-ray structures of six of them. Only [Pd2Cl2(S-2-mercaptopyrimidin-4-one)2(PTA)2] shows a dinuclear structure. The antiproliferative properties of some of these complexes have been tested, and they show in vitro activities (IC50) against a human ovarian cancer cell line A2780 that are comparable to cisplatin, although they are much more efficient against A2780cisR (cisplatin resistant).Peer Reviewe