Maqaal
Buluugga methylene oo tilmaame ah: waxa isbeddelka midabku dhab ahaan muujiyo

Farsamayaqaanad ayaa buluugga methylene ku darta koob shaybaar, hagaajisa pH, dabadeedna sugta in midabku muujiyo aashitonimada. Isbeddel cad ma dhaco. Halkii, waxay ku dartaa dhibic milanka aashitada ascorbic, buluuggiina wuu baaba'aa. Waxay dhalada ku ruxdaa hawada, buluuggiina wuu soo noqdaa. Waa isla midabeeyihii, laakiin laba habdhaqan oo aad u kala duwan. Jahawareerkaasi waa mawduuca maqaalkan oo dhan: buluugga methylene waa tilmaame redox oo ka jawaaba wareejinta elektaroonnada, mana aha tilmaame pH oo ka jawaaba borotoonnada. Marka kala duwanaantaas la caddeeyo, faahfaahin kasta oo kale waxay gashaa meesheedii.
Xeerka wax-ku-oolka ahi wuxuu ku koobnaan karaa hal weedh. Buluuggu wuxuu ka dhigan yahay in qaabka oksaydhaysani jiro. Midab-la'aantu waxay ka dhigan tahay in qaabka ridhakshan lagu sameeyay, leucomethylene blue, uu jiro. Wax kasta oo elektaroonno wareejiya ayaa xaaladda beddeli kara. Aashitooyinka iyo beysasku keligood ma samayn karaan, inkasta oo pH uu beddelo danabka uu isbeddelku ka dhacayo.
Lammaanaha ka dambeeya midabka
Buluugga methylene ee oksaydhaysani waa kaatayonka methylthioninium, nidaam phenothiazinium ah oo fidsan kana kooban saddex giraan, laguna bixiyo cusbada koloriidka, taas oo PubChem ku diiwaangeliso methylthioninium chloride. Biyo khafiif ah gudaheeda, monomeerku wuxuu nuugaa iftiinka meel u dhow 664 nm, nuugistaasina waa buluugga ay ishu aragto. Lammaanihiisa ridhakshan lagu sameeyay, leucomethylene blue, wuxuu leeyahay isla qaab-dhismeedka aasaasiga ah, laakiin naytrojiinka giraanta dhexe ayaa borotoon lagu daray, habka midabka abuura ee chromophore-kuna wuu burburay. Sidaas darteed, wuxuu ku dhow yahay midab-la'aan, iyadoo xariiqdiisa nuugista xooggan ay ku jirto qaybta ultraviolet-ka (diiwaanka PubChem ee qaabka leuco).
Falcelinta guud waxay wareejisaa laba elektaroon, laakiin tirada borotoonnadu waxay ku xiran tahay pH, sababtoo ah qaabka ridhakshan lagu sameeyay wuxuu borotoonno qaataa marka uu ku jiro aashito. Sharaxaadda tixraaca ah ee muuqaalaynta kimistariga redox waxay danabka caadiga ah ku sheegaysaa meel u dhow +0.53 V marka pH uu yahay 0, danabka shuruudaysan ee formal-kana meel u dhow +0.011 V marka pH uu yahay 7, marka loo eego elektaroodka haydarojiinka. Labadaas dhibcood dhexdooda, danabku wuxuu la beddelmaa pH. Voltammetry-ga casriga ah ee daraasadda habdhaqanka redox iyo danabyada midabeeyeyaasha wuxuu helayaa qiyaastii 29.5 mV halkii unug pH, laga bilaabo qiyaastii pH 4 ilaa 10, taas oo la jaanqaadaysa nidaam laba elektaroon iyo hal borotoon ah; iyo qiyaastii 88.5 mV halkii unug pH marka uu ka hooseeyo pH 4, taas oo la jaanqaadaysa nidaam laba elektaroon iyo saddex borotoon ah. Sidaas darteed, danab la soo sheegay oo aan pH-giisa lala sheegin macne ma leh. Had iyo jeer weydii jiirada iyo elektaroodka tixraaca ah ee tiradu ku salaysan tahay, maadaama qiimayaasha loo sheegay marka loo eego elektaroodo tixraac qalin ah aan si toos ah loo barbar dhigi karin qiimayaasha ku salaysan miisaanka haydarojiinka. Qaab-dhismeedka iyo sifooyinka aasaasiga ahi waxay qeexaan chromophore-ka, bog kale oo la socda oo ku saabsan naqshadaynta akhriska redox-na wuxuu lammaanahan ku xiriiriyaa doorashooyinka diyaarinta isku-dhafka.
Meeshaas dhexe ee miisaanka danabka ayuu midabeeyuhu faa'iidada ka helaa. Marka pH uu yahay 7, wuxuu ka mid yahay oksaydhiyeyaasha khafiifka ah: wuxuu leeyahay awood ku filan oo uu elektaroonno uga qaato deeq-bixiyeyaal wanaagsan sida ascorbate ama NAD(P)H, laakiin sidoo kale wuxuu u gudbin karaa oksijiinta milan ama xarumaha birta ferric. Sidaas darteed, wuu wareegaa halkii uu hal xaalad ku xannibmi lahaa. Ridhakshanku midabka ayuu ka saaraa. Hawadu mar kale ayay oksaydhaysaa. Waddadu waa isku mid labada jiho.
Sababta su'aalaha pH ay marar badan u soo baxaan
Saddex ilood oo jahawareer ah ayaa ku soo noqnoqda shaybaarrada iyo fasallada, mid kastana wuxuu leeyahay sixid cad.
Marka hore, pH wuxuu beddelaa danabka, taas oo u ekaan karta jawaab pH. Kordhi pH, lammaanuhuna wuxuu noqdaa mid si sahlan ridhakshan loogu samayn karo marka akhriska elektaroodku go'an yahay; sidaas darteed isla deeq-bixiyihii ayaa midabka si dhakhso badan u tirtira. Laakiin tallaabo borotoon lagu darayo oo keli ahi ma dhaliso isbeddelka cad ee buluugga ilaa midab-la'aanta inta lagu jiro baaxadda caadiga ah. Dib-u-eegis naqdin leh oo 2025 laga sameeyay sifooyinka buluugga methylene waxay sheegaysaa in meesha ugu sarreysa ee 665 nm ay asal ahaan isbeddel la'aan tahay laga bilaabo pH 2 ilaa 12, iyadoo keliya isbeddello yar ay ku dhacaan nuugista iftiinka. Borotoonnadu waxay hagaajiyaan danabka. Elektaroonnadu waxay beddelaan midabka.
Marka labaad, summadda kala-soocidda aqooneed ayaa marin-habaabisa. PubChem waxay hadda ka soo qaadataa ChEBI qeexid door oo midabeeyaha ku tilmaamaysa tilmaame aashito-beys. Summaddaas looma akhrisan karo caddayn muujinaysa in buluugga methylene u dhaqmo sida phenolphthalein ama casaanka methyl. Shaqada caadiga ah ee milannada biyaha ku salaysan, sidaas uma dhaqmo.
Marka saddexaad, isku-dhafka Tashiro ayaa magaca amaahda. Tilmaamaha Tashiro waa isku-dhaf casaanka methyl iyo buluugga methylene ah, kaas oo casaanka methyl bixiyo jawaabta aashito-beys, buluugga methylene-na bixiyo asalka buluugga ah ee muuqaalka, sidaasna isbeddelka casaan ilaa jaalle ugu beddelo isbeddel isku-dhafan oo ka sii cad. Mid ka mid ah diyaarinta Tashiro ee ganacsiga ayaa sheegaysa pH 4.4 ilaa 6.2, halka isku-dhaf qeexan oo ITW Reagents ah uu tilmaamayo casaan-buluug-guduudan marka pH uu yahay 4.4 ilaa cagaar marka pH uu yahay 5.8. Midkoodna ma aha baaxadda isbeddelka buluugga methylene laftiisa. Midabeeyuhu waa walaxda fududaysa kala-garashada midabka, mana aha walaxda dareemaysa pH.
Hal xaalad oo xadka ku dhow ayaa mudan digniin. Agagaarka pH 13, xaalado beys aad u xooggan leh ayaa soo saari kara walxo casaan ilaa casaan khafiif ah oo nooca methylene-violet ah, iyagoo adeegsanaya hydrolysis aan dib loo celin karin. Casaankaas khafiifka ahi waa burbur kiimiko, mana aha barta dhammaadka tilmaame. U qaado calaamad kuu sheegaysa inaad milanka tuurto, ee ha u qaadan akhris.
Meelaha uu uga shaqeeyo tilmaame redox
Adeegsiga dhaqameedku waa titration-ka Lane-Eynon ee sonkorta wax ridhakshanaysa. Milanka Fehling ee kulul, beyska ah waxaa lagu titrate-gareeyaa sonkor, buluugga methylene-na waxaa lagu daraa meel u dhow barta dhammaadka; buluugga haray wuxuu baaba'aa marka awoodda ridhakshanka sonkortu ka badato inta looga baahan yahay copper(II). Habraaca AOAC ee Lane-Eynon wuxuu isku-dhafka ku hayaa karkar si uumiga baxayaa u xakameeyo dib-u-oksaydhaynta hawadu keento, waxaana badanaa la adeegsadaa dhowr dhibcood oo milanka midabeeyaha ah. Isbeddelka midabku wuxuu muujinayaa in aysan jirin naxaas ridhakshan lagu samayn karo oo hadhay; taasina waa hadal redox oo ku saabsan waxa dhalada ku jira, mana aha hadal pH.
Titrimetry-gii hore ayaa isla mabda'aan meelo kale u adeegsaday. Midabeeye khafiif ah ayaa istaarijka beddeli karay qaar ka mid ah titration-yada iodimetric-ka ah ee alkoolku ka dhigayay istaarijka mid aan ku habboonayn, iyadoo uruurinta la adeegsado ay ku dhowdahay 0.05 g halkii litir. Hase yeeshee, midabeeye xad-dhaaf ahi wuxuu halis u yahay inuu abuuro isku-dhis ay samaystaan ayoodiin iyo midabeeyuhu, sida Sinnatt muujiyay 1912. Buug-gacmeedyada la ururiyey waxay sidoo kale midabeeyaha ku taxaan titanometry iyo iodometry. Habka Gal ee aashitada ascorbic ee 1936 wuxuu midabeeyaha ku ridhakshanay waxyaabo laga soo saaray fiitamiin C, dabadeedna midabeeyaha haray ayuu dib ugu titrate-gareeyay titanium trichloride. Habkaasi maanta waa mid taariikhi ah halkii uu ka ahaan lahaa hab joogto loo adeegsado, laakiin wuxuu muujinayaa qaabka guud: deeq-bixiyuhu buluugga ayuu u ridhakshanaa midab-la'aan, baaba'a buluugguna waa barta dhammaadka.
Hababka oksijiinta milan waxay isla lammaanahan u adeegsadaan jihada ka soo horjeedda. Hal hab oo la daabacay ayaa marka hore midabeeyaha ku ridhakshana glucose ku jira ethanol biyo leh oo beys ah, dabadeedna u oggolaada oksijiinta milan inay qaabka leuco ee midab-la'aanta ah dib ugu oksaydhayso buluug ku dhowaad isla markiiba. Akhriska waxaa laga qaadaa meel u dhow 600 nm, ilaa qiyaastii 13 mikroogaraam halkii millilitir, sida ay sharraxeen Okumura iyo Hashitani. Ha ku khaldin tan titration-ka dhaqameed ee Winkler ee oksijiinta milan, kaas oo bartiisa dhammaadku adeegsato istaarij; habraaca hawlgalka caadiga ah ee NOAA Winkler wuxuu qeexayaa qiyaastii 1 boqolkiiba istaarij. Hababka oksijiinta ee buluugga methylene waa koox gaar ah oo jihada isbeddelka midabku rogan tahay.
Dhalada buluugga ah ee fasalka lagu muujiyo waa isla lammaanahan oo cabbir yar ah: glucose ku jira milan beys ah ayaa midabeeyaha buluugga ah u ridhakshana qaabka midab-la'aanta ah marka la daayo, ruxidduna waxay milisaa oksijiin dib ugu oksaydhaysa buluug. Habraaca oo dhammaystiran iyo xakamayntiisu waxay ku jiraan bandhigga dhalada buluugga ah, meelaha xariiqyada nuugista iyo isbeddellada isu-ururintuna waxay ku jiraan bogga spectra iyo saamaynta uruurinta. Maqaalkani wuxuu ku koobnaanayaa habka falcelinta, sababtoo ah habraaca iyo spectra mid walba wuxuu u baahan yahay xaalado u gaar ah.
Jadwalka xaaladaha midabka: xaaladaha, duruufaha iyo xaddidaadaha
Jadwalkani waa tixraaca asalka ah ee maqaalkan. Akhri safka oo dhan ka hor intaadan ku kalsoonaan barta dhammaadka.
| Xaalad | Muuqaal | Duruufda dhalisa | Waxa ay muujiso | Xaddidaad |
|---|---|---|---|---|
| Monomeer oksaydhaysan, khafiif ah, dhexdhexaad ah | Buluug qoto dheer, meesha ugu sarreysa oo u dhow 664 nm | Milan hawo ka buuxdo, deeq-bixiye ma jiro | Xaaladda bilowga ah ee diyaarsan | Uruurin sare marka ay jirto, meesha ugu sarreysa waxay ugu wareegtaa dhanka 610 nm sababta oo ah dimer-samaysanka; sidaas darteed qiimee midabka oo keliya markaad khafiifiso ka dib |
| Qaabka leuco ee ridhakshan lagu sameeyay, dhexdhexaad ah | Midab-la'aan | Deeq-bixiye ayaa jira (glucose ku jira beys, ascorbate, dithionite, NAD(P)H oo leh kiciye) | Awoodda ridhakshanku waxay ka badatay baahida tilmaamaha | Hawadu dib ayay u oksaydhaysaa, sidaas darteed barta dhammaadku waxay dib ugu noqotaa buluug haddii aan hawada laga ilaalin ama xaaladdeeda la jaangoyn |
| Qaabka leuco, aashito ah | Midab-la'aan | Isla deeq-bixiyeyaashii oo ku jira aashito, iyadoo leuco-gu qaato borotoonno dheeraad ah | Isla waxa kor ku xusan, laakiin danab beddelmay | Jiirada danabku way sii qotodheeraataa marka uu ka hooseeyo pH 4, sidaas darteed cabbir-habayn lagu sameeyay pH 7 lama wareejin karo |
| Isku-dhafka Tashiro, aashito ah | Casaan-buluug-guduudan | pH ka hooseeya qiyaastii 4.4 oo ku jira isku-dhafka casaanka methyl iyo buluugga methylene | Aashitonimada, oo uu muujiyo casaanka methyl | Wuxuu muujinayaa jawaabta casaanka methyl, ee ma aha buluugga methylene; ha u soo xigan baaxad pH oo buluugga methylene ah |
| Isku-dhafka Tashiro, meel u dhow pH 5.8 ilaa 6.2 | Cagaar ilaa cawl-cagaar | Isla isku-dhafka oo u dhow dhinaca sare ee isbeddelkiisa | Isla waxa kor ku xusan | Waxay ku xiran tahay diyaarinta isku-dhafka; hubi dhalada, hana ku tiirsanaan xusuusta |
| Burburay, beys aad u xooggan leh | Casaan khafiif ah ilaa casaan | pH u dhow 13, kulayl, ku-jiritaan beys oo muddo dheer ah | Hydrolysis aan dib loo celin karin oo soo saara walxo nooca violet ah | Ruxid laguma soo celin karo; tuur oo mar kale diyaari |
| Iftiinku midabka ka tiray | Buluug yaraaday oo leh spectrum beddelmay | Iftiin muuqda oo xooggan, gaar ahaan marka deeq-bixiyeyaal jiraan | Falcelinno dhinac ah oo iftiinku kaxeeyo, oo ay ku jiraan walxo kooxaha methyl-ka laga saaray | Milannada tixraaca ka ilaali iftiiminta, sida ay muujisay shaqada photoreduction-ka ee iftiinka muuqda |

Sababaha khaladka ee mugdi geliya barta dhammaadka
Hawadu waa waxa ugu horreeya ee laga shakiyo mar kasta oo barta dhammaadku isbeddesho. Qaabka leuco si fudud ayuu dib ugu oksaydhaysmaa, gaar ahaan nidaamyada beyska ah. Sidaas darteed, titration midab-la'aan noqday ayaa mar kale buluug noqon kara marka la daayo ama si xooggan loo wareejiyo. Hawada ka ilaali marka joogtayntu muhiim tahay, jaangoy ruxidda, akhriskana qaado waqti go'an.
Iftiinku waa waxa labaad ee laga shakiyo. Midabeeyuhu falcelin ayuu ku sameeyaa iftiinka, iftiimin iyadoo deeq-bixiyeyaal jiraanna waxay midabka ka tirtiri kartaa waddooyin ay ku jiraan walxo kooxaha methyl-ka laga saaray. Milannada midabeeyaha ee falanqaynta loogu talagalay ku kaydi mugdi, hana cabbirin barta dhammaadka iyadoo ay saaran yihiin laambado xooggan oo miiska shaybaarka ah.
Uruurintu waa tan saddexaad. Kaatayonka oksaydhaysan wuxuu is dul saaraa isagoo samaynaya dimero iyo isku-ururro ka waaweyn, oo leh xariiq nuugis u wareegtay meel u dhow 610 ilaa 615 nm. Sidaas darteed, milan uruursan ayaa u ekaan kara mid ka leexday meesha ugu sarreysa isaga oo aan wasakhayn. Khafiifi ilaa uu galo xaaladda monomeerka ka hor intaadan qiimayn spectra ama baraha dhammaadka.
Laba qallooc oo aan sidaas u muuqan ayaa mudan in la xuso, sababtoo ah waxay si gaar ah u saameeyaan shaqada uruurinta hoose leh. Midabeeyuhu si la cabbiri karo ayuu ugu dhegaa dusha xadka u dhexeeya dhalada iyo biyaha, taas oo qalloocisa milannada tixraaca ee khafiifka ah iyo cabbirrada xawaaraha falcelinta; weelal ama cuvet-yo polymer ah ayaa xal u ah marka saxnaantu muhiim tahay. Sidoo kale, midabeeyaha ganacsigu wuxuu xambaari karaa wasakhooyin thiazine la xiriira, oo ay ku jirto Azure B, kuwaas oo daraasado sifayn oo hore si gaar ah uga saareen. Sidaas darteed, shaqada falanqayntu waa inay qeexdaa darajada midabeeyaha halkii ay ka qaadan lahayd in dhalo kasta oo lagu qoray buluugga methylene ay kiimiko ahaan isku mid tahay. Faahfaahinta spectral-ka ee isbeddelka isu-ururinta waxaa si ula kac ah loogu reebay bogga spectra.
Liis hubin oo gaaban oo miiska shaybaarka ah
Milanka ku deji buffer, pH-na ku qor agta danab kasta iyo bar kasta oo dhammaad. Go'aami xaaladda oksijiinta: karkarinta oo leh dabool uumi ah marka la samaynayo shaqo nooca Lane-Eynon, iyo dabool gaas aan falcelin samayn ama waqti go'an meelaha kale. Ku shaqee uruurin ku filan khafiifnimada si monomeerku u muuqdo, milannada ka ilaali iftiinka, doorbido weelasha polymer-ka marka uruurintu hooseyso, oo diiwaangeli darajada midabeeyaha. Haddii ujeeddadu dhab ahaan tahay pH, qaado tilmaame aashito-beys oo dhab ah ama isku-dhaf Tashiro oo qeexan, baaxadda isku-dhafkana u soo xigso baaxadda isku-dhafka, waligaa ha ugu yeerin baaxadda buluugga methylene.
Fikradda aasaasiga ahi weli way caddahay marka nidaamkan la raaco. Buluugga methylene wuxuu si aan caadi ahayn oo cad u muujinayaa xaaladda oksaydhaynta, sababtoo ah labadiisa xaaladood aad ayay ugu kala duwan yihiin nuugista iftiinka muuqda. Midabka ula dhaqan akhris redox oo laga qaaday pH la sheegay, iyadoo xaaladaha oksijiinta iyo iftiinka la sheegay, darajada midabeeyahana la sheegay; sidaas ayuu booskiisa titration-ka ku mutaysanayaa. Haddii aad ula dhaqanto sidii litmus, si joogto ah ayuu kuu marin-habaabin doonaa.