Organic Polymers for Encapsulation of Drugs, Food Ingredients and Agrochemicals

209 Pages·2023·12.82 MB·English

by  Corrales L.A.P., Licea-Claverie A., Crini G. (ed.)

Organic Polymers
for Encapsulation
of Drugs, Food
Ingredients and
Agrochemicals
Edited by
Lorenzo Antonio Picos Corrales, Angel Licea-Claverie and
Grégorio Crini
Printed Edition of the Special Issue Published in Polymers
www.mdpi.com/journal/polymers
Organic Polymers for Encapsulation of
Drugs, Food Ingredients and
Agrochemicals
Organic Polymers for Encapsulation of
Drugs, Food Ingredients and
Agrochemicals
Editors
Lorenzo Antonio Picos Corrales
Angel Licea-Claverie
Gre´gorio Crini
MDPI‚Basel‚Beijing‚Wuhan‚Barcelona‚Belgrade‚Manchester‚Tokyo‚Cluj‚Tianjin
Editors
LorenzoAntonioPicos AngelLicea-Claverie Gre´gorioCrini
Corrales CentrodeGraduadose Chrono-Environnement
FacultaddeIngenier´ıa Investigacio´nenQu´ımica Universite´ deFranche-Comte´
Culiaca´n InstitutoTecnolo´gico Besanc¸on
UniversidadAuto´noma deTijuana France
deSinaloa Tijuana
Culiacan Mexico
Mexico
EditorialOffice
MDPI
St. Alban-Anlage66
4052Basel,Switzerland
This is a reprint of articles from the Special Issue published online in the open access journal
Polymers(ISSN2073-4360) (availableat:www.mdpi.com/journal/polymers/special issues/organic
poly encapsulation).
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Contents
AbouttheEditors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii
Preface to ”Organic Polymers for Encapsulation of Drugs, Food Ingredients and
Agrochemicals” . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ix
Melissa Garcia-Carrasco, Lorenzo A. Picos-Corrales, Erick P. Gutie´rrez-Grijalva, Miguel A.
Angulo-Escalante,AngelLicea-ClaverieandJ.BasilioHeredia
LoadingandReleaseofPhenolicCompoundsPresentinMexicanOregano(Lippiagraveolens)in
DifferentChitosanBio-PolymericCationicMatrixes
Reprintedfrom: Polymers2022,14,3609,doi:10.3390/polym14173609 . . . . . . . . . . . . . . . . 1
AnaTeixeira,MarisaP.Sa´rria,IneˆsPinto,Begon˜aEspin˜a,AndreiaC.GomesandAlbertoC.
P.Dias
Protection against Paraquat-Induced Oxidative Stress by Curcuma longa Extract-Loaded
PolymericNanoparticlesinZebrafishEmbryos
Reprintedfrom: Polymers2022,14,3773,doi:10.3390/polym14183773 . . . . . . . . . . . . . . . . 21
Mar´ıaCarolinaOta´lora,AndreaWilches-TorresandJovannyA.Go´mezCastan˜o
Spray-DryingMicroencapsulationofPinkGuava(Psidiumguajava)CarotenoidsUsingMucilage
fromOpuntiaficus-indicaCladodesandAloeVeraLeavesasEncapsulatingMaterials
Reprintedfrom: Polymers2022,14,310,doi:10.3390/polym14020310 . . . . . . . . . . . . . . . . . 37
MirelaKopjar,IvanaBuljeta,MarioNosic´,IvanaIvic´,JosipSˇimunovic´ andAnitaPichler
EncapsulationofBlackberryPhenolicsandVolatilesUsingAppleFibersandDisaccharides
Reprintedfrom: Polymers2022,14,2179,doi:10.3390/polym14112179 . . . . . . . . . . . . . . . . 53
Hend Mohamed Hasanin Abou El-Naga, Samah A. El-Hashash, Ensaf Mokhtar Yasen,
StefanoLeporattiandNemanyA.N.Hanafy
Starch-Based Hydrogel Nanoparticles Loaded with Polyphenolic Compounds of Moringa
OleiferaLeafExtractHaveHepatoprotectiveActivityinBisphenolA-InducedAnimalModels
Reprintedfrom: Polymers2022,14,2846,doi:10.3390/polym14142846 . . . . . . . . . . . . . . . . 71
HtetHtetMoeSan,KhentPrimoAlcantara,BryanPaulI.Bulatao,WaraluckChaichompoo,
NonthanethNalinratanaandApichartSuksamrarnetal.
Development of Turmeric Oil—Loaded Chitosan/Alginate Nanocapsules for Cytotoxicity
EnhancementagainstBreastCancer
Reprintedfrom: Polymers2022,14,1835,doi:10.3390/polym14091835 . . . . . . . . . . . . . . . . 91
DohaBerraaouan,KamalEssifi,MohamedAddi,ChristopheHano,Marie-LaureFauconnier
andAbdesselamTahani
HybridMicrocapsulesforEncapsulationandControlledReleaseofRosemaryEssentialOil
Reprintedfrom: Polymers2023,15,823,doi:10.3390/polym15040823 . . . . . . . . . . . . . . . . . 109
AuricaIonelaGugoasa,StefaniaRacovita,SilviaVasiliuandMarcelPopa
Grafted Microparticles Based on Glycidyl Methacrylate, Hydroxyethyl Methacrylate and
Sodium Hyaluronate: Synthesis, Characterization, Adsorption and Release Studies
of Metronidazole
Reprintedfrom: Polymers2022,14,4151,doi:10.3390/polym14194151 . . . . . . . . . . . . . . . . 125
v
Carlos Enrique Osorio-Alvarado, Jose Luis Ropero-Vega, Ana Elvira Farfa´n-Garcı´a and
JohannaMarcelaFlo´rez-Castillo
ImmobilizationSystemsofAntimicrobialPeptideIb´M1inPolymericNanoparticlesBasedon
AlginateandChitosan
Reprintedfrom: Polymers2022,14,3149,doi:10.3390/polym14153149 . . . . . . . . . . . . . . . . 155
Nareekan Chaiwong, Yuthana Phimolsiripol, Pimporn Leelapornpisid, Warintorn
Ruksiriwanich,KittisakJantanasakulwongandPornchaiRachtanapunetal.
Synergistics of Carboxymethyl Chitosan and Mangosteen Extract as Enhancing Moisturizing,
Antioxidant,Antibacterial,andDeodorizingPropertiesinEmulsionCream
Reprintedfrom: Polymers2022,14,178,doi:10.3390/polym14010178 . . . . . . . . . . . . . . . . . 169
WesamA.HatemandYakovLapitsky
AcceleratingPayloadReleasefromComplexCoacervatesthroughMechanicalStimulation
Reprintedfrom: Polymers2023,15,586,doi:10.3390/polym15030586 . . . . . . . . . . . . . . . . . 189
vi
About the Editors
LorenzoAntonioPicosCorrales
LorenzoAntonioPicosCorralesisaResearchProfessorattheAutonomousUniversityofSinaloa
(UAS, since 2012), Mexico, with scientific interests focused on synthesis and characterization of
polymers for drug delivery systems and water treatment. He studied Chemical Engineering at the
Faculty of Chemical-Biological Sciences-UAS. Master in Chemistry by the Technological Institute
of Tijuana (IT-Tijuana), Mexico; his work obtained the 2008 Best Master’s Thesis Award from the
National Technological System. In 2012, he got his Ph.D. in Chemistry (Polymer Science) at the
IT-Tijuana, Mexico, obtaining a DAAD (German Academic Exchange Service, 2010) scholarship for
the “Sandwich PhD Model” at the Technische Universita¨t Dresden, Germany. He has also received
research training at the Leibniz-Institut fu¨r Polymerforschung (IPF) Dresden, Germany, and at the
AutonomousUniversityofBajaCalifornia,Tijuana,Mexico. Atpresent,LorenzoPicosisafull-time
ProfessorattheFacultyofEngineeringCuliaca´n-UASintheEnvironmentalLaboratory,andLecturer
intheDepartmentofCivilEngineering;memberoftheBasicAcademicNucleusofthePostgraduate
Program in Biological Sciences at the Faculty of Biology-UAS. Additionally, he is member of the
National System of Researchers from Mexico. He is a Special Guest Editor of the journal Polymers
andAssistantEditorofthejournalHybridAdvances, andhasalsocontributedasareviewertomore
than15differentjournals.
AngelLicea-Claverie
Angel Licea-Claverie is a full-time Professor at the Instituto Tecnolo´gico de Tijuana, Mexico,
which is part of the Tecnolo´gico Nacional de Me´xico. He has 20 years of experience in the
study of temperature and pH sensitive polymers and 14 years of experience on controlled
radical polymerization techniques. His research group have studied the controlled release of
anti-inflammatory and anticancer drugs from sensitive micelles, polymersomes and nanogels
developed. He is member of the American Chemical Society, Division of Polymer Chemistry, and
ofthePolymerSocietyofMexico,forwhichheservedasNationalPresident2015–2017.
Gre´gorioCrini
Gre´gorioCriniisanenvironmentalpolymerscientistandresearchdirectorattheUniversite´ de
Franche-Comte´,Chrono-environnement,Besanc¸on,France. HereceivedhisPh.D.degreeinorganic
and macromolecular chemistry from the Universite´ de Lille in 1995 under supervision of Professor
Michel Morcellet. He then spent 2 years as a postdoctoral fellow at the G. Ronzoni Institute for
Chemical and Biochemical Research in Milan, Italy, working with Research Director Giangiacomo
TorriandProfessorBenitoCasuonthecharacterizationofpolysaccharide-basedhydrogelsbyNMR
techniques. In 1997, he joined the Universite´ de Franche-Comte´ where he set up a research group
workingontheuseofoligosaccharides(dextrins,cyclodextrins)andpolysaccharides(starch,chitin,
chitosan, cellulose) in industrial applications. In 2000, he completed his authorization to supervise
research activities. His current interests focus on the design of new functional macromolecular
networksandtheenvironmentalaspectsofoligosaccharide,polysaccharide,andnaturalfibre(hemp,
flax)chemistryforappliedresearch. Gre´gorioCRINIhaspublishedmorethan215papers,apatent,
and17books.Heisahighlycitedresearcher(h-indexof45,morethan17,100citations)andsince2021,
hehasbeenlistedasoneoftheworld’smostcitedresearchersbytheAmericanuniversityStanford.
Gre´gorioCRINIhasalsoconductedconsultingprojectsformanycompanies.
vii
Preface to ”Organic Polymers for Encapsulation of
Drugs, Food Ingredients and Agrochemicals”
Activecompounds(e.g.,drugsandfoodingredients)helptoimprovethequalityoflifearound
the world. In order to increase the effectiveness in each intended application, research groups
have worked under the motivation of demonstrating that the encapsulation helps protect guest
compounds against premature degradation and can enhance their transport in aqueous medium,
increasingthepercentageofsubstancethatisavailableforabiologicalactioninacontrolledmanner
over time. For that purpose, the encapsulation of guest molecules has been accomplished using
organicpolymers(natural, synthetic, andsemi-syntheticchains)asplatforms. Thisisaninteresting
topic in which the scholars have designed systems that reach the desired efficiency reducing side
effects and/or contamination derived from the overuse of active compounds. Hence, this reprint
aims to provide an update regarding this topic. The content may be helpful for the colleagues and
studentsworkingonencapsulationofactivecompounds.
Thecontributionofallauthorstothiscollectionisdeeplyappreciated.Itisimportanttohighlight
theactiveparticipationofthereviewersandstaffofthesection“PolymerNetworks”. Theywerekey
personswhohelpedcompletethisReprintBook.
LorenzoAntonioPicosCorrales,AngelLicea-Claverie,andGre´gorioCrini
Editors
ix
polymers
Article
Loading and Release of Phenolic Compounds Present in
Mexican Oregano (Lippia graveolens) in Different Chitosan
Bio-Polymeric Cationic Matrixes
MelissaGarcia-Carrasco1 ,LorenzoA.Picos-Corrales2 ,ErickP.Gutiérrez-Grijalva3 ,
MiguelA.Angulo-Escalante1,AngelLicea-Claverie4,* andJ.BasilioHeredia1,*
1 NutraceuticalsandFunctionalFoodsLaboratory,CentrodeInvestigaciónenAlimentaciónyDesarrollo,A.C.,
CarreteraaEldoradoKm.5.5,Col.CampoElDiez,Culiacán80110,Sinaloa,Mexico
2 FacultaddeIngenieríaCuliacán,UniversidadAutónomadeSinaloa,CiudadUniversitaria,
Culiacán80013,Sinaloa,Mexico
3 CátedrasCONACYT-CentrodeInvestigaciónenAlimentaciónyDesarrollo,A.C.,
CarreteraaEldoradoKm.5.5,Col.CampoElDiez,Culiacán80110,Sinaloa,Mexico
4 CentrodeGraduadoseInvestigaciónenQuímica,TecnológicoNacionaldeMexico/InstitutoTecnológicode
Tijuana,A.P.1166,Tijuana22000,BajaCalifornia,Mexico
* Correspondence:[email protected](A.L.-C.);[email protected](J.B.H.)
Abstract:Mexicanoregano(Lippiagraveolens)polyphenolshaveantioxidantandanti-inflammatory
potential,butlowbioaccessibility. Therefore,inthepresentworkthemicro/nano-encapsulation
ofthesecompoundsintwodifferentmatrixesofchitosan(CS)andchitosan-b-poly(PEGMA )
2000
(CS-b-PPEGMA) is described and assessed. The particle sizes of matrixes of CS (~955 nm) and
Citation:Garcia-Carrasco,M.;
CS-b-PPEGMA(~190nm)increasedby10%and50%,respectively,whenthephenoliccompounds
Picos-Corrales,L.A.;
wereencapsulated,yieldingloadingefficiencies(LE)between90–99%and50–60%,correspondingly.
Gutiérrez-Grijalva,E.P.;
Angulo-Escalante,M.A.; Thereleaseprofilesinsimulatedfluidsrevealedabettercontrolofhost–guestinteractionsbyusing
Licea-Claverie,A.;Heredia,J.B. theCS-b-PPEGMAmatrix,reachingphenoliccompoundsreleaseof80%after24h,whilesingleCS
LoadingandReleaseofPhenolic retainedtheguestcompounds.Thetotalreducingcapacity(TRC)andTroloxequivalentantioxidant
CompoundsPresentinMexican capacity(TEAC)ofthephenoliccompounds(PPHs)areprotectedandincreased(morethanfivetimes)
Oregano(Lippiagraveolens)in whentheyareencapsulated.Thus,thisinvestigationprovidesastandardencapsulationstrategyand
DifferentChitosanBio-Polymeric relevantresultsregardingnutraceuticalsstabilizationandtheirimprovedbioaccessibility.
CationicMatrixes.Polymers2022,14,
3609. https://doi.org/10.3390/
Keywords:chitosan;polyethyleneglycolmethacrylate;oregano;phenoliccompounds;nanoencapsulation;
polym14173609
bioaccessibility
AcademicEditor:KiHyunBae
Received:1July2022
Accepted:25August2022
1. Introduction
Published:1September2022
The secondary metabolites present in plants, such as phenolic compounds, better
Publisher’sNote:MDPIstaysneutral
knownasphytochemicals,havegainedgreatinterestinrecentyearssincetheyplayan
withregardtojurisdictionalclaimsin
importantroleinthepreventionofdifferentdiseasessuchascancer,diabetes,andobesity,
publishedmapsandinstitutionalaffil-
which are related to oxidative stress [1]. Mexican oregano (L. graveolens) is an endemic
iations.
speciesfromnorthwesternMexicomostlyknownforitsculinaryusesbutisalsoarich
sourceofphenoliccompoundsthatcanbringgreatbenefitstohumanhealthduetotheir
pharmacologicalproperties,whichincludetheanti-inflammatory,antifungal,andantibac-
terial activities, among others [2–4]. In this subject, essential oils and polyphenols are
Copyright: © 2022 by the authors.
Licensee MDPI, Basel, Switzerland. themajorsecondarymetabolitesfoundinoreganothatareresponsibleforitsbiological
This article is an open access article properties[2,5]. Previousworkshaveshownthatoreganopolyphenolshavelowbioac-
distributed under the terms and cessibility,andin-vitrodigestionassayshavedemonstratedthatphenolicacids,flavones,
conditionsoftheCreativeCommons andflavanonesoforeganoseemtobesusceptibletothepHchangesduringeachdigestion
Attribution(CCBY)license(https:// stage[6–8]. Thus,despitethebioactivepropertiesoforeganopolyphenols,theymaybe
creativecommons.org/licenses/by/ affected during their journey through the gastrointestinal (GI) tract, mainly due to pH
4.0/).
1
Polymers2022,14,3609
changesfavoringtheionizationofthesecompoundsortheyaredegraded,andthusthe
activecompoundscouldlosetheirproperties[1,9,10].
Thelowbioaccessibilityofpolyphenolsisasubjecthighlyreported;hence,different
alternativeshavebeenproposedtoprotectthesemetabolitesfromdegradation. Among
the technologies useful for this purpose are: (1) spray drying (for microencapsulation),
(2)biopolymeric-typesystemssuchaspectin,alginate,gums,andchitosanusedtoencapsu-
latedifferentphytochemicalcompoundssuchascurcumin,thymol,andcarvacrol[11–17].
Althoughmostoftheseloadingandreleasestudieshavebeencarriedoutwithisolatedcom-
pounds,ithasalsobeenfoundthatwhenthereisacombinationofphenoliccompounds,
theycancreatesynergismbetweenthemandenhancetheiractivity[18].
Thebiopolymerchitosan(CS),whichisobtainedfromanaturalpolysaccharidecalled
chitin,representsabiocompatibleandbiodegradableplatformwithoutstandingperfor-
manceinsorption-orientedprocesses. Thisisoneofthemainpolymericmatrixesusedfor
theencapsulationofsyntheticornaturalagentsduetopolyelectrolytecharacter,which
meansthatthechargeofitsfunctionalgroupscanbemodifieddependingonthepHofthe
medium,wheretheaminoandthehydroxylgroupsgivethischaracter[19–22]. However,
thisbiopolymerisinsolubleinnormaldeionizedwater,limitingbiologicalapplications;
regardingthis,somestudieshavebeenfocusedonmodifyingthesemoleculeswithdifferent
polymerstoimprovetheirsolubility,suchaspolyethyleneglycol(PEG).PEGhasbeenone
ofthepolymerswithbetterbiocompatibility[23]. Modifiedbiopolymershaveshownthe
capacitytoadheretopeptidesequences[24],growthfactors[25],andtheabilitytocontrol
mechanicalpropertiesregardlessofpolymerizationconditions[26].
As it is well known, PEG is one of the few polymers approved by the U.S. FDA;
moreover,thepolyethyleneglycolmethylmethacrylate(PEGMA)propertiesareattributed
to PEG due to their similar structures [27]. In addition, in case a certain percentage
passesintothebloodsystem,theseparticlesavoidaresponsebytheimmunesystem,thus
expanding the areas of application [28,29]. In some approaches, the use of PEGMA is
relatedtotheincreaseinthelowercriticalsolutiontemperature(LCST)ofthesynthesized
◦
copolymers,increasingtheLCSTattemperaturesgreaterthan32 C,whichensuresthatthe
matrixcanremainstableattemperatureshigherthantheLCSTinaqueousmedium[30].
Based on the abovementioned, in the present work the encapsulation of phenolic
compoundsextractedfromtheaerialpartofMexicanoregano(L.graveolens)wascarried
out in systems based on chitosan (CS) and chitosan modified with PEGMA (Chitosan-
block-poly(PEGMA )(CS-b-PPEGMA),theirreleaseprofilesatdifferentpHlevelswere
2000
studiedandtheirantioxidantactivitybeforeandafterencapsulationwasassessed. Forthat,
asimpleencapsulationmethodinvolvingmechanicalstirringwasused.
2. MaterialsandMethods
2.1. Reagents
Polyethyleneglycolmethylmethacrylate2000gmol−1 (PEGMA),ammoniumper-
sulfate(APS,98%,SigmaAldrich,Toluca,Mexico),sodiumchloride(NaCl,Jalmek,San
NicolásdelosGarza,Mexico),chitosan(Lowweight,98%,SigmaAldrich),glacialacetic
acid(99.7%,Fermont,Monterrey,Mexico),deuteriumchloride/deuteriumoxide(D O/DCl
2
35% by weight, 99.9% deuterium, Sigma Aldrich), Folin-Ciocalteu reagent, aluminum
chloride,potassiumacetate,quercetin,DPPHradical,ABTSradical,potassiumpersulfate,
HPLCgradewater,andformicacidwerepurchasedfromSigma-Aldrich(Toluca,Mexico).
Moreover,sodiumhydroxide(97.8%,ChemicalProductsofMonterreySAdeCV,Monterrey,
Mexico)waspurchasedthroughalocalprovider.
2.2. ChitosanPurification
CS was dissolved in an aqueous acetic acid solution at 1% in volume, up to a con-
centration of 10 mg mL−1; afterward, the mixture was filtered under reduced pressure
withBüchner. CSwasprecipitatedfromtheacidicsolutionusing1Msodiumhydroxide
solution. ThealkalineCSsuspensionwasfilteredunderreducedpressurewitha5µm
2