Selective Adsorption and Efficient Degradation of Petroleum Hydrocarbons by a Hydrophobic/Lipophilic Biomass Porous Foam Loaded with Microbials.

Highly efficient elimination of petroleum pollution is of great importance for addressing environmental issues and social sustainability. In this study, we demonstrate a novel strategy for efficient elimination of petroleum pollution by selective adsorption of it by an ultralight hydrophobic/lipophilic microorganism-loaded biomass porous foam (BTS-MSFT4@MTMS) followed by a green degradation of adsorbates under mild conditions. The porous structure of biomass porous foam (MSFT) could provide plenty of room for immobilization of Bacillus thuringiensis (BTS), while a simple surface modification of the MSFT load with a BTS strain (BTS-MSFT4) by methyltrimethoxysilane (MTMS) could change its wettability from hydrophilic to lipophilic, which makes selective adsorption of hydophobic petroleum pollution from water for biodegradation possible. As expected, using a petroleum n-hexadecane solution with a concentration of 3% as a model oily wastewater, the as-prepared BTS-MSFT4@MTMS possesses both a superior selective adsorption of ca. 99% and high degradation activity with a high degradation rate of up to 86.65% within 8 days under the conditions of 37 °C, 120 r min-1, and pH = 7, while the degradation rates for the BTS-MSFT4 and the free BTS strain were measured to be only 81.62 and 65.65%, respectively, under the same conditions. In addition, the results obtained from the study on environment tolerance show that the BTS-MSFT4@MTMS exhibits a strong tolerance under different conditions with various pHs, temperatures, and initial concentrations. Compared with the existing methods for removal of petroleum pollution by direct adsorption of petroleum pollution via superoleophilic porous materials or applying free microorganisms for biodegradation only, which suffers the drawbacks of low selectivity or poor efficiency, our method has great advantages of cost-effectiveness, scalable fabrication, and high efficiency without secondary pollution. Moreover, such a two-in-one strategy by integration of both selective adsorption and biodegradation into biodegradable BTS-MSFT4@MTMS may particularly have great potential for practical application in environmental remediation.

Qualitative analysis of the roots of Salvia miltiorrhiza and Salvia yunnanensis based on NIR, UHPLC and LC-MS-MS.

Near infrared spectroscopy (NIR) was applied to discriminate the roots of salvia miltiorhiza Bunge (Danshen for short) and Salvia yunnanensis C. H. Wright (Zidanshen for short) by means of principal component analysis (PCA), improved and simplified K nearest neighbors (IS-KNN). Furthermore, an ultra-high performance liquid chromatographic (UHPLC) coupled with photodiode-array detector was developed for building fingerprints of lipophilic components of Danshen and Zidanshen, respectively. Basing on NIR information, both PCA and IS-KNN method classified the two kinds of Chinese medical herbs with 100% accuracy. The chromatographic fingerprints of the lipophilic components of Danshen and Zidanshen have 10 and 12 common peaks, respectively. Liquid chromatography coupled with mass spectroscopy (LC-MS-MS) was applied to identify these peaks. Among these, three small peaks in the fingerprints of Zidanshen are not found in Danshen, one of which was identified as α-lapachone, and the other two compounds were not yet identified; a small peak after tanshinone IIA in the fingerprints of Danshen was not found in Zidanshen, which was identified as miltirone. The two herbs have 10 common lipophilic components. The similarity between the two reference chromatograms of Zidanshen and Danshen is 0.902, but the mean similaritie between Zidanshen (or Danshen) fingerprints and its own reference chromatogram is 0.973 (or 0.976). The contents of main lipophilic components are significantly lower in Zidanshen than in Danshen (P < 0.01 or P < 0.05). The results indicate that the two Chinese medical materials are not only different in NIR spectra, but also different in species and quantities of lipophilic components. NIR spectra analysis can identify Danshen and Zidanshen rapidly and accurately. UHPLC coupled with MS analysis demonstrates the detail differences between the two herbs both in species and contents of their lipophilic components.

[Analysis of lipophilic components of Salvia miltiorrhiza roots and S. yunnanensis roots by UPLC and LC-MS/MS].

Fingerprints of lipophilic components in the roots of Salvia miltiorrhiza and S.yunnanensis were analyzed by UPLC-DADand UPLC coupled with mass spectroscopy to evaluate the differences and similarities of the lipophilic components in the two kinds of herbs.The UPLC analysis of 18 batches of S.miltiorrhiza and 16 batches of S.yunnanensis was performed on a 25℃Thermo Accucore C_(18)column(2.1 mm×100 mm,2.6µm)by Shimadzu LC-20AD;mobile phase was 0.026%phosphoric acid(A)-acetonitrile(B)with gradient elution;flow rate was 0.4 m L·min~(-1);detection wavelength was set at 270 nm;injection volume was 2µL.The molecular structures of the lipophilic components were analyzed on a 25℃Thermo Accucore C_(18)column(2.1 mm×100 mm,2.6µm)by Thermo U3000 UPLC Q Exactive Orbitrap LC-MS/MS with a mobile phaseconsisting of 0.1%formic acid water(A)and 0.1%formic acidacetonitrile(B).The mass spectrometry was acquired in positive modes using ESI.There are 10 common peaks in the lipophilic components of S.miltiorrhiza.The similarity between the 16 batches of S.miltiorrhiza and their own reference spectra was greater than 0.942,and the average similarity was 0.973.There are 12 common peaks in the lipophilic components of S.yunnanensis.The similarity between the 18 batches of S.yunnanensis and their own reference spectra was greater than 0.937,and the average similarity was 0.976.The similarity between the reference chromatograms of S.miltiorrhiza and S.yunnanensis was only 0.900.There are three lipophilic components in S.yunnanensis,which are not found in S.miltiorrhiza,and one of which isα-lapachone.There is a lipophilic component in S.miltiorrhiza not found in S.yunnanensis,which may be miltirone.The two herbs contain 8 common lipophilic components including dihydrotanshinoneⅠ,cryptotanshinone,tanshinoneⅠ,tanshinoneⅡ_A,nortanshinone in which the content of tanshinoneⅡ_A,dihydrotanshinoneⅠand cryptotanshinone of S.yunnanensisis significantly lower than that of S.miltiorrhiza(P<0.01),and the contents of tanshinoneⅠand nortanshinone are significantly lower than that of S.miltiorrhiza too(P<0.05).There are significant differences in the types and contents of lipophilic components between the roots of S.miltiorrhiza and S.yunnanensis,and the similarity between the fingerprints of interspecies is much lower than that between the same species.Therefore,the roots of S.miltiorrhiza and S.yunnanensis are two kinds of herbs which are quite different in chemical compounds and compositions.