Copper (II) immobilized on magnetically separable L-arginine-β-cyclodextrin ligand system as a robust and green catalyst for direct oxidation of primary alcohols and benzyl halides to acids in neat conditions

Article abstract of DOI:10.1016/j.jorganchem.2020.121128

Copper (II) immobilized on L-arginine-β-cyclodextrin-functionalized magnetite nanoparticles (nano-Fe₃O₄@L-arginine-CD-Cu(II)) were successfully synthesized and fully characterized using FT-IR, XRD, SEM, EDX, ICP, TGA and VSM techniques. The catalytic activity of these magnetically retrievable nanoparticles was evaluated in the direct oxidation of primary alcohols and benzyl halides to acids in neat conditions that was observed to proceed well and products were obtained in good yields. In addition to showing good catalytic activity, the magnetic catalyst is easy to synthesize and can be recycled at least five times with little loss in activity.

Full text of DOI:10.1016/j.jorganchem.2020.121128

Journal Pre-proof
Copper (II) immobilized on magnetically separable l-arginine-β-cyclodextrin ligand
system as a robust and green catalyst for direct oxidation of primary alcohols and
benzyl halides to acids in neat conditions
Masoumeh Jadidi Nejad, Arefe Salamatmanesh, Akbar Heydari
PII:
S0022-328X(20)30029-2
DOI:
https://doi.org/10.1016/j.jorganchem.2020.121128
JOM 121128
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 20 September 2019
Revised Date: 26 November 2019
Accepted Date: 17 January 2020
Please cite this article as: M.J. Nejad, A. Salamatmanesh, A. Heydari, Copper (II) immobilized on
magnetically separable l-arginine-β-cyclodextrin ligand system as a robust and green catalyst for direct
oxidation of primary alcohols and benzyl halides to acids in neat conditions, Journal of Organometallic
Chemistry (2020), doi: https://doi.org/10.1016/j.jorganchem.2020.121128.
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Copper (II) immobilized on magnetically separable L-arginine-β-cyclodextrin
ligand system as a robust and green catalyst for direct oxidation of primary
alcohols and benzyl halides to acids in neat conditions
1
1
1*
Masoumeh Jadidi Nejad . Arefe Salamatmanesh . Akbar Heydari
1
Chemistry Department, Tarbiat Modares University, P.O. Box 14155-4838, Tehran, Iran.
E-mail: heydar_a@modares.ac.ir; Fax: +98-21-82883455; Tel: +98-21-82883444
*
Abstract
Copper (II) immobilized on L-arginine-β-cyclodextrin-functionalized magnetite nanoparticles
(
nano-Fe O @L-arginine-CD-Cu(II)) was successfully synthesized and fully characterized using
3 4
FT-IR, XRD, SEM, EDX, ICP, TGA and VSM techniques. The catalytic activity of these
magnetically retrievable nanoparticles was evaluated in the direct oxidation of primary alcohols
and benzyl halides to acids in neat conditions that was observed to proceed well and products
were obtained in good yields. In addition to showing good catalytic activity, the magnetic
catalyst is easy to synthesize and can be recycled at least five times with little loss in activity.
Keywords Copper (II) complex; β-cyclodextrin; L-arginine; Magnetite nanoparticles; Benzylic oxidation;
Acids
1
Introduction
Oxidation is a fundamental research field in both laboratorial and industrial levels to synthesize
various useful products [1,2]. Carboxylic acids are important structural motifs found in a wide
range of natural products [3], pharmaceuticals and fine chemicals [4,5], they are also used as
significant organic synthetic precursors to prepare esters, amides and polymers [6]. Therefore,
direct oxidation of benzyl chlorides, benzyl bromides and especially alcohols to carboxylic acids
is one of the most important reactions in organic synthesis [7–9]. Traditionally, acids are
produced from primary alcohols by the use of toxic and hazardous strong oxidants such as
manganese(VII) [10,11], chromium(VI) [12,13], hypervalent iodine [14,15] and activated DMSO
[16,17], resulting in copious waste from at least stiochiometric amounts of these oxidants. Thus,
it is important to develop environmentally friendly new oxidization protocols. During the last
decades, most of the reported catalytic systems for the synthesis of carboxylic acid from alcohol
under mild conditions are based on noble metals such as palladium, gold, ruthenium, iridium,

and platinum, however the limited accessibility and high price of these noble metals constrict
their application in largescale industrial production [18–21].
Non-metal catalytic systems for this oxidation transformation have also been attracted much
attention and some previous studies employed DDQ, [22] thiourea, [23] and quinine-derived urea
[24] as organocatalyst for the oxidation of alcohols. In the search of new aerobic oxidation
procedures for alcohols, promising results have been obtained by using of catalytic systems
including nitroxyl radicals, such as (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) and first-
row transition metals, such as Cu, Fe and Mn [25–32]. Catalysts that contain earth-abundant
elements such as Co, [33] Fe, [34] Mn, [35] Cu, [36] etc. are both economically and
environmentally attractive, however their efficiencies are generally low when compared with the
noble metal catalysts [37] and, in most cases, a large amount of various base additives or
hazardous oxidizing agents (e.g., peroxy acids, and metal oxidants) are also required to promote
the activity and selectivity [38].
In recent years, many catalytic systems involving transition metal complexes with hydrogen
peroxide as mild and cheap green oxidant have been investigated for the oxidation of alcohols
[39–42]. In some researches, various alcohols were transformed into the corresponding
carboxylic acids and ketones in good yields with t-BuOOH (TBHP) in the presence of Bi O as
2
3
catalyst [43]. Also, in 2013 for the first time, the use of tetra-n-butylammonium bromide
TBAB) as an organocatalyst with TBHP for this transformation was reported [44]. Moreover, a
(
variety of transition metal catalysts such as Fe, Mo, Ru, Pd, V, Mn, Cu, etc. with TBHP as an
oxidizing agent have been utilized for oxidation reactions of alcohols [45–52]. Among various
catalytically active transition metal complexes, copper complexes bearing phosphines or nitrogen
ligands have found numerous applications in organic transformations; however, there are still
ongoing efforts to prepare stable copper complexes. β-Cyclodextrin (β-CD) is a water-soluble
cyclic oligosaccharide consisting of seven glucose and toroidal in shape with a hydrophobic
central cavity and a hydrophilic outer surface that is used as phase transfer and interface reaction
catalyst. In addition, it has been shown that β-CD is capable of reversible formation of the host–
guest complexes through non‐covalent bondings in the cavity upon installation of transition
metals and can be used effectively for catalytic organic reactions [53-55]. Host–guest interaction
and metal–ligand coordination are significant noncovalent interactions to form catalytically
active transition-metal complexes for organic reactions [56,57].

In the last decade, we devoted our research to develop new heterogeneous and reusable catalysts
for promoting greener catalytic reactions. Magnetic nanoparticles have attracted much attention
as supports for heterogeneous catalysts due to their ease of separation, recoverability, chemical
stability, high surface area and ability to be functionalized [58].
In continuation of our laboratory interests in developing environmentally procedures [59], now
we have focused on β-CD as a greener supramolecular compound and L-arginine as a
nucleophilic natural amino acid. Copper (II) immobilized on L-arginine-β-cyclodextrin-
functionalized magnetite nanoparticles were successfully synthesized and fully characterized,
then these synthesized magnetic nanoparticles were employed as a highly efficient and
recoverable green catalyst for direct oxidation of primary alcohols and benzyl halides to acids in
neat conditions.
2
Experimental
2
.1 Materials and Instrumentation
All reagents and solvents were purchased from reputable commercial suppliers and used without
further purification. All reactions were carried out in the air. All reported yields are isolated
-1
yields. FT-IR spectra were obtained over the region 400−4000 cm using a Nicolet IR100 FT-IR
with spectroscopic grade KBr. The X-ray diffraction pattern was obtained at room temperature
°
using a Philips X-pert 1710 diffractometer with Co Kα (α = 1.78897 A ), 40 kV voltage, 40 mA
current and in the range 100- 900 (2θ) with a scan speed of 0.020/s. SEM (Philips XL 30 and S-
4
160) was utilized to study the catalyst morphology and size. Magnetic saturation of the catalyst
was obtained using a vibrating magnetometer/ alternating gradient force magnetometer
VSM/AGFM, MDK Co., Iran). Thermal gravimetric analysis was recorded using a thermal
(
°
-1
°
analyzer with a heating rate of 20 C min over a temperature range of 25-1100 C under flowing
1
nitrogen. ICP analyse was performed using a Varlan Vista-Pro ICP-OE spectrometer. H NMR
1
3
and C NMR spectra were recorded on a Bruker Avance (DRX 250 MHz and DRX 500 MHz)
in a pure deuterated CHCl solvent with tetramethylsilane (TMS) as an internal standard.
3
2
.2 Preparation of Fe O @L-arginine
3 4
5
3 2 2 2
mmol FeCl .6H O and 2.5 mmol FeCl .4H O salts were dissolved in 50 ml water under
vigorous stirring. An aqueous ammonia solution (28 %w/w, 30 ml) was then added to the stirring
mixture to reach the reaction pH about 11, followed by adding 1.5 mmol of L-arginine. This

°
mixture was refluxed at 100 C for 8 h. The resulting nanoparticles were collected magnetically
°
and washed several times with water and ethanol and dried in an oven at 80 C.
2
3 4
.3 Preparation of Fe O @L-arginine-CD-Cu(II)
At first tosylation of CD was performed according to the former procedure [53]. Typically, p-
toluenesulfonyl chloride (5mmol) was added to a solution of pyridine containing 10 mmol CD,
°
the suspension was cooled to 0 C and kept for 24 h. Upon completion, cold water was added to
the mixture in order to afford a white precipitate. The resulting precipitate was filtered and dried
in oven. To synthesize the Fe
in dry toluene under stirring conditions. The resulting mixture was added to the suspension of
Fe @L-arginine (0.5 gr) in dry toluene. After that, the mixture was refluxed for 18 h. The
3 4
O @L-arginine-CD, β-cyclodextrin-OTS (0.25 gr) was dispersed
3
O
4
resulting nanoparticles were concentrated by magnetic decantation and washed several times
with toluene (2× 100 mL), ethanol (2× 100 mL) and finally diethyl ether, followed by drying in
an oven.
The resultant nanoparticles were dispersed in 20 mL of water and then 2 mmol of
2 2
Cu(OAC) .2H O in 30 ml of water was added, the resulting suspension was stirred at room
temperature. After 24 h, nanoparticles were separated using an external magnet and washed
several times with water and ethanol and dried in an oven overnight.
2
.4 General procedure for oxidation of primary alcohols and benzyl halides using
Fe O @L-arginine-CD-Cu(II)
3
4
An appropriate primary alcohol (1.0 mmol) or benzyl halide (1.0 mmol) was added into a test
tube containing 40 mg catalyst and 4 mmol of tert-butyl hydroperoxide (TBHP 70 wt%) under
°
solvent free conditions. Then the suspension was magnetically stirred for 5 h at 90 C. The
progress of the reaction was monitored by TLC. After completion of the reaction, an aqueous
solution of potassium hydroxide was added to the resulting mixture followed by separation of the
catalyst from the mixture by an external magnet. After separation of the catalyst, it was washed
with ethanol (2× 10 mL) and dried in an oven for reuse in subsequent reactions under the same
conditions. Then the resulting solution was extracted with ethyl acetate and aqueous phase was
separated, then hydrochloric acid was added dropwise to the aqueous solution to reach the
mixture pH about 11 and finally the obtained mixture was extracted with ethyl acetate. The
organic phase was separated and evaporated to afford the desired product in pure form.

3
Results and Discussion
The procedure for the synthesis of the catalytic system is shown in Scheme 1. Fe O
3
4
nanoparticles were prepared according to conventional co-precipitation method of ferrous and
ferric ions in alkali solution. The abundant surface hydroxyl groups of Fe provide this
3
O
4
possibility for grafting of arginine on these magnetic nanoparticles. Subsequently, the reaction of
modified magnetic nanoparticles with β-CD–OTS, obtained from the treatment of β-CD (β-
cyclodextrin) and TsCl (p-toluenesulfonylchloride), led to the desired magnetic nanoparticles-
supported organocatalyst. Finally, treatment of L-arginine-β-CD-functionalized magnetite
2 3 4
nanoparticles with Cu(OAc) in MeOH for 24h provided Fe O @L-arginine-CD-Cu(II).
According to the previous reports [56,57], and by considering the presence of β-cyclodextrin and
L-arginine functional groups that can act respectively as good host and active ligand for
immobilizing copper species, it can be expected that there are two coordinated Cu(II) ions on
each chain.
Scheme 1. Preparation of nano-Fe O @L-arginine-CD-Cu(II).
3
4

The synthesized catalyst was fully characterized using various instrumental techniques such as
FT-IR, XRD, SEM, EDX, TGA, ICP and VSM. The FT-IR spectra of the magnetic nanoparticles
show the peaks that confirm the successful synthesis of the catalyst [60]. The FT-IR spectra of
3 4 3 4 3 4
Fe O , Fe O @L-arginine, Fe O @L-arginine-CD-Cu(II) are shown in Figure 1. The typical
-1
peak of Fe-O stretching vibration in 567 cm demonsrate the formation of magnetite
nanoparticles. In the spectrum for arginine-functionalized magnetic nanoparticles, the peak
-1
appearing at 1626 cm is ascribed to the COO stretching vibrations. It means that the L-arginine
-1
-1
was supported on the magnetite surface. The bands at 2922 cm and 3414 cm can be attributed
to the stretching vibrations of –CH and –OH groups in β-CD. Meanwhile, the successful
attachment of β-CD on the surface of Fe O @arginine can be clearly confirmed by the observed
2
3
4
-1
characteristic peaks at 1026, 1153 and 1219 cm , which could be attributed to the antisymmetric
glycosidic C–O–C vibration and the coupled C–C/C–O stretching vibration.
(
(
(
c) Fe O @L-arginine-CD-Cu(II)
3 4
b) Fe O @L-arginine
3
4
a) Fe O4
3
-
Wavenumbers (cm
Figure 1. The FT-IR spectra of the Fe O (a), Fe O @L-arginine (b) and Fe O @L-arginine-CD-Cu(II) (c).
3
4
3
4
3
4
The surface morphology of the prepared catalyst was evaluated by scanning electron microscopy
SEM). The SEM image of the catalyst showed that the particles of the catalyst were obtained in
nano scale and these magnetic nanoparticles in the presence of L-arginine-cyclodextrin-Cu(II)
(

have a nearly spherical shape (Figure 2a). Energy-dispersive X-ray (EDX) spectrum of the
obtained nanomaterials (Figure 2b) confirmed the presence of the expected elements in the
structure of Fe O @L-arginine-CD-Cu(II), namely iron, oxygen, nitrogen and copper with wt%
3
4
of 87.49, 8.42, 0.60 and 0.73, respectively.
b
Figure 2. a) SEM and b) EDX analysis of the catalyst.
To determine the crystalline structure of the magnetic nanoparticles, X-ray diffraction (XRD)
°
pattern was studied in a domain of 10–90 (Figure 4). It can be observed that the diffraction
°
°
°
°
°
°
peaks at around 35.17 , 41.53 , 50.53 , 63.61 , 67.77 , and 74.61 corresponding to (220), (311),
400), (422), (511), and (440) are quite identical to characteristic peaks of the standard spinel
(
cubic magnetite (JCPDS card no. 19–0629) and any other characteristic peaks due to the
impurities of other oxides of iron were not detected.

Figure 4. X-ray diffraction pattern of Fe O @L-arginine-CD-Cu(II).
3
4
Thermogravimetric analysis (TGA) was performed to investigate the thermal behavior of the
catalyst. The TGA result of Fe
3
O
4
@L-arginine-CD-Cu(II) is presented in Figure 3. The weight
°
loss observed in TGA curve below 200 C can be mainly attributed to the water desorption from
the magnetite surface (1.76%). Two degradation steps can be detected over the range of 220–550
°
C, which can be attributed to the subsequent decomposition of organic moieties, L-arginine and
β-CD, grafted on the surface of the magnetite nanoparticles. Using TGA analysis, the content of
3 4
organic moiety in Fe O @L-arginine-CD-Cu(II) was estimated to be about 12.52 w/w%.
Moreover, the Cu content of the prepared catalyst was 0.086 mmol per gram of Fe O @L-
3
4
arginine-CD-Cu(II) using ICP-AES.
Figure 3. TGA curve of Fe O @L-arginine-CD-Cu(II).
3
4

Magnetic hysteresis measurements of the nanoparticles were explored in an applied magnetic
field at room temperature, with the field sweeping from −10000 to +10000 Oe using a vibrating
sample magnetometer (VSM). As shown in Figure 5, the saturation magnetization (Ms) value of
nanoparticles is 60.15, demonstrating that the catalyst is superparamagnetic. Some decreasing of
the value of Ms in compare to pure Fe O is attributed to the organic layer on the surface of
3
4
3 4
Fe O [61].
3 4
Figure 5. Magnetization curve of Fe O @L-arginine-CD-Cu(II).
The catalytic performance of Fe O @L-arginine-CD-Cu(II) was investigated in the oxidation of
3
4
benzyl alcohol to benzoic acid as a model reaction (Table 1). As seen in entry 1, using TBHP as
oxidant in the absence of the catalyst no product was observed, also in the presence of pure
3 4
Fe O we observed that only a trace amount of benzyl alcohol was oxidized (Table 1, entry 2).
Using 40 mg catalyst in the presence of H O and meta-chloroperoxybenzoic acid (MCPBA) as
2
2
oxidant gave 20% and 10% yield of benzoic acid, respectively (Table 1, entry 3,4). In the next
step, when the reaction was performed in the presence 40 mg of the catalyst in neat conditions at
°
9
0 C, we observed the formation of the most amount of the desired product, (Table 1, entry 5).
We optimized the catalyst amount and according to the obtained results (Table 1, entries 5-8) 40
mg (0.34 mol%) of the catalyst was chosen as the best catalyst amount. Subsequently, the model
reaction was performed in different temperatures (Table 1, entries 9-12) and the optimized
°
temperature was obtained (90 C). To examine the effect of different solvents, the model reaction
was performed in the presence of various solvents such as: acetonitrile, ethanol, H O, DMF,
2

DMSO, toluene and xylene affording desired product in good to excellent yields (Table 1, entries
1
3-20). As shown in Table 1, the best result was obtained by carrying out the reaction using 40
°
mg (0.34 mol%) of Fe O @L-arginine-CD-Cu(II) at 90 C in neat conditions (Table 1, entry 5).
3
4
Scheme 2. Oxidation reaction of benzyl alcohol.
Table 1. Optimization of reaction conditions for oxidation of benzyl alcohol.
Catalyst
mg)
Copper content
(mol%)
°
a
Entry
Oxidant
Solvent
Temperature ( C)
Yield (%)
(
None
1
2
3
4
5
6
7
8
9
None
TBHP
TBHP
H O
Neat
90
90
90
90
90
90
90
90
RT
70
80
100
90
90
90
90
90
90
90
90
N.R
N.R
20
None
Fe O4
3
Neat
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.34
.34
.34
.39
.17
.26
.34
.34
.34
.34
.34
.34
.34
.34
.34
.34
.34
40
40
40
45
20
30
40
40
40
40
40
40
40
40
40
40
40
Neat
2
2
MCPBA
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
Neat
Trace
92
Neat
Neat
92
Neat
35
Neat
60
Neat
Trace
55
1
1
1
1
1
1
1
1
1
0
1
2
3
4
5
6
7
8
Neat
Neat
80
Neat
93
acetonitrile
Ethanol
60
60
H O
2
40
DMF
Trace
Trace
20
DMSO
Toluene
xylene
1
2
9
0
15
0.34
4
0
mesitylene
15
Reaction conditions: benzyl alcohol (1.0 mmol), Oxidant (4.0 mmol), Catalyst ( 40 mg), 5 h in neat conditions.
a
Isolated yields.
To demonstrate the generality of this protocol, the scope of the reaction was investigated under
the optimized conditions and the results are summarized in Tables 2. We found that these
conditions are useful for a wide range of primary alcohols and benzyl halides. Different benzylic
alcohols, including those with either electron-withdrawing or electron-donating groups, were
oxidized to the benzoic acids in quantitative yield (Table 2, entries 1-9). When allylic and

furfuryl alcohols were employed as substrate, the corresponding acids were generated in high
yields (Table 2, entries 10, 11). Aliphatic alcohol was oxidized slower than the others (Table 2,
entry 12). When various benzyl halides were employed in the reaction, the corresponding acids
were obtained in good to excellent yields (Table 2, entries 13-20). Following the same procedure
as described above, when benzyl cyanide was used, the corresponding acid was obtained in
excellent yield (Table 2, entry 21).
Table 2. Oxidation reaction of primary alcohols and benzyl halides.
Yield
Entry
Substrate
Product
a
(%)
1
92
90
2
3
89
68
4
5
85
90
6

7
80
8
9
89
85
10
87
11
12
13
91
55
92
14
85

15
16
17
18
19
87
80
85
65
80
2
0
1
75
90
2
Reaction conditions: benzyl alcohol or benzyl halide or benzyl cyanide (1.0 mmol), (TBHP 70 wt%) (4.0 mmol), Fe O @L-
3
4
arginine-CD-Cu(II) ( 40 mg), 5 h in neat conditions.
a
Isolated yields.
The plausible mechanism for the oxidation of benzyl halides and benzyl alcohols in the presence
of catalyst is shown in scheme 2. In the first step by using of Cu and TBHP, activated benzyl
halide produced carbonyl group and tert-butanol. In the second step, carbonyl group was
activated and oxidized to benzoic acid.

tBuOOH
tBuO
CuIII
OH
CuII
3
Fe O
4
3
Fe O
4
tBu
O
O
OH
O
O
H O tBuOO
tBuOOH
2
OH
X
X
H O
2
N
C
,
tBuOH
HX
r
B
l,
C
=
tBuOO
X
tBuO
X
X
X
=
O
tBuOH
H
O
OH
tBuOH
OH
OH
tBuO
H
H O
2
OH
tBuOOH
tBuOO
tBuOOH
OH
O
H O
OH
2
OH
OH
3 4
Scheme 3. Proposed mechanism for oxidation of benzyl alcohol, benzyl halide and benzyl cyanide using Fe O @L-
arginine-CD-Cu(II).
The recyclability and reusability are very important points for heterogeneous catalysis systems.
In order to examine the reusability of the catalyst in oxidation reaction of primary alcohols to
acids, the model reaction was repeated under optimized conditions. In each cycle, after
completion of the reaction, the catalyst was magnetically concentrated and washed with ethanol
several times, dried and was used in the next cycle. We found that the catalyst was recovered for
five runs without considerable loss of its activity, as shown in Figure 6.
Figure 6. Recyclability of the synthesized catalyst.

In this research, we also measure the amount of leaching of copper from the heterogeneous
catalyst in the oxidation reaction by ICP analysis. For this purpose, the catalyst was removed by
magnetic decantation after the oxidation reaction of benzyl alcohol to benzoic acid was
completed and the copper content of the filtrate after the first reaction was determined to be only
0
.34%. Moreover, the copper loading amount before and after recycling of the catalyst was
checked by ICP analysis and it was observed that the copper content of this catalyst did not
decrease appreciably after the reaction.
4
Conclusions
In conclusion, we have developed a highly efficient, robust and recoverable green catalyst,
copper immobilized on magnetically separable L-arginine-β-cyclodextrin ligand system, for
direct oxidation of primary alcohols, benzyl halides and benzyl cyanide to acids in neat
conditions that was observed to proceed well and products were obtained in good yields. In
addition, recovery and reusability of the catalyst have been investigated in oxidation reaction of
benzyl alcohol to benzoic acid and the catalyst was reused in at least five cycles without a
significant loss of activity.
Acknowledgments We acknowledge Tarbiat Modares University for financial support of this
work.
Compliance with Ethical Standards
Conflict of interest We declare that no conflict of interest exists.
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Highlights
•
Cu (II) immobilized on L-arginine-β-CD-functionalized magnetite nanoparticles was well
synthesized
•
•
•
•
The synthesized catalyst was fully characterized by using various analytical techniques
The catalyst was used in the oxidation of primary alcohols and benzyl halides to acids
The reactions were carried out in neat conditions to obtain products in good yields
The catalyst was simply recycled and reused at least five times with little loss in activity

Declaration of interests
☒
The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.
☐
The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests: