Ua tau zoo Adsorption Ntawm Phenylethanoid Glycosides Ntawm Mesoporous Carbon

Taw qhia

Cistanche tubulosa yog Orobanchaceae parasitic nroj tsuag (Li li al., 2016; Wang X. li al., 2017), thiab nws tsuas yog loj hlob ntawm cov hauv paus hniav ntawm Tamarix nroj tsuag thiab Calotropis hom (Zhang W. li al., 2016; Yan et ib., 2017).Cistanche tubulosayog thawj zaug sau tseg hauv Shen Nong's Suav Materia Medica hauv ca. 100 BC Kev loj hlob thiab kev cog qoob loo ntawm Cistanche tubulosa xav tau ib puag ncig hnyav, thiab nws tau cog rau hauv cov av qhuav thiab cov suab puam ntawm sab qaum teb hemisphere, xws li cov xeev ntawm Xinjiang, Inner Mongolia, Gansu, Qinghai, thiab Ningxia Autonomous Region hauv Suav teb. (Koj li al., 2016). Cistanche tubulosa yog ib qho tshuaj ntsuab zoo tshaj plaws hauv Suav teb uas muaj lub luag haujlwm ntawm kev txhawb nqa lub raum, tiv thaiv kev laus, txhawb nqa cov ntsiab lus ntawm cov ntshav, thiab moistening cov hnyuv loj kom tsis muaj quav (Gu li al., 2016; Shimada li al., 2017; Cui et al., 2018), thiab nws muaj been lub koob npe nrov li "Ginseng ntawm Deserts" (Song et al., 2016; Wang et al., 2018). Cistanche tubulosa tau raug sau tseg hauv Suav Pharmacopeia raws li qhov tseeb ntawmCistanches Herba(Suav lub npe: Roucon-strong) los ntawm 2005 tsab (Wang T. et al., 2016; Pei et al., 2019).

NATURAL CISTANCHE TUBULOSA rau kev txhim kho kev sib deev PHGS75% ECH 30% ACT 12%

Cov kev tshawb fawb yav dhau los tau qhia ntau yam tshuaj tseem ceeb ntawm Cistanche tubulosa, suav nrog PhGs, iridoids, thiab polysaccharides (Li li al., 2018a). Cov qauv ntawm PhGs feem ntau yog tsim los ntawm cinnamic acid thiab phenyl ethyl cawv uas tau txuas rau -glucopyranose los ntawm ester thiab glycosidic linkages (Luo li al., 2010), thiab PhGs tau suav tias yog cov khoom tseem ceeb ntawm Cistanche tubulosa muaj ntau yam. Kev ua yeeb yam tshuaj (Liao li al., 2018). Txoj kev tshawb no pom tias PhGs muaj ntau yam tshuaj, xws li neuroprotection, tiv thaiv kab mob, tiv thaiv kab mob, tiv thaiv daim siab, thiab antioxidant (Aiello et al., 2015; Shiao et al., 2017; Wu et al., 2018, 2019). Raws li kev soj ntsuam phytochemical, PhGs xws liechinacoside, thiab acteosidetau suav hais tias yog cov khoom tseem ceeb thiab cov cim ntawm Cistanche tubulosa (Li et al., 2017b), uas feem ntau tau xaiv los ua cov khoom sib txuas rau kev ntsuam xyuas zoo ntawm Cistanche tubulosa thiab hom Cistanche tau txawv ntawm cov tebchaw no. PhGs tau tshwm sim ib txwm muaj dej-soluble compounds vim tias lawv muaj ntau pawg hydroxyl thiab phenolic hydroxyl pawg hauv cov molecule. Yog li, PhGs tuaj yeem raug cais tawm ntawm Cistanche tubulosa hauv cov tshuaj aqueous.

Ntau txoj hauv kev rau kev sib cais thiab kev ua kom huv ntawm cov khoom ntuj tsim tau tsim nrog rau adsorption (Liu li al., 2016), membrane sib cais (Zhang li al., 2018b; Li li al., 2019) thiab hnyav extraction, thiab lwm yam (Li. thiab al., 2015a, b; Wang S. et al., 2016; Zhang H. et al., 2016). Txawm li cas los xij, kev sib cais ntawm daim nyias nyias thiab cov kuab tshuaj tshem tawm tsis haum rau kev npaj loj thiab lawv nyuaj rau kev ua tiav cov khoom zoo (Zhang li al., 2018a). Adsorption yog ib txoj hauv kev siv dav dav rau kev sib cais ntawm cov khoom ntuj tsim (Wang S. li al., 2016; Konggidinata li al., 2017). Raws li lawv qhov tshwj xeeb thiab cov qauv pore tsis sib haum, thaj chaw siab, thiab kev ruaj ntseg, cov pa roj carbon mesoporous (qhov pore loj ntawm 2 thiab 50 nm) tau raug pov thawj los ua ib yam khoom zoo rau adsorptive natural products. Txoj kev tshawb no qhia tias mesoporous carbons yog tsim nyog rau adsorbing macromolecules, xws li mesoporous carbons tau siv los ntawm Qin li al. rau kev txhawb nqa ntawm chlorogenic acid los ntawm eucommia ulmoides nplooj (Qin li al., 2018). Li et al. synthesized ob mesoporous carbons los ntawm ib tug hydrothermal kev kho mob mus kom ze thiab ntsuam xyuas cov adsorption kev ua tau zoo ntawm ob mesoporous carbons rau berberine hydrochloride thiab marine los ntawm dej (Li li al., 2018b). Nws tau raug suav tias yog cov khoom cog lus zoo li cov khoom siv tau zoo heev (Zhang li al., 2013; Tian et al., 2015; Zhou et al., 2016). Tsis tas li ntawd, cov pa roj carbon monoxide mesoporous kuj tau siv rau kev tshem tawm cov tshuaj tsw qab, xim, thiab cov hlau hnyav los ntawm cov dej khib nyiab (Kong et al., 2016). Hauv kev tshaj tawm yav dhau los, Liu et al. siv cov macroporous resin rau adsorb PhGs los ntawm Cistanche tubulosa, thiab purity ntawm PhGs nce, tab sis lub peev xwm adsorption thiab desorption tus nqi qis. Piv nrog rau cov macroporous resin, mesoporous carbons muaj cov yam ntxwv ntawm ib cheeb tsam loj, haum pore loj, thiab lub siab pore ntim. Yog li ntawd, cov pa roj carbon mesoporous tau suav tias yog qhov ua tau zoo adsorbent rau PhGs. Hauv txoj kev tshawb no, peb hom mesoporous carbon raug xaiv los ua adsorbents rau kev sib cais thiab kev huv ntawm PhGs los ntawm Cistanche tubulosa.

Lub hom phiaj tseem ceeb ntawm txoj haujlwm no yog tshawb nrhiav qhov ua tau zoo ntawm kev nqus ntawm CMK-3 rau kev sib cais thiab kev ua kom huv ntawm PhGs los ntawm Cistanche tubulosa. Cov teebmeem ntawm qhov sib txawv ntawm qhov sib txawv, pH, thiab qhov kub thiab txias ntawm kev ua haujlwm adsorption ntawm CMK- 3 tau raug tshawb xyuas thiab qhov zoo tshaj plaws adsorption tej yam kev mob ntawm PhGs raug tshuaj xyuas. Mesoporous carbons tau tsim los ntawm FT-IR, BET, TEM, thiab TGA, thiab adsorption isotherms thiab kinetics tau ua thiab tshuaj xyuas kom meej.

NATURAL CISTANCHE TUBULOSA rau kev txhim kho kev sib deev PHGS75% ECH 30% ACT 12%

Kev sim

Khoom siv thiab Reagents

Cistanche tubulosa qia tau yuav los ntawm Congrongtang Biological Technology Co., Ltd. (Xinjiang). Cov qauv ntawmechinacoside cov tshuaj(purities Ntau dua lossis sib npaug li 98%) thiab acteoside (purities Ntau dua lossis sib npaug li 98%) tau yuav los ntawm Sunny Biotech Co., Ltd. (Shanghai). Acetonitrile, methanol, thiab acetic acid ntawm HLPC tau yuav los ntawm Thermo Fisher Scientific Co., Ltd. (Shanghai). Cov ethanol ntawm analytical qib tau yuav los ntawm Yongsheng Fine Chemical Co., Ltd. (Tianjin). Ordered mesoporous carbon (CMK-3), disordered mesoporous carbon (DMC), thiab threedimensional cubic order mesoporous carbon (CMK-8) tau yuav los ntawm Xianfeng Nano Material Technology Co., Ltd. (Nanjing).

Cim xeeb

Lub morphology thiab microstructures ntawm cov qauv npaj tau raug tshawb xyuas siv Transmission electron microscopy (TEM, Tecnai G2 F20) ua haujlwm ntawm 200 KV. Cov qauv TEM tau npaj nyob rau hauv ib puag ncig puag ncig los ntawm kev tso cov tee dej ntawm cov tshuaj ethanol nrog cov ntaub ntawv mesoporous mus rau cov pa roj carbon films txhawb los ntawm Cu daim phiaj. Feem ntau, lub teeb pom kev zoo nrog lub wavelength luv luv tau raug xaiv los ua kom qhov kev daws teeb meem ntawm lub tshuab tsom iav, thiab cov qauv ntawm cov pa roj carbon mesoporous tuaj yeem pom. Cov pab pawg ua haujlwm saum npoo av tau raug ntsuas zoo los ntawm Fourier hloov pauv infrared spectroscopy (FT-IR, AVATAR360) siv kev sib cuam tshuam ntawm cov hluav taws xob hluav taws xob thiab cov teeb meem molecules. FT-IR siv ib qho kev ntsuam xyuas tag nrho cov kev xav, cov xwm txheej yog ib kauj ruam loj ntawm 2 cm-1 thiab scanning ntau yog 4, 000-400 cm-1. Cov ntaub ntawv ntawm lub cev xws li thaj chaw tshwj xeeb, qhov pore loj, thiab qhov pore ntim ntawm mesoporous carbons xam los ntawm Brunauer-Emmett-Teller (BET, ASAP 2460). Cov txheej txheem rau cov adsorbent yog raws li nram no: mesoporous carbons tau degassed ntawm 60◦C rau 12 h, thiab N2 adsorption-desorption curves raug kuaj ntawm −196◦C los xam cov cheeb tsam tshwj xeeb, pore loj, thiab pore ntim ntawm lub cov pa roj carbon ntau. Thermo gravimetric analyzer (TGA, STA 449 F3) yog ib qho cuab yeej uas siv cov thermo gravimetric los kuaj xyuas qhov kub thiab txias ntawm ib yam khoom, thiab TGA ntsuas qhov loj ntawm cov khoom raws li kev ua haujlwm ntawm qhov kub thiab txias hauv kev tswj qhov kub thiab txias. TGA cov ntaub ntawv tau txais los ntawm kev siv TGA nyob rau hauv qhov kub ntawm 30 txog 800◦C ntawm qhov cua kub ntawm 10◦C / min nyob rau hauv cov huab cua.

Kev txheeb xyuas HPLC

Cov ntsiab lus ntawm echinacoside thiab acteoside tau kuaj pom los ntawm kev ua haujlwm siab ua kua chromatography (HPLC, Waters Co., USA). Lub kaw lus suav nrog autosampler, lub twj tso kua mis siab, thiab ultraviolet (UV) ntes. Kev tsom xam tau ua rau ntawm symmetry C18 kem (100Å, 5µm, 4.6 × 250 mm). HPLC siv txoj kev gradient elution los cais thiab kuaj xyuas cov qauv. Qhov ntim ntawm lub voj voog txhaj tshuaj yog 10µm, qhov ntsuas kub yog 30 ◦C, qhov ntsuas qhov ntev ntawm UV spectrophotometer yog 330 nm, tus nqi ntws yog 1 ml / min thiab theem mobile yog (A) acetonitrile thiab (B) acetic acid/dej (1:44, v/v).

Adsorption Equilibrium

Qhov kev sim ua kom zoo tshaj plaws ntawm qhov adsorption mob rau CMK - 3 tau ua los ntawm kev sib xyaw ua keacteoside thiab enchanosidethiab nyob rau hauv qhov kev pom zoo, cov khoom siv raw ntawm Cistanche tubulosa tau ua tiav ntawm qhov kev sim adsorption voj voog thiab tag nrho cov kev sim adsorption tau rov ua dua tsawg kawg 3. Nyob rau hauv tib batch ntawm kev sim, mesoporous carbons ntawm CMK-8 thiab DMC tau khiav ua ke nrog CMK-3. Peb hom mesoporous carbon (CMK- 3, DMC, thiab CMK-8) txhua 10 mg tau ntxiv rau peb lub raj mis, raws li. Tom qab ntawd 15 mL qauv tshuaj nrog qhov pib concentration ntawm C0 (mg / mL) tau ntxiv rau hauv lub raj mis. Lub raj mis tau muab tso rau hauv qhov ntsuas kub tsis tu ncua ntawm 30 ◦C rau 24 teev kom txog thaum lub adsorption equilibrium mus txog. Tom qab ntawd 1 ml ntawm cov tshuaj adsorption tau lim los ntawm 0.22µm lim thiab qhov sib npaug ntawm Ce (mg / mL) ntawm cov qauv tshuaj raug txiav txim los ntawm HPLC.

Kev sim Desorption

Tom qab ntawd qhov kev sim desorption ntawm mesoporous carbon tau ua tiav. Lub adsorbed mesoporous carbon nyob rau hauv 15 mL ntawm methanol / acetic acid (9: 1, v / v) tov tov, uas tau muab tso rau hauv dej da dej ntawm ultrasonic rau 1 h ntawm 3 0◦C. Cov tshuaj desorption tau raug lim los ntawm 0.22 lim ua ntej tshuaj xyuas los ntawm HPLC.

Lub peev xwm adsorption qe (mg / ml) tau soj ntsuam raws li hauv qab no:

qhov twg V yog qhov ntim ntawm cov tshuaj (mL) thiab W yog qhov hnyav ntawm cov pa roj carbon mesoporous (g).

TSEEM CEEB THIAB SIB HLUB

Cim xeeb

Daim duab 1 qhia TEM ntawm peb hom mesoporous carbons. DMC yog ib qho kev tsis sib haum xeeb porous network, CMK-8 yog ib lub network qauv ntawm peb-dimensional ntxeem tau, thiab CMK-3 yog ib tug striped qauv nrog txiav txim ib-dimensional pore, uas zoo ib yam li cov lus qhia (Wang et al., 2006; Luo et al., 2010).

Daim duab 2 qhia txog FT-IR spectrum ntawm cov pa roj carbon mesoporous (CMK-3, DMC, thiab CMK-8) thiab FT-IR spectrum ua ntej thiab tom qab CMK-3 adsorption. Nws tuaj yeem pom los ntawm daim duab 2A tias cov pab pawg ua haujlwm ntawm qhov chaw ntawm cov pa roj carbon mesoporous feem ntau muaj cov pa oxygen. Tag nrho cov duab ntawm lub spectra rau peb hom mesoporous carbons zoo ib yam. Cov pa roj carbon monoxide mesoporous tau pom lub ncov siab ntawm 3,423 cm-1 xa mus rau qhov stretching vibration band ntawm OH. Cov bands nyob rau hauv cheeb tsam ntawm 1,580 thiab 1,629 cm-1 sib haum mus rau stretching vibrations ntawm carbonyl thiab carboxyl C=O. Tsis tas li ntawd, qhov siab tshaj plaws tshwm sim ntawm 1,384 cm-1 tau pom tias stretching vibrations ntawm cawv CO, thiab tensile vibration ntawm 2,922 thiab 2,852 cm-1 sib raug rau CH ntawm methylene thiab methyl pawg, raws li. Qhov no tau qhia tias cov pab pawg uas muaj cov pa oxygen uas muaj nyob rau ntawm qhov chaw ntawm cov pa roj carbon monoxide yuav ua rau muaj kev cuam tshuam tshuaj lom neeg tsis muaj zog ntawm PhGs molecules thiab cov pa roj carbon mesoporous.

Daim duab 2B qhia FT-IR spectra ntawm CMK-3 ua ntej thiab tom qab adsorption, acteoside, thiab enchanoside. Cov yam ntxwv ncov ntawm 1,697 cm−1 muab tau los ntawm C=C ntawm olefin hauv acteoside thiab enchanoside, thaum lub bands nyob rau hauv cheeb tsam ntawm 1,519–1,423 cm−1 sib raug mus rau lub stretching vibration ncov ntawm lub aromatic nplhaib C{ {12}}C hauv acteoside thiab enchanoside. Lub tensile vibration ntawm 1,604 cm−1 yog C=O daim ntawv cog lus thiab lub ncov ntawm 1,157 cm−1 yog tshwm sim los ntawm stretching vibration ntawm ether daim ntawv cog lus nyob rau hauv acteoside thiab enchanoside. Piv nrog rau FT-IR spectrum ntawm CMK-3 ua ntej adsorption, FT-IR spectrum ntawm CMK-3 tom qab adsorption tshwm sim cov peaks tshiab, uas yog cov yam ntxwv peaks ntawm acteoside thiab enchanoside.

N2 adsorption-desorption isotherms yog ib qho tseem ceeb rau adsorption ntawm PhGs ntawm CMK-3 thiab kev sib piv ntawm cov qauv adsorbent. Daim duab 3 qhia txog N2 adsorption-desorption isotherms ntawm CMK-3, CMK-8, DMC, thiab CMK-3 tom qab PhGs adsorption, feem. Raws li pom tau los ntawm daim duab 3, lub isotherm ntawm mesoporous carbons yog zoo ib yam li hom-IV isotherm nyob rau hauv uas hom isotherm no feem ntau yog mesoporous, nyob rau hauv uas qhov ntau ntawm pore loj nyob nruab nrab ntawm 2 thiab 50 nm (Sanz Pérez li al. , 2019). Qhov sib txawv ntawm adsorption thiab desorption isotherm raug xa mus rau hysteresis voj los ntawm capillary condensation cov tshuaj tiv thaiv. Rau cov tshuaj tiv thaiv capillary condensation, capillary condensation tshwm sim thawj zaug hauv qhov pores tsawg tshaj plaws (Barsotti li al., 2016). Qhov no qhia tau hais tias CMK-3 muaj mesopore me dua li DMC thiab CMK-8, uas yog raws li cov txiaj ntsig ntawm Table 1. Lub isotherm ntawm CMK-3 nthuav tawm H1 hysteresis voj uas yog qhia tau hais tias qhov ceev pore filling cuam tshuam nrog capillary condensation thiab lub pore qauv ntawm CMK -3 yog tsim nyog. Lub isotherm ntawm DMC nthuav tawm lub voj H3 hysteresis, hom hysteresis no muaj qhov tsis zoo ntawm qhov pores vim yog lub network ntawm qhov pores uas ua rau cov qauv tsis tau hais tawm ntawm cov ntxeem tau adsorbent. CMK-8 isotherms nthuav tawm H2 hysteresis voj, qhia tias pore qauv nyuaj thiab pore loj faib tsis sib xws.

N2 adsorption-desorption isotherms ntawm CMK-3 tau muab piv ua ntej thiab tom qab adsorption ntawm PhGs. Lub isotherm ntawm CMK-3 tom qab adsorption kuj zoo ib yam li hom-IV isotherm hauv daim duab 3B. Nws tau qhia tias CMK-3 khaws nws cov qauv mesoporous tom qab adsorption. Raws li tuaj yeem pom los ntawm Table 1, qhov tshwj xeeb nto thiab qhov pore ntim ntawm CMK-3 tom qab adsorption pom qhov txo qis, qhov tshwj xeeb nto ntawm CMK-3 ua ntej thiab tom qab adsorption poob ntawm 1,{{18} }}98.02 txog 227.75 m2 / g, thiab qhov pore ntim ntawm qhov txo qis ntawm 1.32 txog 0.42 cm3 / g. Nws tau qhia tias PhGs molecules tau adsorbed ntawm CMK-3.

Table 1 summarizes the BET-specific surface area, pore volume, and pore size of the four samples. The BET surface areas of CMK-3, DMC, and CMK-8 were 1,098.02, 430.42, and 596.00 m2 /g and the pores volume were 1.32, 0.70, and 0.85 m3 /g, respectively. The pore size of CMK-3 was 4.31 nm, lower than that of CMK-8 (9.58 nm) and DMC (5.18 nm). It can be seen that the pore volume and specific surface area follow the order: CMK-3 >CMK-8 >DMC, while pore size follows the order: DMC >CMK-8 >CMK-3.

Daim duab 4 qhia txog TGA nkhaus ntawm peb hom mesoporous carbons (CMK-3, CMK-8, thiab DMC). Raws li pom tau los ntawm daim duab 4, peb hom mesoporous carbons tag nrho muaj ob theem sib txawv ntawm qhov poob loj: thawj theem ntawm qhov poob yog vim evaporation ntawm noo noo nyob rau hauv mesoporous carbons ua ntej 100◦C, lub thib ob loj poob theem ntawm CMK- 3, DMC thiab CMK-8 kwv yees tshwm sim ntawm 660, 427, thiab 615◦C, raws li, uas sib haum rau oxidative thermal decomposition ntawm mesoporous carbons cov ntaub ntawv. Nws tuaj yeem pom tias qhov kub ntawm qhov kub ntawm CMK{10}} siab dua CMK-3 thiab CMK{12}}, thiab qhov thermal stability ntawm CMK{13}} zoo dua li ntawm CMK -8 thiab DMC.

Kev sib piv ntawm Peb Mesoporous Carbons Adsorption Performance Vim tias peb cov adsorbents feem ntau yog tsim los ntawm cov pa roj carbon, qhov adsorption kev sib cuam tshuam ntawm PhGs thiab mesoporous carbons tau suav tias yog tib yam. Yog li ntawd, nws tau txiav txim siab tias qhov sib txawv ntawm kev ua haujlwm adsorption tau muab los ntawm qhov sib txawv ntawm lub cev qauv ntawm mesoporous carbons. Table 2 qhia txog kev ua haujlwm adsorption ntawm peb hom mesoporous carbons. Nws tuaj yeem pom los ntawm Table 2 tias peb hom mesoporous carbons tag nrho tuaj yeem adsorb PhGs, thiab CMK-3 muaj kev ua haujlwm zoo dua li CMK-8 thiab DMC. Qhov no qhia tau hais tias qhov pore loj ntawm mesoporous carbons loj dua PhGs molecules, thiab qhov pore loj tsis yog qhov tseem ceeb cuam tshuam rau lub peev xwm adsorption rau peb cov pa roj carbon ntau. Lub peev xwm adsorption thiab desorption tus nqi ntawm CMK-3 tau mus txog 189.37 mg / g thiab 94.96%, feem. Lub peev xwm adsorption ntawm CMK-3 tau siab dua li ntawm CMK-8. Vim tias qhov pore ntim thiab thaj chaw tshwj xeeb ntawm CMK-3 loj dua DMC thiab CMK-8, nws tau qhia tias qhov pore ntim thiab thaj chaw tshwj xeeb yog qhov tseem ceeb cuam tshuam rau kev ua haujlwm adsorption.

Optimization of Adsorption Conditions Kev ua kom zoo dua ntawm adsorption sim rau CMK-3 tau ua tiav siv ob qho tib si sib xyawacteoside thiab enchanoside. Kub, pH, thiab concentration yog lub ntsiab tseem ceeb ntawm CMK -3 adsorption kev ua tau zoo. Yog li, cov teebmeem ntawm peb qhov cuam tshuam rau CMK-3 adsorption kev ua tau zoo raug tshawb xyuas.

Cov txiaj ntsig ntawm Cov Qauv Cuam Tshuam rau Adsorption Performance ntawm CMK-3

Cov nyhuv ntawm cov qauv concentration ntawm cov adsorption kev ua tau zoo ntawm CMK {{0}} yog qhia nyob rau hauv daim duab 5. Raws li cov concentration nce, lub peev xwm ntawm adsorption nce. Lub peev xwm adsorption tsis nce ntxiv nrog qhov nce ntawm cov qauv concentration thaum cov qauv concentration tau mus txog ntawm 0.41 mg / g. Ntawm qhov pib qis qis ntawm cov qauv, cov chaw ua haujlwm adsorbent tau txaus rau adsorption ntawm ib qho me me ntawm PhGs molecules. Nyob rau hauv sib piv, nyob rau hauv ib tug siab pib concentration ntawm cov qauv, tus nqi ruaj khov ntawm cov chaw nquag ntawm cov adsorbents tsis muaj peev xwm adsorb nce tus nqi ntawm PhGs molecules. Yog li, lub peev xwm adsorption ntawm CMK-3 rau PhGs molecules zoo li sib npaug.

NATURAL CISTANCHE TUBULOSA rau kev txhim kho kev sib deev PHGS75% ECH 30% ACT 12%

Qhov cuam tshuam ntawm pH ntawm Adsorption Performance ntawm CMK-3

Daim duab 6 qhia txog cov txiaj ntsig ntawm pH ntawm kev ua haujlwm adsorption ntawm CMK-3. Nws tuaj yeem pom los ntawm daim duab 6 tias qhov zoo tshaj pH tus nqi yog 6 rau qhov adsorption ntawm PhGs los ntawm CMK-3. Cov laj thawj yog raws li hauv qab no: PhGs muaj ntau pawg phenolic hydroxyl thiab koom rau cov tsis muaj zog acidic molecules, thiab cov pH sib txawv cuam tshuam rau ionization thiab stability ntawm PhGs molecules. Lub ionization ntawm phenolic hydroxyl pawg yuav inhibited ntawm tus nqi pH qis, thaum lub stability ntawm phenolic hydroxyl pawg ntawm PhGs yuav txo qis ntawm tus nqi pH siab. Qhov inhibited ionization ntawm phenolic hydroxyl pawg ntawm PhGs ua rau txo qis hauv electrostatic kev sib cuam tshuam ntawm PhGs thiab CMK-3, txo qhov adsorption kev ua tau zoo ntawm CMK-3 rau PhGs. Yog li, qhov zoo tshaj pH yog 6 rau CMK- 3 adsorption.

Qhov cuam tshuam ntawm qhov kub thiab txias ntawm Adsorption Performance ntawm CMK-3

Kub yog ib qho tseem ceeb parameter nyob rau hauv cov txheej txheem adsorption. Qhov kub tsis tsuas yog cuam tshuam rau qhov sib txawv ntawm PhGs molecules ntawm sab nraud ciam teb interface tab sis kuj nyob rau hauv cov adsorbent pores. Daim duab 7 qhia qhov tshwm sim ntawm qhov kub thiab txias ntawm lub peev xwm adsorption ntawm CMK-3. Lub peev xwm adsorption ntawm CMK-3 nce nrog kub nce ntawm 30 txog 60◦C. Nws tau raug tshaj tawm tias qhov laj thawj tseem ceeb yog qhov chaw ua haujlwm tau nce nrog qhov kub thiab txias vim qhov endothermic xwm ntawm cov txheej txheem, thiab intra-particle diffusion ntawm cov adsorbents tau nce nrog qhov nce ntawm qhov kub ntawm adsorption (Peng li al., 2015) . Tsis tas li ntawd, kev txav mus los ntawm PhGs molecules tau nce ntxiv thiab lawv qhov kev tawm tsam tsis kam txo nrog qhov kub thiab txias. Lub peev xwm adsorption txo qis nrog qhov kub thiab txias thaum qhov kub ntawm 60-80 ◦C. Nws tau qhia tias qhov ntsuas kub adsorption muaj qhov zoo tshaj plaws thiab tias PhGs molecules yuav tsis ruaj khov ntawm qhov kub siab. Yog li ntawd, qhov zoo tshaj plaws adsorption kub yog xaiv los ntawm 60 ◦C.

Qhov zoo tshaj plaws adsorption tej yam kev mob ntawm CMK{{0}} yog raws li nram no: tus qauv concentration yog 0.41 mg/g, cov tshuaj pH yog 6, thiab cov adsorption kub yog 60◦C. Nyob rau hauv cov xwm txheej zoo, lub peev xwm adsorption ntawm PhGs nyob rau hauv crude extract ntawm CMK -3 yog 358.09 ± 4.13 mg / g, uas yog ntau tshaj peb npaug ntawm adsorption peev ntawm PhGs ntawm macroporous resins (HPD300, 94.93 mg / g) (Liu et al., 2013). Lub caij no, tus nqi desorption ntawm CMK-3 yog 94.67% siab dua li ntawm macroporous resin.

Adsorption Isotherms Cov

Cov adsorption isotherms muaj nyob rau hauv daim duab 8A. Nrog rau qhov nce ntawm qhov sib npaug ntawm qhov sib npaug, lub peev xwm adsorption rau PhGs tau nce thiab mus txog qhov ua kom saturation. Txhawm rau nkag siab ntxiv txog kev ua haujlwm adsorption ntawm PhGs ntawm CMK-3, cov adsorption isotherms ntawm CMK-3 tau tshawb xyuas siv Langmuir thiab Freundlich qauv. Cov tsis muaj adsorption tau los ntawm cov qauv sib txawv muab qee cov ntaub ntawv tseem ceeb ntawm adsorption mechanisms. Daim duab 8B, thiab C tau piav qhia txog CMK-3 adsorption isotherms qauv los ntawm Langmuir thiab Freundlich qauv.

Tus qauv Langmuir tau ua raws li qhov kev xav tias adsorption tshwm sim ntawm qhov chaw tshwj xeeb hauv cov adsorbent, tsis muaj kev cuam tshuam loj tshwm sim ntawm hom adsorbed, thiab cov adsorbent tau saturated tom qab ib txheej ntawm

adsorbent molecules tsim rau ntawm qhov chaw adsorbent. Linearized Langmuir isotherm equation tuaj yeem sau tau raws li hauv qab no:

Tus qauv Freundlich feem ntau yog siv los piav txog cov yam ntxwv adsorption ntawm ntau txheej thiab ntau qhov chaw (Wu li al., 2017). Nws daim ntawv linearized yog muab raws li hauv qab no:

qhov twg qm (mg / g) yog qhov theoretical siab tshaj plaws monolayer adsorption muaj peev xwm, KL (mL / mg) yog Langmuir tas li hais txog lub zog adsorption cuam tshuam txog kev sib raug zoo ntawm adsorbate thiab adsorbent (Wu li al., 2017; He et al. , 2019), KF [(mg/g)•(mL/mg)1/n] thiab n yog Freundlich constants. KF yog qhov taw qhia ntawm tus txheeb ze adsorption muaj peev xwm, n muaj feem xyuam rau qhov loj ntawm lub adsorption tsav tsheb thiab heterogeneity ntawm qhov chaw sib khi, thiab 1 / n qhia qhov zoo ntawm adsorption.

Qhov tsis sib xws ntawm cov qauv isotherm tau sau tseg hauv Table 3. Cov qauv Langmuir tau zoo dua li Freundlich qauv los piav qhia cov ntaub ntawv adsorption ntawm PhGs ntawm CMK-3, uas qhia tau tias qhov adsorption ntawm PhGs ntawm CMK{{2 }} yog ib qho yooj yim monolayer adsorption txheej txheem (Wang F. li al., 2017). Tsis tas li ntawd, muaj cov pa oxygen

cov pab pawg ua haujlwm nyob rau saum npoo ntawm CMK{{0}} txhim kho cov adsorption ntawm PhGs. Qhov siab tshaj plaws adsorption tus nqi (qm) tuaj yeem ncav cuag 380.70 mg / g uas zoo ib yam li tus nqi sim. Tsis tas li ntawd, 1 / n tus nqi ntawm PhGs tau suav tias yog 0.22, uas yog<0.5. It indicated that the adsorption of the PhGs on the CMK-3 could take place easily (Fu et al., 2007; Gan et al., 2018). This indicated that the adsorption of PhGs on CMK-3 was not completely a physical adsorption process. PhGs contain multiple hydroxyl groups which might form hydrogen bonds with the oxygen-containing functional groups on the CMK-3 and offer weak chemical adsorption for the adsorption. Therefore, CMK-3 adsorption of PhGs was a complex adsorption process combining physical adsorption with chemisorption. 

Adsorption Kinetics

CMK-3 adsorption muaj peev xwm raug tshawb xyuas raws li lub sijhawm ua haujlwm los txiav txim siab lub sijhawm adsorption equilibrium hauv daim duab 9A. Qhov kev tshawb fawb qhia tau hais tias qhov sib npaug adsorption tus nqi maj mam txo qis thiab maj mam txo qis thaum lub peev xwm adsorption nce mus txog qhov sib npaug. Nws tau pom tias qhov sib npaug adsorption tau mus txog tom qab 14 teev. Tus nqi pib sai sai tuaj yeem yog vim qhov siab concentration gradient ntawm PhGs thiab CMK-3 hauv kev daws teeb meem thiab qhov chaw ntawm CMK-3 muaj ntau qhov chaw ua haujlwm.

Adsorption kinetics tau soj ntsuam los ntawm daim ntawv thov ntawm pseudo-thawj-order, pseudo-thib ob-order, thiab intra-particle diffusion qauv. Cov duab kos duab ntawm pseudo-thawj-order, pseudo-second-order qauv, thiab intra-particle diffusion qauv rau adsorption ntawm PhGs mus rau CMK-3 yog qhia nyob rau hauv daim duab 9B-D, raws li.

Lub linear daim ntawv ntawm cov qauv kinetics yog qhia raws li nram no:

Pseudo-thawj-order (Li et al., 2017a):

Pseudo-thib ob-order (Tang et al., 2018):

qhov twg K1 (1 / min) thiab K2 (g / mg·min−1 ) yog tus nqi tsis tu ncua ntawm pseudo-thawj tus nqi sib npaug thiab pseudo-thib ob-txoj kev sib npaug, feem. qe (mg / g) yog theoretical adsorption peev ntawm qhov sib npaug.

Intra-particle diffusion qauv:

qhov twg Kp yog qhov intra-particle diffusion tas li (mg / g min) thiab C yog qhov cuam tshuam ntawm thaj tsam txheej txheej (mg / g).

Cov nqi suav ntawm qe, tus nqi tsis tu ncua, thiab kev sib raug zoo coefficient yog qhia hauv Table 4. Tus qauv pseudo-thib ob-order tau muab tus nqi R 2 ntawm 0.998, thaum tus nqi R 2 ntawm tus pseudo-thawj- xaj qauv yog 0.84. Nws txhais tau hais tias tus qauv pseudo-thib ob-txiav txim siab nthuav tawm txoj kev sib raug zoo dua li tus qauv pseudo-thawj thawj-order. Daim duab 9C qhia tau hais tias cov phiaj xwm kab ntawm t/qe vs. t qhia pom zoo nrog cov ntaub ntawv sim los ntawm cov qauv pseudo-thib ob-kev txiav txim. Qhov xam qe ntawm pseudo-thib ob-kev txiav txim tau zoo ib yam li cov ntaub ntawv sim (Table 4). Cov txiaj ntsig no tau qhia tias pseudo-thib ob-kev txiav txim yog tus qauv kinetics zoo dua li pseudo-thawj-order.

Txawm li cas los xij, qhov kev ntsuam xyuas cov txiaj ntsig ntawm tus qauv pseudo-thib ob-kev txiav txim tsis tuaj yeem txiav txim siab lub peev xwm adsorption mechanism. Nws feem ntau tau lees paub tias adsorption kinetics tau tswj hwm los ntawm diffusion mechanism, uas muaj sab nraud diffusion, ciam txheej diffusion, thiab intra-particle diffusion (Wong et al., 2019). Tus qauv intra-particle diffusion tau siv los txiav txim siab tias intra-particle diffusion yog tus nqi-limiting kauj ruam.

Lub intra-particle diffusion tau hais tias yog tus nqi txwv cov kauj ruam thaum qt vs. t1/2 yog linear. Lub intra-particle diffusion yog tib theem tswj tus nqi thaum lub nkhaus dhau los ntawm lub hauv paus chiv keeb. Nws tuaj yeem pom los ntawm daim duab 9D, qhov sib txawv ntawm qhov sib txawv tau tswj hwm los ntawm ob theem sib txawv. Thawj theem ntawm qhov nkhaus sawv cev rau saum npoo adsorption. Qhov thib ob theem qhia intra-particle diffusion hauv CMK-3 pores. Raws li intra-particle diffusion zajlus tsis dhau los ntawm lub hauv paus chiv keeb, tus qauv qhia tau hais tias lub adsorption mechanism yog ntau tshaj ib tug mechanism thiab intra-particle diffusion tsis yog tus nqi-limiting kauj ruam xwb. Yog li, nws tuaj yeem txiav txim siab tias cov txheej txheem ntawm PhGs adsorption ntawm CMK-3 yog qhov nyuaj uas ob qho tib si sab nraud adsorption thiab intra-particle diffusion tshwm sim ib txhij.

Kev sim rov ua dua

Reusability yog ib qho tseem ceeb hauv kev xav txog kev siv thiab tus nqi ntawm adsorbents hauv kev siv tswv yim. Yog li ntawd, qhov kev ua tau zoo ntawm cyclic adsorption ntawm CMK -3 rau cov extract crude tau sim. Daim duab 10 qhia txog cov txiaj ntsig ntawm cyclic adsorption ntawm CMK-3 rau cov extract ntawm Cistanche tubulosa. Nws tuaj yeem pom los ntawm daim duab 10 tias qhov muaj peev xwm adsorption ntawm CMK -3 hloov ntawm 358.09 ± 4.13 mg / g rau 320.78 ± 5.62 mg / g tom qab peb lub voj voog ntawm adsorption, uas qhia tias CMK-3 tau zoo rov ua dua, thiab CMK-3 tuaj yeem siv rov qab siv dua los nqus PhGs.

Cov lus xaus

Cov khoom adsorption ntawm PhGs ntawm peb hom mesoporous carbons tau tshawb xyuas thiab cov pa roj carbon mesoporous ua ntej thiab tom qab adsorption tau tshwm sim. Cov txiaj ntsig tau pom tias CMK-3 muaj thaj chaw tshwj xeeb tshaj plaws thiab qhov pore ntim ntawm peb qhov adsorbents (CMK- 3, DMC, thiab CMK-8), thiab nws tuaj yeem nqus tau PhGs molecules zoo dua. tshaj DMC thiab CMK-8 los ntawm covExtract ntawm Cistanche tubulosa.Vim tias cov pab pawg ua haujlwm muaj pa oxygen nyob rau saum npoo ntawm CMK-3 tuaj yeem muab ntau qhov chaw ua haujlwm adsorption rau PhGs molecules. Tsis tas li ntawd, hydrogen bonds tau tsim los ntawm hydroxyl pawg ntawm PhGs thiab cov pa oxygen-muaj cov haujlwm ua haujlwm ntawm CMK- 3. Lub peev xwm adsorption ntawm crude extract rau PhGs yog 358. -3 yog 95.02%. Cov ntaub ntawv adsorption tau nthuav tawm tias adsorption ntawm PhGs ua raws li Langmuir qauv thiab pseudo-thib ob-order qauv, tus qauv intra-particle diffusion qhia tias tus nqi-txheej cov kauj ruam ntawm adsorption yog intra-particle diffusion qauv. CMK -3 tuaj yeem siv los ua qhov muaj peev xwm adsorbent kom muaj txiaj ntsig zoo adsorb PhGs los ntawm Cistanche tubulosa.

NATURAL CISTANCHE TUBULOSA EXTRACT CISTANCHE HERB EXTRACT PHGS75% ECH 30% ACT 12%