Open Access

New bactericide derived from Isatin for treating oilfield reinjection water

  • Gang Chen1,
  • Hui-jun Su1,
  • Min Zhang1,
  • Fang Huo1,
  • Jie Zhang1,
  • Xiao-jiang Hao2Email author and
  • Jing-rui Zhao3
Chemistry Central Journal20126:90

DOI: 10.1186/1752-153X-6-90

Received: 21 May 2012

Accepted: 13 August 2012

Published: 28 August 2012

Abstract

Isatin, an extract from Strobilanthes cusia (Nees) Kuntze, was the base for synthesizing derivatives that were screened for antibacterial activity against oilfield water-borne bacteria. The bacterial groups are sulfate reducing, iron and total. The derivatives were characterized by spectrums and they showed good to moderate activity against sulfate reducing bacteria.

https://static-content.springer.com/image/art%3A10.1186%2F1752-153X-6-90/MediaObjects/13065_2012_Article_487_Figa_HTML.gif

Background

The roots and the leaves of the plant, Strobilanthes cusia (Nees) Kuntze of the Acanthaceae family that is widely distributed in northern and central China, have been used in traditional Chinese medicine to treat a variety of ailments caused by microorganisms and virus. It is suggested that the demonstrated use can be extended to processing oilfield water to remove or reduce bacteria before the water is re-injected into formations via wells.

The alkaloid isatin or indole-2-3-dione (Figure 1) is a compound found in Strobilanthes cusia (Nees) Kuntze and many other plants such as genus Isatis, Calanthe discolor LINDL, Couroupita guianensis Aubl. and in mammalian tissue [1]. It has versatile bioactivity [2] and it is used to synthesize a large variety of heterocyclic compounds in preparing drugs [37]. Isatin Schiff bases are reported to have antibacterial activity against Bacillus subtilis[8], Gram(+) and Gram(−) bacterial strains [9] and Magnaporthe grisea[10] among others. The compound has been produced industrially and can thus be used for large-scale applications such as treating oilfield water before re-injection.
https://static-content.springer.com/image/art%3A10.1186%2F1752-153X-6-90/MediaObjects/13065_2012_Article_487_Fig1_HTML.jpg
Figure 1

Development of new bactericide for oilfield reinjection water treatment from traditional Chinese medicine.

Base synthesis and identification

Synthesis of isatin derivatives

Isatin (1 mmol) was dissolved in methanol (20 ml) and a methanol solution of 1.2 mmol amino compound (10 ml) was added dropwise, until the disappearance of isatin, as evidenced by thin-layer chromatography. The solvent was removed in vacuo and the residue was separated by column chromatography (silica gel, petroleum ether/ ethyl acetate = 1:1 ~ 1:3 v/v), to give the product. Single crystals of the compound 4 suitable for X-ray analysis was obtained on slow evaporation of a methanol solution (30 ml) of the product (30 mg) over a period of 7 d.

X-ray data collection and structure refinement

Intensity data for colorless crystals of compound 4 was collected at 150 K on a Bruker SMART 1000 CCD fitted with Mo Ka radiation. The data sets were corrected for absorption based on multiple scans [11] and reduced using standard methods [12]. The structures was solved by direct-methods [13] and refined by a full-matrix leastsquares procedure on F2 with anisotropic displacement parameters for non-hydrogen atoms, carbon-and nitrogen bound hydrogen atoms in their calculated positions and a weighting scheme of the form w = 1/σ2(Fo2 ) + (αP)2 + bP where P = (Fo2 + 2Fc2)/3) [14]. Crystal data and refinement details were given in Table 1.
Table 1

Experimental data of compound A and B

Empirical formula

C8H6N2O2

Formula weight

162.15

Temperature

293(2)

Wavelength (Mo Kα)

0.71073

Crystal system

Monoclinic

Space group

P2(1)

Crystal data

 

a (Ǻ)

3.8800(6)

b (Ǻ)

10.180(9)

c (Ǻ)

9.0500(6)

α (º)

90.00

β (º)

93.90(3)

γ (º)

90.00

Volume

356.63(12)

Z

2

Density (mg/m3)

1.510

Absorption coefficient

0.112

F (000)

168

Crystal size

0.20 × 0.22 × 0.30 mm3

Theta range for data collection (°)

1.9 to 27.3

Index ranges

−4 ≤ h ≤ 5;

−13 ≤ k ≤ 12;

−11 ≤ l ≤ 12

Reflections collected

3112

Independent reflections

2190

Reflections theta (°)

2.26 to 28.27

Absorption correction transmission

0.9440 to 0.9861

Reflections with I ≥ 2σ(I)

1427

Number of parameters

109

Goodness-of-fit on F2

1.006

Final R indices [I>2 s(I)]

R1 = 0.1884;

wR2 = 0.1323

R indices (all data)

R1 = 0.0674;

wR2 = 0.1027

Refine different density

−0.224 to 0.176

Microbiological monitoring

Viable counts of SRB, TGB and FB were determined with the “most probable number” method, People’s Republic of China Standard of Petroleum and Natural Gas Industry, the national method of the bactericidal agent’s performance, SY/T 5890–1993). The produced water containing the three kinds of bacteria was gathered from Zichang Oilfield Factory, Yanchang Oilfield.

Results and discussion

Chemistry

The isatin derivatives were synthesized as shown in Scheme 1. All the isatin derivatives were characterized by 1 H-NMR (400 MHz) and MS (EI) spectra and the results were summarized in Table 2. The entire spectra consist with the anticipated structures.
https://static-content.springer.com/image/art%3A10.1186%2F1752-153X-6-90/MediaObjects/13065_2012_Article_487_Sch1_HTML.gif
Scheme 1

Synthesis of isatin derivatives by condensation reaction.

Table 2

The 1 H-NMR (400 MHz) and MS (EI) spectra of the isatin derivatives

Comp. no.

Structure

1 H-NMR (400 MHz) and MS (EI) spectra

1

https://static-content.springer.com/image/art%3A10.1186%2F1752-153X-6-90/MediaObjects/13065_2012_Article_487_IEq1_HTML.gif

/

2

https://static-content.springer.com/image/art%3A10.1186%2F1752-153X-6-90/MediaObjects/13065_2012_Article_487_IEq2_HTML.gif

/

3

https://static-content.springer.com/image/art%3A10.1186%2F1752-153X-6-90/MediaObjects/13065_2012_Article_487_IEq3_HTML.gif

/

4

https://static-content.springer.com/image/art%3A10.1186%2F1752-153X-6-90/MediaObjects/13065_2012_Article_487_IEq4_HTML.gif

1 H-NMR (D6-Acetone), δ: 8.05 (1 H, d, J =7.2 Hz), 7.36 (1 H, t, J = 7.6 Hz), 7.04 (1 H, t, J = 7.6 Hz), 6.95 (1 H, d, J = 7.6 Hz), 6.84 (1 H, d, J = 7.6 Hz); MS m/z: 162 (M+)

5

https://static-content.springer.com/image/art%3A10.1186%2F1752-153X-6-90/MediaObjects/13065_2012_Article_487_IEq5_HTML.gif

1 H-NMR (D6-DMSO), δ: 12.40 (1 H, s), 11.08 (1 H, s), 9.06 (1 H, s), 8.95 (1 H, s), 7.66 (1 H, d, J = 7.6 Hz), 7.30 (1 H, t, J = 7.6), 7.10 (1 H, t, J = 7.6 Hz), 6.90 (1 H, d, J = 8.0 Hz); MS m/z: 204 (M+)

6

https://static-content.springer.com/image/art%3A10.1186%2F1752-153X-6-90/MediaObjects/13065_2012_Article_487_IEq6_HTML.gif

1 H-NMR (D6-DMSO), δ: 12.46 (1 H, s), 11.02 (1 H, s), 9.05 (1 H, s), 8.96 (1 H, s), 7.64 (1 H, d, J = 7.6 Hz), 7.34 (1 H, t, J = 7.6), 7.08 (1 H, t, J = 7.6 Hz), 6.91 (1 H, d, J = 8.0 Hz); MS m/z: 220 (M+)

7

https://static-content.springer.com/image/art%3A10.1186%2F1752-153X-6-90/MediaObjects/13065_2012_Article_487_IEq7_HTML.gif

1 H-NMR (D6-DMSO), δ: 12.01 (1 H, s), 11.01 (1 H, s), 9.23 (1 H, s), 8.90 (1 H, s), 7.54 (1 H, d, J = 7.6 Hz), 7.30 (1 H, t, J = 7.6), 6.86 (1 H, d, J = 8.0 Hz), 2.48 (1 H, s); MS m/z: 218 (M+)

8

https://static-content.springer.com/image/art%3A10.1186%2F1752-153X-6-90/MediaObjects/13065_2012_Article_487_IEq8_HTML.gif

1 H-NMR (D6-DMSO), δ: 10.92 (1 H, s), 9.56 (1 H, s), 7.32 (2 H, m), 6.86 (4 H, m), 6.74 (3 H, m); MS m/z: 238 (M+)

9

https://static-content.springer.com/image/art%3A10.1186%2F1752-153X-6-90/MediaObjects/13065_2012_Article_487_IEq9_HTML.gif

1 H-NMR (CDCl3), δ: 9.14 (1 H, s), 7.32 (1 H, d, J = 7.2 Hz), 7.08 (2 H, d, J = 8.8 Hz), 6.99 (3 H, m), 6.93 (1 H, d, J = 8.0 Hz), 6.79 (1 H, t, J = 7.6 Hz), 3.88 (3 H, s); MS m/z: 253 (M+)

10

https://static-content.springer.com/image/art%3A10.1186%2F1752-153X-6-90/MediaObjects/13065_2012_Article_487_IEq10_HTML.gif

1 H-NMR (CDCl3), δ: 9.98 (1 H, s), 7.64 (1 H, d, J = 7.2 Hz), 7.42 (1 H, d, J = 7.2 Hz), 7.14 (2 H, d, J = 8.8 Hz), 7.02 (3 H, m), 6.81 (1 H, d, J = 8.0 Hz); MS m/z: 256 (M+)

Besides, single crystal of compound 4 was analysized by X-ray, which confirms the assignment of the structure from spectroscopic data. The values of the geometric parameters of compound 4 are within normal ranges and experimental errors. The X-ray structural analysis confirmed the assignment of its structure from spectroscopic data. The molecular structure is depicted in Figure 2, and a packing diagram of compound 4 is depicted in Figure 3. Geometric parameters of compound 4 are in the usual ranges. The indol-2-one ring system is substantially planar. In the crystal structure, intermolecular N—H—N and O—H—O hydrogen bonds (Table 3) are effective in the stabilization of the structure and are responsible for the formation of a one-dimensional network. The angle of C1—C2—N2 is 115.734°, and the angle of C2—N2—O2 is 112.199°.
https://static-content.springer.com/image/art%3A10.1186%2F1752-153X-6-90/MediaObjects/13065_2012_Article_487_Fig2_HTML.jpg
Figure 2

An ORTEP-3 drawing of compound 4, with the atom-numbering scheme and 30% probability displacement ellipsoids.

https://static-content.springer.com/image/art%3A10.1186%2F1752-153X-6-90/MediaObjects/13065_2012_Article_487_Fig3_HTML.jpg
Figure 3

Packing of compound 4, dashed lines indicating hydrogen bonds.

Table 3

Hydrogen-bond geometry in the crystal of compound 4 (Å, °)

D—H···A

D—H

H···A

D···A

D—H···A

N1—H1A···N2i

0cxx.86

2.10

2.831 (8)

142

O2—H2A···O1ii

0.82

1.92

2.698 (5)

159

*Symmetry codes: (i) − x + 1, y + 1/2, −z + 2; (ii) − x + 1, y − 1/2, −z + 2.

Bioactivity

Produced water is a consequence of an oilfield exploitation that uses waterflood or steam injection or has an aquifer linked to the reservoir. The most usual disposal ways for high volumes of produced water is re-injected after treatment, which will meet some requirements imposed by environmental regulations [15]. Microbiologically influenced corrosion (MIC) caused by growth of sulfate reducing bacteria (SRB), iron bacteria (IB) and total general bacteria (TGB) in oil pipelines, is considered a major problem for water treatment in the oil industry [16]. MIC can result in different types of attack: pitting, crevices, dealloying and erosion in pipelines [17]. Corrosion products produced by microorganisms are production of hydrogen sulfide, molecular hydrogen, hydrogen ions and destabilization of metal oxide films. In addition, microbial degradation of crude oil can lead to increased acidity in the oil phase, and oil containing acids is a problem concerning corrosion of pipelines. The reported results showed that the interaction of IB, SRB and TGB accelerated the corrosion rate, and the corrosion in the mixture of IB, SRB and TGB was more serious than in a single microbial system. If this is the case, different treatment system to inhibit corrosion should be considered, among which bactericide agent has received the greatest acceptance. Currently, oxidizer, aldehyde, quatemary ammonium salt and heterocycle compounds has been used as bactericide agents, and Cl2, ClO2, formaldehyde, pentane-1, 5-dial, trichloroisocyanuric acid (TCCA) and ect [18], but the toxicity tests have been conducted on a limited selection.

In this work, isatin and amino compounds condensed to form the new C = N bond, and it is the isostere of C = O in the structure of isatin, which may ensure the bioactivity of these derivatives similar to isatin. The antifungal activity of these compounds against oilfield microorganism was tested under the concentration of 0.20 g/L and 0.02 g/L, and the results were summarized in Table 4.
Table 4

The antifungal activity of isatin derivatives against MIC

Compound

Concentration

Microbiotic concentration /mL

  

SIB

IB

TGB

110.0

110.0

110.0

1

0.20 g/L

2.5

25.0

70.0

0.02 g/L

2.5

25.0

110.0

2

0.20 g/L

0.9

6.0

70.0

0.02 g/L

0.9

2.0

110.0

3

0.20 g/L

0.5

2.5

13.0

0.02 g/L

0.6

2.0

110.0

4

0.20 g/L

0.6

13.0

13.0

0.02 g/L

0.0

70.0

70.0

5

0.20 g/L

0.6

110.0

110.0

0.02 g/L

0.0

110.0

110.0

6

0.20 g/L

0.5

25.0

110.0

0.02 g/L

0.9

25.0

110.0

7

0.20 g/L

0.0

25.0

2.5

0.02 g/L

0.6

25.0

2.5

8

0.20 g/L

0.0

110.0

70.0

0.02 g/L

0.0

110.0

110.0

9

0.20 g/L

0.0

6.0

110.0

0.02 g/L

0.0

13.0

110.0

10

0.20 g/L

0.0

0.5

13.0

 

0.02 g/L

0.6

0.9

110.0

From the table, it can be found that isatin is antifungal active against SRB, but inactive against IB and TGB under both concentrations. For the 5-substitued isatin, compound 2 and 3, the antifungal active against SRB is similar to isatin, slightly more potent against IB, but both, as well as isatin, are inactive against TGB. From the results of the 3-imine indole-2-one (compound 4–10), it was found that the SRB inhibitions are more effective potent under both concentration. While only compound 10 is active against IB with the microbial concentration of 0.5 /mL under the concentration of 0.20 g/L and 0.9 /mL under the concentration of 0.02 g/L. Only compound 7 is active against TGB with the microbial concentration of 2.5 /mL under both concentration.

Declarations

Authors’ Affiliations

(1)
College of Chemistry and Chemical Engineering, Xi’an Shiyou University
(2)
State Key Laboratory of Phytochemistry and Plant Resources in West China, Kunming Institute of Botany, Chinese Academy of Sciences
(3)
Shannxi Hai’an Industry Co., LTD

References

  1. Yoshikawa M, Murakami T, Kishi A, Sakurama T, Matsuda H, Nomura M, Matsuda H, Kubo M: Novel indole S, O-bisdesmoside, calanthoside, the precursor glycoside of tryptanthrin, indirubin, and isatin, with increasing skin blood flow promoting effects, from two Calanthe species (Orchidaceae). Chem Pharm Bull. 1998, 46 (5): 886-888. 10.1248/cpb.46.886.View Article
  2. Chen G, Hao XJ: Recent studies on the bioactivities of isatin. Natural Product Research and Development. 2010, 22: 356-360.
  3. Chen G, Hao XJ, Sun QY, Ding J: Rapid eco-friendly synthesis and bioactivities of 3-nitromethylene-1,3-dihydro-indol-2-one analogues. Chemical Papers. 2010, 64 (5): 673-377. 10.2478/s11696-010-0047-1.View Article
  4. Chen G, He HP, Ding J, Hao XJ: Synthesis and antitumor activity evaluation of regioselective spiro [pyrrolidine-2, 3'-oxindole] compounds. Heterocyclic Communication. 2009, 15 (5): 355-361.View Article
  5. Chen G, Yang J, Gao S, He HP, Li SL, Di YT, Chang Y, Lu Y, Hao XJ: Spiro[pyrrolidine-2,3'-oxindole] derivatives synthesized by novel regionselective 1,3-dipolar cycloadditions. Mol Divers. 2012, 16: 151-156. 10.1007/s11030-011-9342-1.View Article
  6. Chen G, Zhang J, Tang Y, Hao XJ, Mu SZ: Micheal addition between isatin and acrylate derivatives. Letters in Organic Chemistry. 2011, 8 (9): 614-617. 10.2174/157017811799304269.View Article
  7. DaSilva JFM, Garden SJ: da C Pinto A: The chemistry of isatins: a review from 1975 to 1999. The Journal of the Brazilian Chemical Society. 2001, 12: 273-324. 10.1590/S0103-50532001000300002.View Article
  8. Cerchiaro G, Aquilano K, Filomeni G, Rotilio G, Ciriolo MR, Ferreira AMDC: Isatin-schiff base copper(II) complexes and their influence on cellular viability. J Inorg Biochem. 2005, 99: 1433-1440. 10.1016/j.jinorgbio.2005.03.013.View Article
  9. Sridhara SK, Saravanana M, Ramesh A: Synthesis and antibacterial screening of hydrazones, Schiff and Mannich bases of isatin derivatives. Eur J Med Chem. 2001, 36: 615-625. 10.1016/S0223-5234(01)01255-7.View Article
  10. Chen G, Wang Y, He HP, Li SL, Zhou LG, Hao XJ: Synthesis of 3-imine/methylene-indole-2-one compounds and the bioactivty screen on inhibition of germination of Magnaporthe grisea spores. Acta Botanica Yunnanica. 2007, 29 (6): 712-721.
  11. Sheldrick GM: SADABS. 2003, Germany: University of Göttingen, Version 2.10
  12. Otwinowski Z, Minor W: Methods in enzymology, vol276. Macromolecular crystallography. Edited by: Part A, Carter CW Jr, Sweet RM. 1997, New York: Academic Press
  13. Sheldrick GM: SHELXL97. 1997, Germany: University of Göttingen
  14. Sheldrick GM: SHELXS97. 1997, Germany: University of Göttingen
  15. Carlson V, Bennett EO, Rowe JA: Microbial flora in a number of oilfield water-injection system. SPE. 1961, 1553-G-
  16. Kajiyama F, Okamura K: Evaluating cathodic protection reliability on steel pipe in microbially active soils. Corrosion. 1999, 55 (1): 74-80. 10.5006/1.3283968.View Article
  17. Rupi P: Assessment and control of mic in the oil industry in the 20th century. Corrosion. 2000, 00390-
  18. Liu HT, Huang L, Li T, Gu YL: Application and progress in bactericide of sulfate reducing bacteria. Journal of Chinese Society for Corrosion and Protection. 2009, 29 (2): 154-160.

Copyright

© Chen et al.; licensee Chemistry Central Ltd. 2012

This article is published under license to BioMed Central Ltd. This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://​creativecommons.​org/​licenses/​by/​2.​0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.