Table of Contents for This Article:
1. Kev loj hlob ntawm Amino Acids
2. Cov yam ntxwv zoo
3. Tshuaj muaj pes tsawg leeg
4. Kev faib tawm
5. Synthesis
6. Physicochemical zog
7. Toxicity
8. Antimicrobial kev ua haujlwm
9. Rheological zog
10. Kev siv hauv kev lag luam tshuaj pleev ib ce
11. Kev siv hauv cov tshuaj pleev ib ce txhua hnub
Amino Acid Surfactants (AAS)yog ib chav kawm ntawm surfactants tsim los ntawm kev sib txuas cov pab pawg hydrophobic nrog ib lossis ntau dua Amino Acids. Hauv qhov no, Amino Acids tuaj yeem yog hluavtaws lossis muab los ntawm cov protein hydrolysates lossis cov khoom siv txuas ntxiv dua qub. Daim ntawv no suav nrog cov ntsiab lus ntawm feem ntau ntawm cov txheej txheem hluavtaws muaj rau AAS thiab cov txiaj ntsig ntawm txoj kev sib txawv ntawm cov khoom siv physicochemical ntawm cov khoom kawg, suav nrog solubility, dispersion stability, toxicity thiab biodegradability. Raws li cov chav kawm ntawm surfactants nyob rau hauv kev xav tau ntau ntxiv, ntau yam ntawm AAS vim lawv cov qauv sib txawv muaj ntau txoj hauv kev lag luam.
Muab hais tias surfactants tau siv dav hauv cov tshuaj detergents, emulsifiers, corrosion inhibitors, tertiary roj rov qab thiab tshuaj, cov kws tshawb fawb tsis tau tso tseg rau cov surfactants.
Surfactants yog cov khoom lag luam uas sawv cev tshaj plaws uas tau noj ntau nyob rau txhua hnub thoob ntiaj teb thiab tau muaj kev cuam tshuam tsis zoo rau cov dej hauv dej.Cov kev tshawb fawb tau pom tias kev siv dav dav ntawm cov tshuaj surfactants tuaj yeem muaj kev cuam tshuam tsis zoo rau ib puag ncig.
Niaj hnub no, tsis muaj tshuaj lom, biodegradability thiab biocompatibility yuav luag yog qhov tseem ceeb rau cov neeg siv khoom raws li kev siv hluav taws xob thiab kev ua haujlwm ntawm surfactants.
Biosurfactants yog ib puag ncig tus phooj ywg ruaj khov surfactants uas tau tsim los ntawm cov kab mob xws li kab mob, fungi, thiab poov xab, los yog secreted extracellularly.Yog li ntawd, biosurfactants tseem tuaj yeem npaj los ntawm kev tsim qauv molecular los ua cov qauv amphiphilic, xws li phospholipids, alkyl glycosides thiab acyl Amino Acids.
Amino Acid surfactants (AAS)yog ib qho ntawm cov surfactants, feem ntau yog tsim los ntawm cov tsiaj los yog ua liaj ua teb derived raw cov ntaub ntawv. Ob xyoo dhau los, AAS tau nyiam ntau qhov kev txaus siab los ntawm cov kws tshawb fawb los ua cov surfactants tshiab, tsis yog vim lawv tuaj yeem tsim los ntawm cov khoom siv txuas ntxiv dua tshiab, tab sis kuj vim tias AAS tau yooj yim degradable thiab tsis muaj teeb meem los ntawm cov khoom lag luam, ua rau lawv muaj kev nyab xeeb dua rau cov khoom lag luam. ib puag ncig.
AAS tuaj yeem txhais tau tias yog chav kawm ntawm surfactants suav nrog Amino Acids uas muaj Amino Acid pawg (HO 2 C-CHR-NH 2) lossis Amino Acid residues (HO 2 C-CHR-NH-). 2 thaj chaw ua haujlwm ntawm Amino Acids tso cai rau cov khoom siv ntawm ntau yam surfactants. Tag nrho ntawm 20 tus qauv Proteinogenic Amino Acids paub tias muaj nyob hauv cov xwm txheej thiab muaj lub luag haujlwm rau txhua qhov kev xav ntawm lub cev hauv kev loj hlob thiab kev ua neej nyob. Lawv txawv ntawm ib leeg tsuas yog raws li qhov seem R (Daim duab 1, pk a yog qhov tsis zoo logarithm ntawm cov kua qaub dissociation tas li ntawm cov tshuaj). Qee qhov tsis yog-polar thiab hydrophobic, qee qhov yog polar thiab hydrophilic, qee qhov yog yooj yim thiab qee qhov yog acidic.
Vim tias Amino Acids yog cov khoom siv txuas ntxiv dua tshiab, surfactants synthesized los ntawm Amino Acids kuj muaj peev xwm ua kom muaj kev ruaj ntseg thiab zoo ib puag ncig. Cov qauv yooj yim thiab ntuj, tsis muaj tshuaj lom thiab biodegradability sai feem ntau ua rau lawv zoo tshaj rau cov pa surfactants. Siv cov khoom siv txuas ntxiv dua tshiab (xws li Amino Acids thiab cov roj zaub), AAS tuaj yeem tsim los ntawm ntau txoj kev siv tshuab biotechnological thiab txoj kev tshuaj lom neeg.
Nyob rau hauv lub xyoo pua 20th, Amino Acids tau pom thawj zaug siv los ua cov substrates rau kev sib txuas ntawm surfactants.AAS feem ntau yog siv los ua cov tshuaj tua kab mob hauv tshuaj thiab tshuaj pleev ib ce.Tsis tas li ntawd, AAS tau pom tias muaj kev ua haujlwm lom neeg tawm tsam ntau yam kab mob ua rau cov kab mob, qog, thiab kab mob. Xyoo 1988, qhov muaj cov nqi qis AAS tau tsim kev tshawb fawb txog kev ua haujlwm saum npoo av. Niaj hnub no, nrog rau txoj kev loj hlob ntawm biotechnology, qee cov Amino Acids kuj tseem tuaj yeem ua ke ua lag luam ntawm qhov loj los ntawm cov poov xab, uas tsis ncaj qha ua pov thawj tias AAS ntau lawm yog ib puag ncig zoo.
01 Kev Txhim Kho ntawm Amino Acids
Raws li thaum ntxov xyoo pua 19th, thaum ib txwm tshwm sim Amino Acids tau pom thawj zaug, lawv cov qauv tau kwv yees kom muaj nuj nqis heev - siv tau los ua cov khoom siv raw rau kev npaj amphiphiles. Thawj txoj kev tshawb fawb txog kev sib txuas ntawm AAS tau tshaj tawm los ntawm Bondi hauv xyoo 1909.
Hauv txoj kev tshawb no, N-acylglycine thiab N-acylalanine tau qhia ua pawg hydrophilic rau surfactants. Cov hauj lwm tom qab tau koom nrog kev sib txuas ntawm lipoAmino Acids (AAS) siv glycine thiab alanine, thiab Hentrich li al. luam tawm ib series ntawm kev tshawb pom,suav nrog thawj daim ntawv thov patent, ntawm kev siv acyl sarcosinate thiab acyl aspartate ntsev ua surfactants hauv cov khoom siv tu tsev (xws li tshuaj zawv plaub hau, tshuaj ntxuav tes thiab tshuaj txhuam hniav).Tom qab ntawd, ntau tus kws tshawb fawb tau tshawb xyuas qhov kev sib txuas thiab kev siv lub cev ntawm acyl Amino Acids. Txog rau tam sim no, lub cev loj ntawm cov ntaub ntawv tau luam tawm ntawm kev sib txuas, cov khoom siv, cov ntawv thov kev lag luam thiab biodegradability ntawm AAS.
02 Cov yam ntxwv zoo
Cov tsis-polar hydrophobic fatty acid chains ntawm AAS tuaj yeem sib txawv hauv cov qauv, saw ntev thiab tus lej.Cov txheej txheem sib txawv thiab kev ua haujlwm siab ntawm AAS piav qhia lawv cov kev sib xyaw ua ke dav dav thiab cov khoom siv hluav taws xob thiab cov khoom siv roj ntsha. Cov pab pawg thawj coj ntawm AAS yog tsim los ntawm Amino Acids lossis peptides. Qhov sib txawv ntawm lub taub hau pab pawg txiav txim siab qhov adsorption, kev sib sau ua ke thiab kev ua haujlwm lom neeg ntawm cov surfactants. Cov pab pawg ua haujlwm hauv pawg thawj coj txiav txim siab hom AAS, suav nrog cationic, anionic, nonionic, thiab amphoteric. Kev sib xyaw ua ke ntawm hydrophilic Amino Acids thiab hydrophobic long-chain feem ua ib qho qauv amphiphilic uas ua rau cov molecule zoo heev. Tsis tas li ntawd, lub xub ntiag ntawm asymmetric carbon atoms nyob rau hauv lub molecule pab tsim chiral molecules.
03 Tshuaj muaj pes tsawg leeg
Txhua Peptides thiab Polypeptides yog cov khoom lag luam Polymerization ntawm ze li ntawm 20 α-Proteinogenic α-Amino Acids. Tag nrho 20 α-Amino Acids muaj cov carboxylic acid functional group (-COOH) thiab ib pawg amino functional (-NH 2), ob qho tib si txuas rau tib tetrahedral α-carbon atom. Amino Acids txawv ntawm ib leeg los ntawm cov pab pawg R sib txawv uas txuas rau α-carbon (tshwj tsis yog rau lycine, qhov twg pawg R yog hydrogen.) Cov pab pawg R yuav txawv ntawm cov qauv, qhov loj thiab nqi (acidity, alkalinity). Cov kev sib txawv no kuj txiav txim siab qhov solubility ntawm Amino Acids hauv dej.
Amino Acids yog chiral (tshwj tsis yog glycine) thiab ua haujlwm kho qhov muag los ntawm qhov xwm txheej vim tias lawv muaj plaub qhov sib txawv sib txawv txuas rau alpha carbon. Amino Acids muaj ob qhov ua tau zoo; lawv yog cov tsis sib tshooj daim iav duab ntawm ib leeg, txawm tias qhov tseeb tias L-stereoisomers muaj ntau dua. Cov R-pawg tam sim no nyob rau hauv qee cov Amino Acids (Phenylalanine, Tyrosine thiab Tryptophan) yog aryl, ua rau lub siab tshaj plaws UV nqus ntawm 280 nm. Cov acidic α-COOH thiab cov theem pib α-NH 2 hauv Amino Acids muaj peev xwm ntawm ionization, thiab ob qho tib si stereoisomers, qhov twg lawv yog, tsim cov ionization equilibrium qhia hauv qab no.
R-COOH ↔ R-COO-+ H+
R-NH3+↔ R-NH2+ H+
Raws li pom nyob rau hauv ionization equilibrium saum toj no, cov amino acids muaj tsawg kawg yog ob pawg tsis muaj zog acidic; Txawm li cas los xij, pawg carboxyl yog acidic ntau dua piv rau protonated amino pawg. pH 7.4, pawg carboxyl yog deprotonated thaum cov amino pawg protonated. Amino acids uas tsis yog-ionizable R pawg yog hluav taws xob nruab nrab ntawm pH no thiab tsim zwitterion.
04 Classification
AAS tuaj yeem muab faib ua plaub yam, uas tau piav qhia hauv qab no nyob rau hauv lem.
4.1 Raws li keeb kwm
| Raws li lub hauv paus chiv keeb, AAS tuaj yeem muab faib ua 2 pawg raws li hauv qab no. ① Natural Qeb Qee qhov sib xyaw ua ke uas muaj cov amino acids kuj muaj peev xwm txo qis qhov nro / cuam tshuam ntawm lub ntsej muag, thiab qee qhov tseem tshaj qhov ua tau zoo ntawm glycolipids. Cov AAS no tseem hu ua lipopeptides. Lipopeptides yog cov sib xyaw ua ke uas tsis muaj qhov hnyav, feem ntau yog tsim los ntawm hom Bacillus.
Xws li AAS tau muab faib ua 3 subclasses:surfactin, iturin thiab fengycin.
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| Tsev neeg ntawm nto-active peptides encompasses heptapeptide variants ntawm ntau yam tshuaj,raws li qhia hauv daim duab 2a, uas C12-C16 unsaturated β-hydroxy fatty acid saw txuas rau peptide. Lub nto-active peptide yog ib tug macrocyclic lactone nyob rau hauv uas lub nplhaib kaw los ntawm catalysis ntawm C-terminus ntawm β-hydroxy fatty acid thiab peptide. Hauv subclass ntawm iturin, muaj rau lub ntsiab sib txawv, uas yog iturin A thiab C, mycosubtilin thiab bacillomycin D, F thiab L.Nyob rau hauv txhua rooj plaub, cov heptapeptides txuas nrog C14-C17 chains ntawm β-amino fatty acids (cov chains tuaj yeem muaj ntau haiv neeg). Nyob rau hauv cov ntaub ntawv ntawm ekurimycins, cov amino pawg ntawm β-txoj hauj lwm tuaj yeem tsim ib qho amide daim ntawv cog lus nrog C-terminus yog li tsim cov qauv macrocyclic lactam.
Cov subclass fengycin muaj fengycin A thiab B, uas tseem hu ua plipastatin thaum Tyr9 yog D-configured.Lub decapeptide txuas nrog C14-C18 saturated lossis unsaturated β-hydroxy fatty acid saw. Structurely, plipastatin kuj yog ib tug macrocyclic lactone, muaj ib tug Tyr sab saw ntawm txoj hauj lwm 3 ntawm lub peptide ib theem zuj zus thiab tsim ib tug ester daim ntawv cog lus nrog lub C-terminal residue, yog li tsim ib lub nplhaib sab hauv (raws li yog rooj plaub rau ntau Pseudomonas lipopeptides).
② Synthetic Qeb AAS kuj tuaj yeem raug tsim los ntawm kev siv ib qho ntawm cov acidic, yooj yim thiab nruab nrab amino acids. Cov amino acids uas siv rau kev sib txuas ntawm AAS yog glutamic acid, serine, proline, aspartic acid, glycine, arginine, alanine, leucine, thiab protein hydrolysates. Cov subclass ntawm surfactants no tuaj yeem npaj los ntawm cov tshuaj, enzymatic, thiab chemoenzymatic txoj kev; Txawm li cas los xij, rau kev tsim khoom ntawm AAS, tshuaj synthesis yog qhov ua tau zoo dua. Piv txwv xws li N-lauroyl-L-glutamic acid thiab N-palmitoyl-L-glutamic acid.
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4.2 Raws li aliphatic saw hloov pauv
Raws li cov aliphatic saw substituents, amino acid-based surfactants tuaj yeem muab faib ua 2 hom.
Raws li txoj hauj lwm ntawm tus neeg hloov
| ①N-hloov AAS Hauv N-hloov cov tebchaw, ib pawg amino yog hloov los ntawm pawg lipophilic lossis pawg carboxyl, uas ua rau poob ntawm qhov pib. Qhov piv txwv yooj yim ntawm N-hloov AAS yog N-acyl amino acids, uas yog qhov tseem ceeb anionic surfactants. n-substituted AAS muaj ib daim ntawv cog lus amide txuas ntawm hydrophobic thiab hydrophilic feem. Lub amide daim ntawv cog lus muaj peev xwm tsim ib daim ntawv cog lus hydrogen, uas pab txhawb kev degradation ntawm no surfactant nyob rau hauv ib puag ncig acidic, yog li ua rau nws biodegradable.
②C-hloov AAS Hauv C-hloov cov tebchaw, kev hloov pauv tshwm sim ntawm pawg carboxyl (ntawm amide lossis ester daim ntawv cog lus). Hom C-hloov cov tebchaw (xws li esters lossis amides) yog qhov tseem ceeb cationic surfactants.
③N- thiab C-hloov AAS Hauv hom surfactant, ob pawg amino thiab carboxyl yog qhov hydrophilic. Hom no yog qhov tseem ceeb ntawm amphoteric surfactant. |
4.3 Raws li tus naj npawb ntawm hydrophobic tails
Raws li tus naj npawb ntawm pawg thawj coj thiab cov tails hydrophobic, AAS tuaj yeem muab faib ua plaub pawg. Ncaj-chain AAS, Gemini (dimer) hom AAS, Glycerollipid hom AAS, thiab bicephalic amphiphilic (Bola) hom AAS. ncaj-chain surfactants yog cov surfactants uas muaj cov amino acids uas tsuas yog ib qho hydrophobic tail (Daim duab 3). Gemini hom AAS muaj ob hom amino acid polar taub hau pawg thiab ob hydrophobic tails ib molecule (Daim duab 4). Hauv hom qauv no, ob txoj hlua ncaj nraim AAS txuas ua ke los ntawm lub spacer thiab yog li tseem hu ua dimers. Hauv Glycerollipid hom AAS, ntawm qhov tod tes, ob lub hydrophobic tails txuas rau tib lub taub hau amino acid pawg. Cov surfactants no tuaj yeem suav tias yog cov analogs ntawm monoglycerides, diglycerides thiab phospholipids, thaum nyob rau hauv Bola-type AAS, ob pawg amino acid lub taub hau yog txuas los ntawm tus Tsov tus tw hydrophobic.
4.4 Raws li hom ntawm pawg thawj coj
① Cationic AAS
Lub taub hau pab pawg ntawm hom surfactant no muaj cov nqi zoo. Qhov ntxov tshaj plaws cationic AAS yog ethyl cocoyl arginate, uas yog pyrrolidone carboxylate. Cov yam ntxwv tshwj xeeb thiab muaj ntau yam ntawm cov surfactant no ua rau nws muaj txiaj ntsig zoo hauv cov tshuaj tua kab mob, tshuaj tua kab mob, tshuaj tiv thaiv kab mob, cov plaub hau txias, thiab ua rau lub qhov muag thiab tawv nqaij thiab yooj yim biodegradable. Singare thiab Mhatre synthesized arginine-based cationic AAS thiab soj ntsuam lawv cov khoom physicochemical. Hauv txoj kev tshawb no, lawv tau thov cov txiaj ntsig siab ntawm cov khoom tau siv Schotten-Baumann cov tshuaj tiv thaiv. Nrog nce alkyl saw ntev thiab hydrophobicity, qhov kev ua ntawm surfactant tau pom tias nce ntxiv thiab Critical Mcelle Concentration (cmc) kom txo. Lwm qhov yog quaternary acyl protein, uas feem ntau yog siv los ua cov tshuaj kho plaub hau.
② Anionic AAS
Hauv anionic surfactants, pawg polar taub hau ntawm cov surfactant muaj qhov tsis zoo. Sarcosine (CH 3 -NH-CH 2 -COOH, N-methylglycine), ib qho amino acid feem ntau pom nyob rau hauv hiav txwv urchins thiab hiav txwv hnub qub, yog tshuaj muaj feem xyuam rau glycine (NH 2 -CH 2 -COOH,), ib qho yooj yim amino acid pom. nyob rau hauv mammalian hlwb. -COOH,) yog tshuaj muaj feem xyuam rau glycine, uas yog ib qho yooj yim amino acid pom nyob rau hauv mammalian hlwb. Lauric acid, tetradecanoic acid, oleic acid thiab lawv cov halides thiab esters feem ntau yog siv los ua ke sarcosinate surfactants. Sarcosinates yog qhov mob me me thiab yog li ntawd feem ntau siv hauv cov tshuaj ntxuav qhov ncauj, tshuaj zawv plaub hau, tshuaj tsuag shaving foams, tshuaj pleev thaiv hnub, tshuaj ntxuav tawv nqaij, thiab lwm yam khoom siv tshuaj pleev ib ce.
Lwm cov khoom lag luam muaj anionic AAS suav nrog Amisoft CS-22 thiab AmiliteGCK-12, uas yog cov npe lag luam rau sodium N-cocoyl-L-glutamate thiab potassium N-cocoyl glycinate, feem. Amilite feem ntau yog siv los ua tus neeg sawv cev foaming, detergent, solubilizer, emulsifier thiab dispersant, thiab muaj ntau yam kev siv hauv cov tshuaj pleev ib ce, xws li tshuaj zawv plaub hau, da dej soaps, ntxuav lub cev, tshuaj txhuam hniav, tshuaj ntxuav lub ntsej muag, xab npum ntxuav, tshuaj tiv thaiv kab mob thiab cov khoom siv hauv tsev. Amisoft yog siv los ua cov tawv nqaij mos thiab cov plaub hau ntxuav, feem ntau hauv lub ntsej muag thiab lub cev ntxuav, thaiv cov tshuaj detergents, cov khoom tu lub cev, tshuaj zawv plaub hau thiab lwm yam khoom tu tawv nqaij.
③zwitterionic lossis amphoteric AAS
Amphoteric surfactants muaj ob qho tib si acidic thiab cov chaw yooj yim thiab tuaj yeem hloov lawv cov nqi los ntawm kev hloov pH tus nqi. Nyob rau hauv alkaline xov xwm lawv coj zoo li anionic surfactants, thaum nyob rau hauv acidic ib puag ncig lawv coj zoo li cationic surfactants thiab nyob rau hauv nruab nrab media xws li amphoteric surfactants. Lauryl lysine (LL) thiab alkoxy (2-hydroxypropyl) arginine yog tib lub npe hu ua amphoteric surfactants raws li cov amino acids. LL yog ib qho khoom siv condensation ntawm lysine thiab lauric acid. Vim nws cov qauv amphoteric, LL yog insoluble nyob rau hauv yuav luag txhua hom kuab tshuaj, tshwj tsis yog rau alkaline heev los yog acidic kuab tshuaj. Raws li cov organic hmoov, LL muaj qhov zoo heev adhesion rau hydrophilic nto thiab tsis tshua muaj coefficient ntawm kev sib txhuam, muab cov surfactant zoo heev lubricating muaj peev xwm. LL yog dav siv nyob rau hauv daim tawv nqaij cream thiab cov plaub hau conditioners, thiab kuj yog siv los ua lubricant.
④ Nonionic AAS
Nonionic surfactants yog tus cwj pwm los ntawm cov pawg polar taub hau yam tsis muaj nqi raug cai. yim tshiab ethoxylated nonionic surfactants tau npaj los ntawm Al-Sabagh li al. los ntawm cov roj-soluble α-amino acids. Hauv cov txheej txheem no, L-phenylalanine (LEP) thiab L-leucine tau ua ntej esterified nrog hexadecanol, tom qab ntawd los ntawm amidation nrog palmitic acid muab ob amides thiab ob esters ntawm α-amino acids. Cov amides thiab esters tom qab ntawd ua rau muaj kev sib txuam nrog ethylene oxide los npaj peb phenylalanine derivatives nrog ntau tus lej ntawm polyoxyethylene units (40, 60 thiab 100). Cov nonionic AAS tau pom tias muaj cov tshuaj ntxuav tes zoo thiab ua npuas dej.
05 Synthesis
5.1 Basic synthetic route
Hauv AAS, pawg hydrophobic tuaj yeem txuas rau amine lossis carboxylic acid qhov chaw, lossis los ntawm cov saw hlau ntawm cov amino acids. Raws li qhov no, plaub txoj kev siv hluavtaws yog muaj, raws li pom hauv daim duab 5.
Fig.5 Cov txheej txheem synthesis ntawm amino acid-based surfactants
| Txoj kev 1. Amphiphilic ester amines yog tsim los ntawm cov tshuaj tiv thaiv esterification, nyob rau hauv cov ntaub ntawv ntawm surfactant synthesis feem ntau ua tiav los ntawm refluxing fatty alcohols thiab amino acids nyob rau hauv lub xub ntiag ntawm ib tug dehydrating neeg sawv cev thiab ib tug acidic catalyst. Hauv qee cov tshuaj tiv thaiv, sulfuric acid ua ob qho tib si catalyst thiab lub cev qhuav dej.
Txoj kev 2. Activated amino acids react nrog alkylamines los tsim amide bonds, uas ua rau cov synthesis ntawm amphiphilic amidoamines.
Txoj kev 3. Amido acids yog synthesized los ntawm reacting amine pawg ntawm amino acids nrog Amido Acids.
Txoj kev 4. Long-chain alkyl amino acids tau tsim los ntawm cov tshuaj tiv thaiv ntawm amine pawg nrog haloalkanes. |
5.2 Kev nce qib hauv kev sib xyaw thiab kev tsim khoom
5.2.1 Synthesis ntawm ib leeg-chain amino acid/peptide surfactants
N-acyl lossis O-acyl amino acids lossis peptides tuaj yeem tsim los ntawm enzyme-catalyzed acylation ntawm amine lossis hydroxyl pawg nrog fatty acids. Daim ntawv tshaj tawm ntxov tshaj plaws ntawm cov kuab tshuaj tsis muaj lipase-catalyzed synthesis ntawm amino acid amide lossis methyl ester derivatives siv Candida antarctica, nrog cov txiaj ntsig ntawm 25% mus rau 90% nyob ntawm lub hom phiaj amino acid. Methyl ethyl ketone kuj tau siv los ua cov kuab tshuaj hauv qee cov tshuaj tiv thaiv. Vonderhagen et al. kuj tau piav qhia txog lipase thiab protease-catalyzed N-acylation cov tshuaj tiv thaiv ntawm cov amino acids, protein hydrolysates thiab / lossis lawv cov derivatives uas siv cov dej sib tov thiab cov kuab tshuaj organic (xws li, dimethylformamide / dej) thiab methyl butyl ketone.
Thaum ntxov, qhov teeb meem tseem ceeb ntawm enzyme-catalyzed synthesis ntawm AAS yog qhov tsis tshua muaj txiaj ntsig. Raws li Valivety et al. Cov txiaj ntsig ntawm N-tetradecanoyl amino acid derivatives tsuas yog 2% -10% txawm tias tom qab siv cov lipases sib txawv thiab incubating ntawm 70 ° C rau ntau hnub. Montet et al. kuj tau ntsib teeb meem hais txog qhov tsis tshua muaj txiaj ntsig ntawm cov amino acids nyob rau hauv cov synthesis ntawm N-acyl lysine siv fatty acids thiab zaub roj. Raws li lawv, qhov siab tshaj plaws tawm los ntawm cov khoom yog 19% nyob rau hauv hnyav-dawb tej yam kev mob thiab siv organic solvents. tib qhov teeb meem tau ntsib los ntawm Valivety li al. nyob rau hauv lub synthesis ntawm N-Cbz-L-lysine los yog N-Cbz-lysine methyl ester derivatives.
Hauv txoj kev tshawb no, lawv tau thov tias cov txiaj ntsig ntawm 3-O-tetradecanoyl-L-serine yog 80% thaum siv N-tiv thaiv serine ua substrate thiab Novozyme 435 ua ib qho catalyst nyob rau hauv ib puag ncig molten tsis muaj kuab tshuaj. Nagao thiab Kito tau kawm O-acylation ntawm L-serine, L-homoserine, L-threonine thiab L-tyrosine (LET) thaum siv lipase Cov txiaj ntsig ntawm cov tshuaj tiv thaiv (lipase tau txais los ntawm Candida cylindracea thiab Rhizopus delemar hauv aqueous buffer nruab nrab) thiab tau tshaj tawm tias cov txiaj ntsig ntawm acylation ntawm L-homoserine thiab L-serine tau qis me ntsis, thaum tsis muaj acylation ntawm L-threonine thiab LET tshwm sim.
Ntau tus kws tshawb fawb tau txhawb nqa kev siv pheej yig thiab yooj yim muaj cov substrates rau kev sib txuas ntawm cov nqi-zoo AAS. Tso et al. tau thov tias kev npaj cov roj txiv roj raws li surfactants ua haujlwm zoo tshaj plaws nrog immobilized lipoenzyme. Lawv tau sau tseg tias cov txiaj ntsig ntawm cov khoom yuav zoo dua txawm tias lub sijhawm siv tshuaj tiv thaiv (6 hnub). Gerova et al. tshawb xyuas cov synthesis thiab deg kev ua si ntawm chiral N-palmitoyl AAS raws li methionine, proline, leucine, threonine, phenylalanine thiab phenylglycine nyob rau hauv ib tug cyclic/racemic sib tov. Pang thiab Chu tau piav qhia txog kev sib txuas ntawm cov amino acid raws li monomers thiab dicarboxylic acid raws monomers hauv kev daws A series ntawm kev ua haujlwm thiab biodegradable amino acid-based polyamide esters tau tsim los ntawm kev sib xyaw ua ke hauv kev daws teeb meem.
Cantaeuzene thiab Guerreiro tau tshaj tawm cov esterification ntawm carboxylic acid pawg ntawm Boc-Ala-OH thiab Boc-Asp-OH nrog cov saw ntev aliphatic cawv thiab diols, nrog dichloromethane ua hnyav thiab agarose 4B (Sepharose 4B) ua catalyst. Nyob rau hauv txoj kev tshawb no, cov tshuaj tiv thaiv ntawm Boc-Ala-OH nrog fatty alcohols mus txog 16 carbons muab zoo yields (51%), thaum rau Boc-Asp-OH 6 thiab 12 carbons tau zoo dua, nrog ib tug coj yield ntawm 63% [64. ]. 99.9%) nyob rau hauv yields li ntawm 58% mus rau 76%, uas yog synthesized los ntawm kev tsim ntawm amide bonds nrog ntau yam ntev-chain alkylamines los yog ester bonds nrog fatty alcohols los ntawm Cbz-Arg-OMe, qhov twg papain ua raws li ib tug catalyst.
5.2.2 Synthesis ntawm gemini-based amino acid/peptide surfactants
Amino acid-based gemini surfactants muaj ob txoj hlua ncaj nraim AAS molecules txuas lub taub hau-rau-lub taub hau rau ib leeg los ntawm ib pawg spacer. Muaj 2 lub tswv yim ua tau rau chemoenzymatic synthesis ntawm gemini-type amino acid-based surfactants (Figures 6 thiab 7). Nyob rau hauv daim duab 6, 2 amino acid derivatives yog reacted nrog lub compound raws li ib tug spacer pab pawg neeg thiab ces 2 hydrophobic pawg yog qhia. Nyob rau hauv daim duab 7, 2 txoj hlua ncaj nraim yog txuas ncaj qha ua ke los ntawm ib pawg bifunctional spacer.
Kev txhim kho ntxov tshaj plaws ntawm enzyme-catalyzed synthesis ntawm gemini lipoamino acids tau pioneered los ntawm Valivety li al. Yoshimura et al. tshawb xyuas cov synthesis, adsorption thiab aggregation ntawm cov amino acid-based gemini surfactant raws li cystine thiab n-alkyl bromide. Cov synthesized surfactants tau muab piv nrog cov sib txuam monomeric surfactants. Faustino et al. piav qhia txog kev sib txuas ntawm anionic urea-raws li monomeric AAS raws li L-cystine, D-cystine, DL-cystine, L-cysteine, L-methionine thiab L-sulfoalanine thiab lawv cov khub ntawm gemini los ntawm kev coj ua, sib npaug ntawm qhov nro thiab khov kho. -state fluorescence characterization ntawm lawv. Nws tau pom tias tus nqi cmc ntawm gemini tau qis dua los ntawm kev sib piv monomer thiab gemini.
Fig.6 Synthesis of gemini AAS siv AA derivatives thiab spacer, tom qab ntawd los ntawm kev ntxig ntawm pawg hydrophobic
Fig.7 Synthesis of gemini AASs siv bifunctional spacer thiab AAS
5.2.3 Synthesis ntawm glycerollipid amino acid/peptide surfactants
Glycerollipid amino acid / peptide surfactants yog ib chav kawm tshiab ntawm lipid amino acids uas yog cov qauv analogues ntawm glycerol mono- (los yog di-) esters thiab phospholipids, vim lawv cov qauv ntawm ib los yog ob fatty chains nrog ib qho amino acid txuas rau glycerol qaum. los ntawm ester daim ntawv cog lus. Lub synthesis ntawm cov surfactants pib nrog kev npaj ntawm glycerol esters ntawm cov amino acids ntawm qhov kub thiab txias thiab nyob rau hauv lub xub ntiag ntawm ib tug acidic catalyst (xws li BF 3). Enzyme-catalyzed synthesis (siv hydrolases, proteases thiab lipases ua catalysts) kuj yog ib qho kev xaiv zoo (Daim duab 8).
Cov enzyme-catalyzed synthesis ntawm dilaurylated arginine glycerides conjugates siv papain tau tshaj tawm. Synthesis ntawm diacylglycerol ester conjugates los ntawm acetylarginine thiab kev ntsuam xyuas ntawm lawv cov physicochemical zog kuj tau qhia.
Fig.8 Synthesis ntawm mono thiab diacylglycerol amino acid conjugates
spacer: NH-(CH2)10-NH: compoundB1
Tus Qauv Zauv: NH-C6H4-NH: compoundB2
spacer: CH2-CH2:qib B3
Fig.9 Synthesis of symmetric amphiphiles derived from Tris(hydroxymethyl)aminomethane
5.2.4 Synthesis of bola-based amino acid/peptide surfactants
Amino acid-raws li bola-hom amphiphiles muaj 2 amino acids uas txuas nrog tib cov saw hydrophobic. Franceschi et al. piav qhia txog kev sib txuas ntawm bola-hom amphiphiles nrog 2 amino acids (D- lossis L-alanine lossis L-histidine) thiab 1 alkyl saw ntawm qhov ntev sib txawv thiab tshawb xyuas lawv cov haujlwm saum npoo. Lawv sib tham txog kev sib txuas thiab sib sau ua ke ntawm cov tshiab bola-hom amphiphiles nrog cov amino acid feem (siv ib qho tsis tshua muaj β-amino acid lossis cawv) thiab C12-C20 spacer pawg. Cov tsis tshua muaj β-amino acids uas siv tau tuaj yeem yog cov suab thaj aminoacid, ib qho azidothymin (AZT)-derived amino acid, norbornene amino acid, thiab cov amino cawv tau los ntawm AZT (Daim duab 9). cov synthesis ntawm symmetrical bola-hom amphiphiles muab tau los ntawm tris (hydroxymethyl) aminomethane (Tris) (Daim duab 9).
06 Physicochemical zog
Nws paub zoo tias cov amino acid raws li surfactants (AAS) muaj ntau haiv neeg thiab muaj ntau yam hauv cov xwm txheej thiab muaj kev siv tau zoo hauv ntau daim ntawv thov xws li solubilization zoo, zoo emulsification zog, kev ua haujlwm siab, kev ua haujlwm siab thiab ua haujlwm zoo rau cov dej tawv (calcium ion). kam rau ua).
Raws li cov khoom siv surfactant ntawm cov amino acids (xws li nto nro, cmc, theem tus cwj pwm thiab Kafft kub), cov lus xaus hauv qab no tau mus txog tom qab kev tshawb fawb dav dav - qhov kev ua ntawm AAS yog superior rau nws cov pa surfactant counterpart.
6.1 Critical Mcelle Concentration (cmc)
Qhov tseem ceeb micelle concentration yog ib qho ntawm cov tsis tseem ceeb ntawm surfactants thiab tswj hwm ntau qhov chaw ua haujlwm xws li solubilization, cell lysis thiab nws cov kev cuam tshuam nrog biofilms, thiab lwm yam. Feem ntau, ua kom cov saw ntev ntawm hydrocarbon Tail (nce hydrophobicity) ua rau txo qis. nyob rau hauv cmc tus nqi ntawm cov tshuaj surfactant, yog li nce nws cov dej num nto. Surfactants raws li cov amino acids feem ntau muaj qis dua cmc piv rau cov pa surfactants.
Los ntawm kev sib xyaw ua ke ntawm cov taub hau thiab cov tails hydrophobic (mono-cationic amide, bi-cationic amide, bi-cationic amide-based ester), Infante et al. synthesized peb arginine-raws li AAS thiab kawm lawv cmc thiab γcmc (nto nro ntawm cmc), uas qhia tau hais tias cov cmc thiab γcmc qhov tseem ceeb poob nrog nce hydrophobic Tail ntev. Hauv lwm txoj kev tshawb fawb, Singare thiab Mhatre pom tias cmc ntawm N-α-acylarginine surfactants tau txo qis nrog kev nce tus naj npawb ntawm hydrophobic tail carbon atoms (Table 1).
Yoshimura et al. tshawb xyuas cmc ntawm cysteine-derived amino acid-raws li gemini surfactants thiab pom tias cmc poob thaum cov carbon saw ntev nyob rau hauv hydrophobic saw tau nce los ntawm 10 mus rau 12. Kev nce ntxiv ntawm cov saw hlau ntev mus rau 14 ua rau kev nce hauv cmc, uas tau lees paub tias cov saw ntev gemini surfactants muaj qhov qis dua rau kev sib sau.
Faustino et al. qhia txog kev tsim cov micelles sib xyaw hauv cov tshuaj aqueous ntawm anionic gemini surfactants raws li cystine. Cov gemini surfactants kuj tau muab piv nrog cov qauv monomeric surfactants (C 8 Cys). Cov txiaj ntsig ntawm cmc ntawm lipid-surfactant sib tov tau tshaj tawm tias qis dua li cov ntshiab surfactants. gemini surfactants thiab 1,2-diheptanoyl-sn-glyceryl-3-phosphocholine, dej-soluble, micelle-forming phospholipid, muaj cmc nyob rau hauv millimolar theem.
Shrestha thiab Aramaki tau tshawb xyuas qhov tsim ntawm viscoelastic worm zoo li micelles nyob rau hauv cov kev daws teeb meem ntawm cov amino acid-raws li anionic-noionic surfactants nyob rau hauv tsis muaj admixture ntsev. Hauv txoj kev tshawb no, N-dodecyl glutamate tau pom tias muaj qhov kub thiab txias dua Kafft; Txawm li cas los xij, thaum nruab nrab nrog cov amino acid L-lysine, nws tsim cov micelles thiab cov tshuaj pib coj tus cwj pwm zoo li cov kua Newtonian ntawm 25 ° C.
6.2 Zoo solubility dej
Cov dej zoo solubility ntawm AAS yog vim muaj cov CO-NH daim ntawv cog lus ntxiv. Qhov no ua rau AAS ntau biodegradable thiab ib puag ncig tus phooj ywg dua li cov pa surfactants sib xws. Cov dej solubility ntawm N-acyl-L-glutamic acid yog qhov zoo dua vim nws 2 pawg carboxyl. Cov dej solubility ntawm Cn (CA) 2 kuj yog qhov zoo vim tias muaj 2 pawg ionic arginine hauv 1 molecule, uas ua rau muaj txiaj ntsig zoo dua adsorption thiab diffusion ntawm lub xovtooj ntawm tes thiab txawm tias muaj txiaj ntsig zoo ntawm cov kab mob hauv qis dua.
6.3 Kafft kub thiab Kafft point
Kafft kub tuaj yeem nkag siab raws li tus cwj pwm tshwj xeeb solubility ntawm surfactants uas nws solubility nce siab tshaj qhov kub thiab txias. Ionic surfactants muaj ib tug nyiam los tsim cov khoom hydrates, uas tuaj yeem ua dej los ntawm dej. Ntawm qhov kub thiab txias (qhov hu ua Kafft kub), feem ntau pom muaj qhov ua kom zoo thiab tsis tu ncua ntawm solubility ntawm surfactants. Kafft point ntawm ib qho ionic surfactant yog nws qhov kub thiab txias ntawm cmc.
Cov yam ntxwv solubility no feem ntau pom rau ionic surfactants thiab tuaj yeem piav qhia raws li hauv qab no: solubility ntawm cov surfactant dawb monomer yog txwv qis dua qhov kub ntawm Kafft mus txog rau qhov Kafft point, qhov twg nws solubility maj mam nce vim micelle tsim. Txhawm rau ua kom tiav solubility, nws yog ib qho tsim nyog los npaj cov tshuaj surfactant ntawm qhov kub siab tshaj qhov Kafft point.
Lub Kafft kub ntawm AAS tau kawm thiab muab piv nrog cov pa hluavtaws surfactants.Shrestha thiab Aramaki tau kawm Kafft kub ntawm arginine-based AAS thiab pom tias qhov tseem ceeb micelle concentration nthuav tawm tus cwj pwm sib sau ua ke hauv daim ntawv ntawm pre-micelles saum toj 2-5. × 10-6 mol-L -1 ua raws li ib txwm micelle tsim (Ohta li al. synthesized rau ntau hom N-hexadecanoyl AAS thiab tham txog kev sib raug zoo ntawm lawv cov Kafft kub thiab cov amino acid residues.
Hauv kev sim, nws tau pom tias Kafft kub ntawm N-hexadecanoyl AAS nce nrog txo qhov loj ntawm cov amino acid residues (phenylalanine yog ib qho kev zam), thaum tshav kub ntawm solubility (heat uptake) nce nrog txo qhov loj ntawm amino acid residues (nrog rau kev zam ntawm glycine thiab phenylalanine). Nws tau txiav txim siab tias nyob rau hauv ob qho tib si alanine thiab phenylalanine systems, DL kev sib cuam tshuam muaj zog dua li LL kev sib cuam tshuam hauv cov khoom ntawm N-hexadecanoyl AAS ntsev.
Brito et al. Kev txiav txim siab ntawm Kafft kub ntawm peb series ntawm cov amino acid-raws li surfactants tshiab siv qhov sib txawv scanning microcalorimetry thiab pom tias hloov cov trifluoroacetate ion mus rau iodide ion ua rau muaj qhov tseem ceeb ntawm Kafft kub (kwv yees li 6 ° C), los ntawm 47 ° C mus rau 53 ° C. C. Lub xub ntiag ntawm cis-ob daim ntawv cog lus thiab qhov tsis txaus ntseeg tam sim no nyob rau hauv cov saw ntev Ser-derivatives coj mus rau qhov txo qis hauv Kafft kub. n-Dodecyl glutamate tau tshaj tawm tias muaj Kafft kub dua. Txawm li cas los xij, neutralization nrog cov amino acid hauv paus L-lysine ua rau tsim cov micelles hauv kev daws teeb meem uas coj zoo li Newtonian kua dej ntawm 25 ° C.
6.4 Nto nro
Qhov nro ntawm surfactants muaj feem xyuam rau cov saw ntev ntawm qhov hydrophobic. Zhang et al. Kev txiav txim siab saum npoo ntawm sodium cocoyl glycinate los ntawm Wilhelmy phaj txoj kev (25 ± 0.2) ° C thiab txiav txim siab qhov nro ntawm tus nqi ntawm cmc li 33 mN-m -1, cmc li 0.21 mmol-L -1. Yoshimura et al. txiav txim siab qhov nro ntawm 2C n Cys hom amino acid raws li qhov ntom ntom ntom ntom ntawm 2C n Cys-raws li cov neeg ua haujlwm nto. Nws tau pom tias qhov nro ntawm cmc txo qis nrog cov saw ntev (txog n = 8), thaum qhov sib txawv tau hloov mus rau surfactants nrog n = 12 lossis ntev saw ntev.
Cov nyhuv ntawm CaC1 2 ntawm qhov nro ntawm dicarboxylated amino acid-based surfactants kuj tau kawm. Hauv cov kev tshawb fawb no, CaC1 2 tau ntxiv rau cov kev daws teeb meem ntawm peb dicarboxylated amino acid-type surfactants (C12 MalNa 2, C12 AspNa 2, thiab C12 GluNa 2). Lub toj siab qhov tseem ceeb tom qab cmc tau muab piv thiab nws tau pom tias qhov nro ntawm qhov chaw poob qis heev ntawm CaC1 2 concentrations. Qhov no yog vim cov nyhuv ntawm calcium ions ntawm kev npaj ntawm cov surfactant ntawm cov roj-dej interface. Ntawm qhov tod tes, cov ntsev ntawm N-dodecylaminomalonate thiab N-dodecylaspartate, kuj tseem yuav luag tas li mus txog 10 mmol-L -1 CaC1 2 concentration. Tshaj li 10 mmol-L -1, qhov nro ntawm qhov chaw nce siab, vim yog kev tsim cov nag lossis daus ntawm calcium ntsev ntawm surfactant. Rau cov ntsev disodium ntawm N-dodecyl glutamate, nruab nrab ntxiv ntawm CaC1 2 ua rau muaj qhov txo qis hauv qhov nro, thaum txuas ntxiv nce hauv CaC1 2 concentration tsis ua rau muaj kev hloov pauv tseem ceeb.
Txhawm rau txiav txim siab qhov adsorption kinetics ntawm gemini-hom AAS ntawm cov pa roj-dej interface, lub zog ntawm qhov nro tau txiav txim siab siv txoj kev ua npuas siab tshaj plaws. Cov txiaj ntsig tau pom tias lub sijhawm sim ntev tshaj plaws, 2C 12 Cys dynamic nto nro tsis hloov. Qhov txo qis ntawm qhov dynamic nto nro tsuas yog nyob ntawm qhov concentration, qhov ntev ntawm hydrophobic tails, thiab tus naj npawb ntawm hydrophobic tails. Ua kom cov concentration ntawm surfactant, txo cov saw ntev raws li cov xov tooj ntawm cov chains ua rau kev lwj sai dua. Cov txiaj ntsig tau txais rau ntau dua ntawm C n Cys (n = 8 txog 12) tau pom tias nyob ze rau γ cmc ntsuas los ntawm Wilhelmy txoj kev.
Hauv lwm txoj kev tshawb fawb, qhov dynamic deg tensions ntawm sodium dilauryl cystine (SDLC) thiab sodium didecamino cystine tau txiav txim los ntawm Wilhelmy phaj txoj kev, thiab ntxiv rau, qhov sib npaug ntawm qhov sib npaug ntawm lawv cov kev daws teeb meem tau txiav txim siab los ntawm txoj kev poob ntim. Cov tshuaj tiv thaiv ntawm disulfide bonds tau tshawb xyuas ntxiv los ntawm lwm txoj kev thiab. Qhov sib ntxiv ntawm mercaptoethanol rau 0.1 mmol-L -1SDLC cov tshuaj ua rau muaj kev nce ceev ntawm qhov nro ntawm 34 mN-m -1 txog 53 mN-m -1. Txij li thaum NaClO tuaj yeem oxidize cov disulfide bonds ntawm SDLC rau sulfonic acid pawg, tsis muaj kev sib sau ua ke thaum NaClO (5 mmol-L -1) ntxiv rau 0.1 mmol-L -1 SDLC tov. Kev sib kis ntawm electron microscopy thiab dynamic light scattering tshwm sim tau pom tias tsis muaj kev sib sau ua ke hauv cov tshuaj. Qhov nro ntawm SDLC tau pom tias nce los ntawm 34 mN-m -1 txog 60 mN-m -1 nyob rau lub sijhawm ntawm 20 min.
6.5 Binary nto kev sib tshuam
Nyob rau hauv lub neej sciences, ib tug xov tooj ntawm pab pawg tau kawm lub vibrational zog ntawm mixs ntawm cationic AAS (diacylglycerol arginine-raws li surfactants) thiab phospholipids nyob rau hauv lub gas-dej interface, thaum kawg txiav txim siab hais tias qhov no tsis yog-zoo tagnrho vaj tse ua rau cov feem ntau ntawm electrostatic kev sib cuam tshuam.
6.6 Aggregation zog
Dynamic lub teeb tawg yog feem ntau siv los txiav txim siab cov khoom sib xyaw ntawm cov amino acid-raws li monomers thiab gemini surfactants ntawm qhov siab tshaj cmc, yielding pom tseeb hydrodynamic txoj kab uas hla DH (= 2R H ). Cov aggregates tsim los ntawm C n Cys thiab 2Cn Cys yog qhov loj thiab muaj qhov dav dav faib piv rau lwm cov surfactants. Tag nrho cov surfactants tshwj tsis yog 2C 12 Cys feem ntau tsim cov aggregates txog 10 nm. micelle qhov ntau thiab tsawg ntawm gemini surfactants yog qhov loj dua li ntawm lawv cov monomeric counterparts. Kev nce hauv hydrocarbon saw ntev kuj ua rau muaj kev nce hauv micelle loj. aw et al. piav qhia txog kev sib sau ua ke ntawm peb qhov sib txawv stereoisomers ntawm N-dodecyl-phenyl-alanyl-phenyl-alanine tetramethylammonium hauv aqueous tov thiab pom tias cov diastereoisomers muaj tib qhov tseem ceeb aggregation concentration hauv aqueous tov. Iwahashi et al. tshawb xyuas los ntawm ncig dichroism, NMR thiab vapor siab osmometry qhov tsim ntawm chiral aggregates ntawm N-dodecanoyl-L-glutamic acid, N-dodecanoyl-L-valine thiab lawv cov methyl esters hauv cov kuab tshuaj sib txawv (xws li tetrahydrofuran, acetonitrile, 1,4 -dioxane thiab 1,2-dichloroethane) nrog cov khoom sib hloov tau tshawb xyuas los ntawm ncig dichroism, NMR thiab vapor siab osmometry.
6.7 Interfacial adsorption
Lub interfacial adsorption ntawm amino acid-raws li surfactants thiab nws cov kev sib piv nrog nws cov pa counterpart kuj yog ib qho ntawm cov kev tshawb fawb qhia. Piv txwv li, lub interfacial adsorption zog ntawm dodecyl esters ntawm aromatic amino acids tau los ntawm LET thiab LEP tau tshawb xyuas. Cov txiaj ntsig tau pom tias LET thiab LEP tau nthuav tawm cov cheeb tsam sab hauv qis ntawm cov roj-kua interface thiab ntawm dej / hexane interface, raws li.
Bordes et al. tshawb xyuas tus cwj pwm kev daws teeb meem thiab adsorption ntawm cov roj-dej interface ntawm peb dicarboxylated amino acid surfactants, disodium ntsev ntawm dodecyl glutamate, dodecyl aspartate, thiab aminomalonate (nrog 3, 2, thiab 1 carbon atoms ntawm ob pawg carboxyl, raws li). Raws li tsab ntawv ceeb toom no, cmc ntawm dicarboxylated surfactants yog 4-5 npaug siab dua li ntawm cov ntsev monocarboxylated dodecyl glycine. Qhov no yog vim qhov tsim ntawm hydrogen bonds ntawm dicarboxylated surfactants thiab cov nyob sib ze molecules los ntawm cov pab pawg amide nyob rau hauv.
6.8 Theem tus cwj pwm
Isotropic discontinuous cubic theem tau pom rau surfactants ntawm qhov siab heev. Surfactant molecules nrog lub taub hau loj heev yuav ua rau cov sib sau ua ke ntawm qhov zoo me me curvature. marques et al. tau kawm txog theem tus cwj pwm ntawm 12Lys12/12Ser thiab 8Lys8/16Ser systems (saib daim duab 10), thiab cov txiaj ntsig tau pom tias 12Lys12/12Ser system muaj cov theem sib cais ntawm thaj tsam micellar thiab vesicular tov, thaum lub 8Lys8/16Ser system. 8Lys8/16Ser system qhia txog kev hloov pauv tsis tu ncua (elongated micellar theem cheeb tsam nruab nrab ntawm cheeb tsam me me micellar theem thiab cheeb tsam vesicle theem). Nws yuav tsum raug sau tseg tias rau thaj tsam vesicle ntawm 12Lys12/12Ser system, vesicles ib txwm nyob nrog micelles, thaum lub vesicle cheeb tsam ntawm 8Lys8/16Ser system tsuas muaj vesicles.
Catanionic sib tov ntawm lysine- thiab serine-raws li surfactants: symmetric 12Lys12/12Ser khub (sab laug) thiab asymmetric 8Lys8/16Ser khub (txoj cai)
6.9 Emulsifying muaj peev xwm
Koj et al. tshuaj xyuas lub peev xwm emulsifying, interfacial nro, dispersibility, thiab viscosity ntawm N-[3-dodecyl-2-hydroxypropyl]-L-arginine, L-glutamate, thiab lwm yam AAS. Hauv kev sib piv nrog hluavtaws surfactants (lawv cov pa nonionic thiab amphoteric counterparts), cov txiaj ntsig tau pom tias AAS muaj peev xwm emulsifying muaj zog dua li cov pa surfactants.
Baczko et al. synthesized tshiab anionic amino acid surfactants thiab tshawb xyuas lawv qhov haum raws li chiral oriented NMR spectroscopy solvents. Ib tug series ntawm sulfonate-raws li amphiphilic L-Phe los yog L-Ala derivatives nrog txawv hydrophobic tails (pentyl ~ tetradecyl) tau synthesized los ntawm reacting amino acids nrog o-sulfobenzoic anhydride. Wu et al. synthesized sodium ntsev ntawm N-fatty acyl AAS thiabtshawb xyuas lawv lub peev xwm emulsification hauv roj-hauv-dej emulsions, thiab cov txiaj ntsig tau pom tias cov surfactants ua tau zoo dua nrog ethyl acetate raws li cov roj theem dua li n-hexane raws li cov roj theem.
6.10 Kev nce qib hauv synthesis thiab ntau lawm
Cov dej tsis muaj zog tuaj yeem nkag siab tias lub peev xwm ntawm surfactants los tiv thaiv cov ions xws li calcium thiab magnesium hauv cov dej tawv, piv txwv li, muaj peev xwm zam nag lossis daus rau hauv calcium soaps. Surfactants nrog lub siab tawv dej kuj tseem ceeb heev rau cov tshuaj detergent formulations thiab cov khoom tu tus kheej. Cov dej tsis muaj zog tuaj yeem ntsuas tau los ntawm kev suav cov kev hloov pauv hauv solubility thiab kev ua haujlwm saum npoo ntawm cov surfactant nyob rau hauv muaj cov calcium ions.
Lwm txoj hauv kev los ntsuas cov dej tsis zoo yog suav cov feem pua lossis grams ntawm surfactant xav tau rau cov calcium xab npum uas tsim los ntawm 100 g ntawm sodium oleate kom tawg hauv dej. Hauv cov cheeb tsam uas muaj dej nyuaj, cov ntsiab lus siab ntawm calcium thiab magnesium ions thiab cov ntxhia hauv cov ntsiab lus tuaj yeem ua rau qee qhov kev siv tswv yim nyuaj. Feem ntau cov sodium ion yog siv los ua lub txee ion ntawm ib qho hluavtaws anionic surfactant. Txij li thaum lub divalent calcium ion yog khi rau ob qho tib si surfactant molecules, nws ua rau cov surfactant los precipitate ntau yooj yim los ntawm kev daws ua detergency tsawg dua.
Txoj kev tshawb fawb ntawm cov dej tsis haum ntawm AAS tau pom tias cov kua qaub thiab cov dej tsis sib haum tau muaj kev cuam tshuam los ntawm ib pawg carboxyl ntxiv, thiab cov kua qaub thiab cov dej tsis sib haum tau nce ntxiv nrog qhov nce ntawm qhov ntev ntawm pawg spacer ntawm ob pawg carboxyl. . Qhov kev txiav txim ntawm cov kua qaub thiab cov dej tsis haum yog C 12 glycinate <C 12 aspartate < C 12 glutamate. Muab piv cov dicarboxylated amide daim ntawv cog lus thiab cov dicarboxylated amino surfactant, feem, nws tau pom tias qhov pH ntau ntawm tom kawg tau dav dua thiab nws cov dej num saum npoo tau nce ntxiv nrog rau qhov sib ntxiv ntawm cov kua qaub. Cov dicarboxylated N-alkyl amino acids pom cov nyhuv chelating nyob rau hauv lub xub ntiag ntawm calcium ions, thiab C 12 aspartate tsim dawb gel. c 12 glutamate pom qhov ua haujlwm siab ntawm qhov siab Ca 2+ concentration thiab yuav tsum tau siv rau hauv dej hiav txwv desalination.
6.11 Dispersibility
Dispersibility hais txog lub peev xwm ntawm surfactant los tiv thaiv coalescence thiab sedimentation ntawm surfactant hauv kev daws.Dispersibility yog ib qho khoom tseem ceeb ntawm surfactants uas ua rau lawv tsim nyog siv rau hauv cov tshuaj ntxuav tes, tshuaj pleev ib ce thiab tshuaj.Tus neeg sawv cev dispersing yuav tsum muaj ib qho ester, ether, amide los yog amino bond ntawm pawg hydrophobic thiab cov pawg hydrophilic terminal (los yog ntawm cov kab ncaj nraim hydrophobic pawg).
Feem ntau, anionic surfactants xws li alkanolamido sulfates thiab amphoteric surfactants xws li amidosulfobetaine yog tshwj xeeb tshaj yog zoo li dispersing agents rau calcium soaps.
Ntau qhov kev tshawb fawb tau txiav txim siab qhov sib txawv ntawm AAS, qhov twg N-lauroyl lysine tau pom tias tsis zoo nrog dej thiab nyuaj rau kev siv cov tshuaj pleev ib ce.Nyob rau hauv cov koob no, N-acyl-hloov cov amino acids yooj yim dispersibility thiab siv nyob rau hauv kev lag luam tshuaj pleev ib ce los txhim kho formulations.
07 Kev toxicity
Cov pa surfactants, tshwj xeeb tshaj yog cov cationic surfactants, muaj tshuaj lom heev rau cov kab mob hauv dej. Lawv mob toxicity yog vim qhov tshwm sim ntawm adsorption-ion kev cuam tshuam ntawm surfactants ntawm tes-dej interface. Txo cov cmc ntawm surfactants feem ntau ua rau muaj zog interfacial adsorption ntawm surfactants, uas feem ntau ua rau lawv toxicity siab. Kev nce hauv qhov ntev ntawm cov saw hlau hydrophobic ntawm surfactants kuj ua rau muaj kev nce ntxiv ntawm cov tshuaj tua kab mob.Feem ntau AAS muaj tsawg lossis tsis muaj tshuaj lom rau tib neeg thiab ib puag ncig (tshwj xeeb yog cov kab mob hauv hiav txwv) thiab tsim nyog siv los ua cov khoom xyaw zaub mov, tshuaj thiab tshuaj pleev ib ce.Ntau tus kws tshawb fawb tau pom tias cov amino acid surfactants maj mam thiab tsis ua rau tawv nqaij. Arginine-raws li surfactants paub tias muaj tshuaj lom tsawg dua li lawv cov khoom sib xyaw ua ke.
Brito et al. tau kawm txog physicochemical thiab toxicological zog ntawm amino acid-raws li amphiphiles thiab lawv [derivatives los ntawm tyrosine (Tyr), hydroxyproline (Hyp), serine (Ser) thiab lysine (Lys)] spontaneous tsim ntawm cationic vesicles thiab muab cov ntaub ntawv ntawm lawv mob toxicity rau Daphnia Magna (IC 50). Lawv tau tsim cov cationic vesicles ntawm dodecyltrimethylammonium bromide (DTAB) / Lys-derivatives thiab / los yog Ser-/Lys-derivative mixs thiab kuaj lawv cov ecotoxicity thiab hemolytic peev xwm, qhia tias tag nrho cov AAS thiab lawv cov vesicle-muaj cov khoom sib xyaw tsis tshua muaj tshuaj lom tshaj li cov pa DTAB surfactant. .
Rosa et al. tshawb xyuas kev khi (kev koom ua ke) ntawm DNA kom ruaj khov amino acid-based cationic vesicles. Tsis zoo li cov pa cationic surfactants, uas feem ntau zoo li muaj tshuaj lom, kev sib cuam tshuam ntawm cationic amino acid surfactants zoo li tsis muaj tshuaj lom. Lub cationic AAS yog raws li arginine, uas spontaneously tsim vesicles ruaj khov nyob rau hauv ua ke nrog rau tej yam anionic surfactants. Amino acid-based corrosion inhibitors kuj tau tshaj tawm tias tsis muaj tshuaj lom. Cov surfactants tau yooj yim ua ke nrog siab purity (txog 99%), tus nqi qis, yooj yim biodegradable, thiab soluble tag nrho hauv aqueous media. Ntau cov kev tshawb fawb tau pom tias sulfur-muaj amino acid surfactants zoo tshaj hauv kev tiv thaiv corrosion.
Hauv kev tshawb fawb tsis ntev los no, Perinelli li al. Tshaj tawm qhov txaus siab toxicological profile ntawm rhamnolipids piv rau cov pa surfactants. Rhamnolipids paub tias ua raws li permeability enhancers. Lawv kuj tau tshaj tawm cov txiaj ntsig ntawm rhamnolipids ntawm epithelial permeability ntawm cov tshuaj macromolecular.
08 Antimicrobial kev ua haujlwm
Cov tshuaj tua kab mob ntawm cov tshuaj surfactants tuaj yeem ntsuas los ntawm qhov tsawg kawg nkaus inhibitory concentration. Cov tshuaj tiv thaiv kab mob ntawm arginine-based surfactants tau kawm kom ntxaws. Cov kab mob Gram-negative tau pom tias muaj kev tiv thaiv ntau dua rau arginine-based surfactants dua li cov kab mob Gram-positive. Cov tshuaj tiv thaiv kab mob ntawm cov surfactants feem ntau yog nce los ntawm kev muaj hydroxyl, cyclopropane los yog unsaturated bonds nyob rau hauv acyl chains. Castillo et al. qhia tau hais tias qhov ntev ntawm acyl chains thiab tus nqi zoo txiav txim siab HLB tus nqi (hydrophilic-lipophilic tshuav nyiaj li cas) ntawm cov molecule, thiab cov no muaj feem cuam tshuam rau lawv lub peev xwm los cuam tshuam cov membranes. Nα-acylarginine methyl ester yog lwm chav kawm tseem ceeb ntawm cationic surfactants nrog broad-spectrum antimicrobial kev ua si thiab Nws yog nkag tau yooj yim biodegradable thiab muaj tsawg los yog tsis muaj toxicity. Kev tshawb fawb txog kev sib cuam tshuam ntawm Nα-acylarginine methyl ester-based surfactants nrog 1,2-dipalmitoyl-sn-propyltrioxyl-3-phosphorylcholine thiab 1,2-ditetradecanoyl-sn-propyltrioxyl-3-phosphorylcholine, qauv daim nyias nyias, thiab nrog cov kab mob nyob hauv lub xub ntiag los yog tsis muaj kev thaiv sab nraud tau qhia tias chav kawm ntawm surfactants muaj cov tshuaj tua kab mob zoo Cov txiaj ntsig tau pom tias cov surfactants muaj cov tshuaj tua kab mob zoo.
09 Rheological zog
Cov khoom rheological ntawm surfactants ua lub luag haujlwm tseem ceeb hauv kev txiav txim siab thiab kwv yees lawv cov ntawv thov hauv kev lag luam sib txawv, suav nrog zaub mov, tshuaj, roj rho tawm, kev saib xyuas tus kheej thiab cov khoom siv hauv tsev. Ntau cov kev tshawb fawb tau ua los tham txog kev sib raug zoo ntawm viscoelasticity ntawm amino acid surfactants thiab cmc.
10 Daim ntawv thov hauv kev lag luam tshuaj pleev ib ce
AAS yog siv rau hauv kev tsim ntawm ntau yam khoom tu tus kheej.potassium N-cocoyl glycinate tau pom tias ua rau ntawm daim tawv nqaij thiab siv hauv kev ntxuav lub ntsej muag kom tshem tawm cov sludge thiab pleev. n-Acyl-L-glutamic acid muaj ob pawg carboxyl, uas ua rau nws cov dej ntau dua. Ntawm cov AAS no, AAS raws li C 12 fatty acids tau siv dav hauv kev ntxuav lub ntsej muag kom tshem tawm cov sludge thiab pleev. AAS nrog C 18 saw yog siv los ua emulsifiers hauv cov khoom tu tawv nqaij, thiab N-Lauryl alanine ntsev yog paub los tsim cov nplaum nplaum uas tsis ua rau tawv nqaij thiab yog li siv tau rau hauv kev tsim cov khoom tu menyuam. N-Lauryl-based AAS siv hauv cov tshuaj txhuam hniav muaj cov tshuaj ntxuav tes zoo ib yam li xab npum thiab muaj zog enzyme-inhibiting efficacy.
Ob peb xyoos dhau los, kev xaiv surfactants rau cov tshuaj pleev ib ce, cov khoom siv tu tus kheej thiab cov kws tshuaj tau tsom mus rau cov tshuaj toxicity tsawg, me me, maj mam kov thiab kev nyab xeeb. Cov neeg siv khoom ntawm cov khoom no tau paub txog qhov muaj peev xwm ua rau khaus, toxicity thiab ib puag ncig yam.
Niaj hnub no, AAS tau siv los tsim ntau cov tshuaj zawv plaub hau, cov plaub hau zas plaub hau thiab cov xab npum da dej vim lawv muaj ntau yam zoo dua lawv cov khoom siv tshuaj pleev ib ce thiab cov khoom tu tus kheej.Protein-based surfactants muaj cov khoom tsim nyog tsim nyog rau cov khoom tu tus kheej. Qee qhov AAS muaj peev xwm ua yeeb yaj kiab, thaum lwm tus muaj peev xwm ua kom zoo.
Amino acids yog ib qho tseem ceeb tshwm sim moisturizing yam nyob rau hauv lub stratum corneum. Thaum cov kab mob epidermal tuag, lawv dhau los ua ib feem ntawm stratum corneum thiab cov proteins intracellular tau maj mam degraded rau cov amino acids. Cov amino acids tom qab ntawd thauj mus ntxiv rau hauv stratum corneum, qhov chaw uas lawv nqus cov rog lossis rog zoo li cov khoom siv rau hauv epidermal stratum corneum, yog li txhim kho elasticity ntawm daim tawv nqaij. Kwv yees li 50% ntawm lub ntuj moisturizing ntawm daim tawv nqaij yog tsim los ntawm cov amino acids thiab pyrrolidone.
Collagen, ib qho khoom siv tshuaj pleev ib ce, kuj muaj cov amino acids uas ua rau cov tawv nqaij mos.Cov teeb meem ntawm daim tawv nqaij xws li roughness thiab dullness yog feem ntau vim tsis muaj cov amino acids. Ib txoj kev tshawb fawb pom tau tias sib xyaw cov amino acid nrog cov tshuaj pleev kom tshem tawm cov tawv nqaij kub hnyiab, thiab cov chaw cuam tshuam rov qab mus rau lawv lub xeev qub yam tsis tau ua keloid nti.
Amino acids kuj tau pom tias muaj txiaj ntsig zoo hauv kev saib xyuas cov cuticles puas.Qhuav, shapeless plaub hau yuav qhia tau hais tias ib tug txo nyob rau hauv lub concentration ntawm amino acids nyob rau hauv ib tug heev puas stratum corneum. Amino acids muaj peev xwm nkag mus rau cuticle mus rau hauv cov plaub hau ncej thiab nqus noo noo los ntawm daim tawv nqaij.Qhov peev xwm ntawm cov amino acid raws li surfactants ua rau lawv muaj txiaj ntsig zoo hauv cov tshuaj zawv plaub hau, cov plaub hau dyes, cov plaub hau softeners, cov plaub hau txias, thiab muaj cov amino acids ua rau cov plaub hau muaj zog.
11 Daim ntawv thov hauv cov tshuaj pleev ib ce txhua hnub
Tam sim no, muaj ntau qhov kev thov rau cov amino acid-raws li detergent formulations thoob ntiaj teb.AAS paub tias muaj peev xwm ntxuav tau zoo dua, muaj peev xwm ua npuas dej thiab cov khoom muag muag, uas ua rau lawv haum rau cov tshuaj ntxuav tsev, tshuaj zawv plaub hau, ntxuav lub cev thiab lwm yam kev siv.Ib qho aspartic acid-derived amphoteric AAS tau tshaj tawm tias yog cov tshuaj ntxuav tes zoo nrog cov khoom siv chelating. Kev siv cov tshuaj ntxuav tes uas muaj N-alkyl-β-aminoethoxy acids tau pom los txo cov tawv nqaij khaus. Cov tshuaj ntxuav tes ua kua uas muaj N-cocoyl-β-aminopropionate tau tshaj tawm tias yog cov tshuaj ntxuav tes zoo rau cov roj stains ntawm cov hlau. Ib qho aminocarboxylic acid surfactant, C 14 CHOHCH 2 NHCH 2 COONa, kuj tau pom tias muaj cov tshuaj tua kab mob zoo dua thiab siv los ntxuav cov ntaub pua plag, plaub hau, iav, thiab lwm yam. Cov 2-hydroxy-3-aminopropionic acid-N, N- acetoacetic acid derivative paub tias muaj peev xwm ua kom zoo thiab yog li muab kev ruaj ntseg rau cov tshuaj bleaching.
Kev npaj ntawm detergent formulations raws li N-(N'-long-chain acyl-β-alanyl)-β-alanine tau raug tshaj tawm los ntawm Keigo thiab Tatsuya nyob rau hauv lawv patent rau zoo dua ntxuav muaj peev xwm thiab stability, yooj yim ua npuas ncauj tawg thiab zoo ntaub softening . Kao tau tsim cov tshuaj ntxuav tais diav raws li N-Acyl-1 -N-hydroxy-β-alanine thiab tshaj tawm cov tawv nqaij qis, dej tsis kam thiab siab stain tshem tawm lub zog.
Lub tuam txhab Nyij Pooj Ajinomoto siv cov tshuaj lom neeg tsawg thiab yooj yim degradable AAS raws li L-glutamic acid, L-arginine thiab L-lysine ua cov khoom xyaw tseem ceeb hauv tshuaj zawv plaub hau, tshuaj ntxuav tes thiab tshuaj pleev ib ce (Daim duab 13). Lub peev xwm ntawm enzyme additives nyob rau hauv detergent formulations kom tshem tawm cov protein fouling kuj tau qhia. N-acyl AAS muab tau los ntawm glutamic acid, alanine, methylglycine, serine thiab aspartic acid tau raug tshaj tawm rau lawv siv los ua cov tshuaj ntxuav tes zoo hauv cov tshuaj aqueous. Cov surfactants no tsis nce viscosity txhua, txawm tias qhov kub thiab txias heev, thiab tuaj yeem hloov tau yooj yim los ntawm cov khoom siv foaming kom tau homogeneous foams.
Lub sij hawm xa tuaj: Jun-09-2022