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Quantification of Chemotaxis-Related Alkane Accumulation in Acinetobacter Baylyi Using Raman Microspectroscopy

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Quantification of Chemotaxis-Related Alkane Accumulation in Acinetobacter Baylyi Using Raman Microspectroscopy Analytical Chemistry This document is confidential and is proprietary to the American Chemical Society and its authors. Do not copy or disclose without written permission. If you have received this item in error, notify the sender and delete all copies. Quantification of chemotaxis -related alkane accumulation in Acinetobacter baylyi using Raman microspectroscopy Journal: Analytical Chemistry Manuscript ID ac-2016-02297e.R3 Manuscript Type: Article Date Submitted by the Author: n/a Complete List of Authors: Li, Hanbing; Lancaster University, Lancaster Environment Centre L Martin, Francis; Lancaster University, Centre for Biophotonics Zhang, Dayi; Lancaster University, ACS Paragon Plus Environment Page 1 of 25 Analytical Chemistry 1 2 3 4 Quantification of chemotaxis-related alkane accumulation in 5 6 Acinetobacter baylyi using Raman microspectroscopy 7 a a,b a, 8 Hanbing Li , Francis Luke L Martin , Dayi Zhang * 9 10 a Lancaster Environment Centre, Lancaster University, Lancaster, LA1 4YQ, UK 11 12 b School of Pharmacy and Biomedical Sciences, University of Central Lancashire, 13 14 Preston PR1 2HE, UK 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 *Corresponding author Dr Dayi Zhang, Lancaster Environment Centre, Lancaster 32 33 University, Lancaster, LA1 4YQ, UK; Tel.: +44(0)1524510288 ; Fax: 34 +44(0)1524510082 ; Email: [email protected] 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 1 ACS Paragon Plus Environment Analytical Chemistry Page 2 of 25 1 2 3 Abstract 4 5 Alkanes are one of the most widespread contaminants in the natural environment, 6 7 primarily as a consequence of biological synthesis and oil spills. Many indigenous 8 9 microbes metabolize alkanes, and the chemotaxis and accumulation in some strains 10 has been identified. For the first time, we apply Raman microspectroscopy to identify 11 12 such chemotaxis-related affinity, and quantify the alkane concentrations via spectral 13 14 alterations. Raman spectral alterations were only found for the alkane chemo- 15 attractant bacteria Acinetobacter baylyi ADP1, not for Pseudomonas fluorescence , 16 17 which exhibits limited chemotaxis towards alkane. The significant alterations were 18 19 attributed to the strong chemotactic ability of A. baylyi enhancing the affinity and 20 accumulation of alkane molecules on cell membranes or cellular internalization. 21 22 Spectral fingerprints of A. baylyi significantly altered after 1-h exposure to pure 23 24 alkanes (dodecane or tetradecane) and alkane mixtures (mineral oil or crude oil), but 25 not monocyclic aromatic hydrocarbons (MAHs) or polycyclic aromatic hydrocarbons 26 27 (PAHs). A semi-log linear regression relationship between Raman spectral alterations 28 29 and alkane concentrations showed its feasibility in quantifying alkane concentration in 30 environmental samples. Pure alkanes or alkane mixtures exhibited different limits of 31 32 detection and regression slopes, indicating that the chemotaxis-related alkane 33 34 accumulation in A. baylyi is dependent on the carbon chain length. This work 35 provides a novel biospectroscopy approach to characterize the chemotaxis-related 36 37 alkane bioaccumulation, and has immense potential for fast and high-throughput 38 39 screening bacterial chemotaxis. 40 41 42 43 Keywords: Acinetobacter baylyi ; Chemotaxis; Alkane; Affinity; Bioaccumulation; 44 45 Raman microspectroscopy; Spectral fingerprints 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 2 ACS Paragon Plus Environment Page 3 of 25 Analytical Chemistry 1 2 3 Introduction 4 5 Many hazardous chemicals have been released into the environment through various 6 7 industrial activities. Particularly, with industrial development and urbanization 8 9 processes, the increasing usage of crude oil has consequently been associated with 10 numerous oil spill accidents and contaminated sites. Since 1969, there have been >40 11 12 large oil spill incidents worldwide, including the Exxon Valdez oil spill in Prince 13 1,2 3 14 William Sound in 1989 , the Deepwater Horizon oil spill in Gulf of Mexico and the 15 Xingang oil spill in Dalian 4 in 2010. These incidents have resulted in large areas of 16 17 oil-contaminated sites, damaged ecological systems and threats to human health 5,6. 18 7-9 19 Chemical analysis of alkanes predominantly includes gravimetric , 20 fluorophotometry 10,11 , infrared (IR) absorption 12 , gas chromatography flame 21 22 ionization detector (GC-FID)13 or gas chromatography mass spectrometry (GC-MS) 23 14 24 methods , but samples require pre-treatment using solvent extraction or solid-phase 25 microextraction (SPME)15 . To evaluate alkane bioavailability or bioaccessibility, 26 27 some whole-cell bioreporters have been developed 16 and even applied in real-world 28 4,17 29 cases , but they suffer from relatively low reproducibility. Considering the rapid 30 response required to oil spill incidents, it is necessary to develop some real-time and 31 32 non-destructive screening tools to achieve fast and reliable detection of crude oil 33 34 contamination. 35 36 In the natural environment, alkanes are the main components of crude oil and 37 carbon sources for many bacteria, and alkane chemotaxis has been found in some 38 39 species 18 . Chemotaxis-related affinity to alkanes facilitates bacterial movement in 40 41 alkane gradients and contributes to their elevated abilities to access and utilize alkane 42 substrates19 . In Pseudomonas aeruginosa PAO1, the tlpS gene, which is located 43 44 downstream of the alkane monooxygenase alkB1 gene, is believed to encode a 45 46 methyl-accepting chemotaxis protein (MCP) that confers the chemotactic response to 47 hexadecane 20 . Another Pseudomonas strain, P. putida GPo1, has the alkN gene 48 49 encoding an MCP for alkane chemotaxis 21 . Flavimonas oryzihabitans is reported to 50 51 exhibit weak chemotactic responses to hexadecane but its mechanisms remain 52 unknown 22 . The alkane chemotaxis machinery of marine alkane degrader Alcanivorax 53 54 dieselolei consists of eight cytoplasmic chemotaxis proteins, including MCP and 55 23 56 flagellar proteins . Acinetobacter baylyi is the bacterial species with the strongest 57 alkane chemotaxis and accumulation 16,24-26 . In A. baylyi , the putative gene encoding 58 59 60 3 ACS Paragon Plus Environment Analytical Chemistry Page 4 of 25 1 2 3 an MCP is chpA which has high similarity to cheY (fused chemotactic sensory 4 5 histidine kinase) and ompR (two-component response regulator) in Escherichia coli , 6 suggesting potentially similar chemotaxis machinery. A. baylyi cells have high affinity 7 8 only to alkane droplets, but not to other hydrophobic molecules 16 , suggesting that the 9 10 MCP has high recognition specificity to linear alkanes. Meanwhile, alkane 11 chemotaxis further helps microbial accumulation, internalization and degradation of 12 13 alkanes by providing enhanced opportunities to seek out linear alkanes. The fimbriae 14 15 on the surface of Acinetobacter cells are postulated to drive the access to alkane 16 droplets for cellular uptake 27-29 . Trapped alkane droplets on the cell surface are 17 18 subsequently transported into bacterial cells after being emulsified by biosurfactant 19 30-32 20 mediation . 21 22 Raman microspectroscopy has been widely applied in biological molecule 23 detection, as a fast, reproducible and non-destructive approach generating a chemical 24 25 fingerprint 33 . It has been well developed to identify bacteria and study their responses 26 34-37 27 to their environment . Most spectrally-identified biological molecules are well 28 characterized, such as purine, pyrimidine, amino acids and proteins38-42 . Though many 29 30 approaches, such as swarm plates 43 , capillary assays 44 , temporal stimulation of 31 45 46 32 tethered cells and automated tracking of swimming cells , have been applied to test 33 the bacterial chemotaxis towards specific chemicals, there is still no study exploring 34 35 Raman spectral alterations during chemotaxis-related affinity and bioaccumulation 36 37 processes. The chemotactic behaviour of alkanes hints at the possibility that alkane 38 molecules will accumulate on the membrane and/or in the cytoplasm of bacterial cells, 39 40 potentially allowing them to be identified in Raman spectra. 41 42 In the present study, we used the Raman microspectroscopy to distinguish the 43 44 spectral alterations and quantify alkane concentrations based on the chemotaxis- 45 46 related alkane accumulation of A. baylyi . For the first time, we demonstrate that 47 chemotaxis-related alkane affinity and accumulation is measurable by Raman 48 49 microspectroscopy and the MCP of A. baylyi is highly specific to alkane molecules, 50 51 instead of monocyclic aromatic hydrocarbons (MAHs) or polycyclic aromatic 52 hydrocarbons (PAHs). Not only contributing to fast quantification of aqueous alkane 53 54 concentrations, this method also has the potential as a screening tool in characterising 55 56 chemotaxis-related affinity and accumulation towards various chemicals. 57 58 59 60 4 ACS Paragon Plus Environment Page 5 of 25 Analytical Chemistry 1 2 3 Experimental section 4 5 Strains and Growth Conditions 6 7 8 The two bacterial strains used in this study were the alkane chemotactic Acinetobacter 9 baylyi ADP1 and chemotaxis-negative Pseudomonas fluorescence . Both strains were 10 11 grown in minimal medium with 20 mM sodium succinate as the sole carbon source, at 12 13 30°C and 150 rpm for 16 h. The 1.0 litre minimal medium contained 1.0 g (NH 4)2SO 4, 14 . 2.5 g KH 2PO 4, 0.1 g MgSO 4 7H 2O, 0.005 g FeSO 4 7H 2O, 0.25 g nitrilotriacetic acid 15 16 (NTA), 0.55 g NaOH, and 1 mL Bauchop and Elsden solution. Strains were further 17 18 centrifuged at 4,000 rpm for 5 min and washed three times using sterile deionized 19 water, and finally suspended in minimal medium for further experimentation. 20 21 Hydrocarbon exposure 22 23 24 Unless specifically stated otherwise, all chemicals in this study were of analytical 25 grade and purchased from Sigma Aldrich (UK).
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