Kyushu University Academic Staff Educational and Research Activities Database
List of Papers
ANDREW ROBERTSON Last modified date:2021.07.09

Associate Professor / Faculty of Engineering / Faculty of Engineering


Papers
1. Douglas Philp, Andrew Robertson, Recognition-induced control of a Diels-Alder reaction, Chemical Communications, 10.1039/a800559a, 8, 879-880, 1998.04, The rational design of a system which is capable of controlling the stereochemical outcome of a Diels-Alder reaction between a maleimide and a furan is presented..
2. Andrew Robertson, Douglas Philp, Neil Spencer, Recognition-induced control of a Diels-Alder cycloaddition, Tetrahedron, 10.1016/S0040-4020(99)00633-X, 55, 37, 11365-11384, 1999.09, The rational design of systems which are capable of accelerating and/or controlling the stereochemical outcome of the Diels-Alder cycloaddition reaction between a furan and a maleimide is presented. The origins of the acceleration and control of the cycloaddition reactions are traced by kinetic studies - allied to molecular mechanics calculations - to the formation of complexes in which the dienes and the dieneophiles are placed in the appropriate arrangements for reaction, and, more importantly, to the formation of intramolecular hydrogen bonds in the cycloadducts..
3. Hideomi Kijima, Masayuki Takeuchi, Andrew Robertson, Seiji Shinkai, Christopher Cooper, Tony D. James, Exploitation of a novel 'on-off' photoinduced electron-transfer (PET) sensor against conventional 'off-on' PET sensors, Chemical Communications, 10.1039/a906825b, 19, 2011-2012, 1999.10, A novel PET sensor for sugar sensing which changes its fluorescence intensity in an 'on-off' manner was designed from (tetraphenylporphyrinato)tin(IV)..
4. Atsushi Sugasaki, Masato Ikeda, Masayuki Takeuchi, Andrew Robertson, Seiji Shinkai, Efficient chirality transcription utilizing a cerium(IV) double decker porphyrin
A prototype for development of a molecular memory system, Journal of the Chemical Society - Perkin Transactions 1, 10.1039/a904890a, 22, 3259-3264, 1999.11, A cerium(IV) double decker porphyrin 2 bearing two pairs of 4-pyridyl groups and two pairs of 3,5-dimethoxyphenyl groups was synthesized. In the presence of chiral dicarboxylic acid guests with a two carbon spacer [e.g., (1R,2R)-cyclohexane-1,2-dicarboxylic acid and Boc-L-aspartic acid] 2 gave a CD-active species. The plots of the CD intensity vs. the guest concentration showed a sigmoidal curvature, a sign of homotropic, positive allosterism. Analysis according to the Hill equation indicated that the guests were bound autoacceleratively. Even after the chiral guests were removed by the addition of excess pyridine, 2 remained CD-active because of its inherent chirality. Thereafter, the CD intensity decreased very slowly as a result of internal rotation of the porphyrin subunits. Thermodynamic analysis of this racemization process gave ΔG 298 = 23.0 kcal mol-1, ΔH 298 = 18.1 kcal mol-1 and ΔS 298 = -16.4 cal mol-1 K-1. Observations and calculations indicate that the chiral memory can be preserved for 3 days at 0°C and for one year at -37°C. In conclusion, this is a rare artificial system for which a homotropic, positive allosterism is observable and in which the guest chirality is transcribed and stored..
5. Masato Ikeda, Masayuki Takeuchi, Atsushi Sugasaki, Andrew Robertson, Tomoyuki Imada, Seiji Shinkai, Strong Positive Allosterism which Appears in Molecular Recognition with Cerium(IV) Double Decker Porphyrins
'Correlation between the Number of Binding Sites and Hill Coefficients, Supramolecular Chemistry, 10.1080/10610270008029453, 12, 3, 321-345, 2000, Cerium(IV) double decker porphyrins bearing one-to-four pairs of 4-pyridyl groups (3a, 3a′, 3bp, 3bd, 3c, and 3d) were synthesized from tetraarylporphyrins bearing mono-, bis-, tris-, and tetrakis(4-pyridyl) groups. In 3b bearing two pairs of 4-pyridyl groups, there exist two isomers in which the 4-pyridyl groups are either proximal or distal (3bp and 3bd, respectively). In a mixed solvent of dichloromethane: ethyl acetate (30:1 v/v), 3a′ bearing one pair of 4-pyridyl groups and three pairs of phenyl groups did not interact with any dicarboxylic acids whereas 3d bearing four pairs of 4-pyridyl groups interacted only with dicarboxylic acid guests with a dimethylene spacer [e.g., BOC-L-aspartic acid (L-4) and (1R,2R)-cyclohexane-1,2-dicarboxylic acid ((1R,2R)-5)]. Interestingly, the complexation process monitored by CD spectroscopy showed a positive homotropic allosterism which satisfied the Hill equation giving constants K = 2.63×1011M-4 and n = 3.9 for L-4 and K = 2.75×109 M-4 and n = 4.0 for (1R,2R)-5. The continuous variation plots (Job plots) also supported the formation of the 1:4 3d/dicarboxylic acid guest complexes. The results consistently indicate that four pairs of 4-pyridyl groups in 3d allosterically bind these guests. In 3d, the two porphyrin rings can still rotate, but once the rotation is suppressed by the first guest binding, the subsequent binding of the second, third and fourth guests can occur cooperatively. This is the origin of the present positive homotoropic allosterism. A similar positive homotropic allosterism was also observed for 3bp and 3bd with n = 1.5 and 1.7, respectively and 3c with n = 3.0. The X-ray crystallographic study of the 3d·[(1R,2R)-5]4 complex showed that the two porphyrin planes are warped outward to relax the electrostatic repulsion and chirally twisted. The two carboxylic acid groups form intermolecular hydrogen bonds (but not intramolecular bridge-type hydrogen bonds) with the pyridyl groups because of the close packing effect of rigid host 3d and rigid guest (1R,2R)-5. In conclusion, this is a rare example of positive homotropic allosterism in an artificial system which is frequently seen in nature where the biological events must be efficiently regulated in response to signals..
6. Andrew Robertson, Andrew J. Sinclair, Douglas Philp, Minimal self-replicating systems, Chemical Society Reviews, 10.1039/a803602k, 29, 2, 141-152, 2000.01, Examples of chemical systems capable of templating and catalysing their own synthesis - self-replicating systems -have begun to appear in the chemical literature over the last 15 years. For the biologist, these systems represent a link with the origin of life - their study can shed light on prebiotic chemical evolution. However, for the synthetic chemist, they represent the ultimate synthetic machine, capable of templating the production of a large number of perfect copies of themselves from a single original molecule. In this Review, we describe the design and synthesis of synthetic minimal replicating systems and provide a general overview and critique of the field..
7. Andrew Robertson, Seiji Shinkai, Cooperative binding in selective sensors, catalysts and actuators, Coordination Chemistry Reviews, 10.1016/s0010-8545(00)00243-5, 205, 1, 157-199, 2000.01, This article is concerned with the incorporation of cooperative molecular recognition and metal ion coordination in the design of selective sensors that signal binding events through their optical properties. Sensors that rely on non-specific hydrophobic effects are first considered before looking at the use of specific, directed intermolecular interactions to achieve greater specificity and chiral discrimination. The natural development of the same design concepts to produce catalysts and actuating devices with similar discriminatory abilities is also discussed..
8. Andrew Robertson, M. Ikeda, M. Takeuchi, Seiji Shinkai, Allosteric binding of K+ to crown ether macrocycles appended to a lanthanum double decker system, Bulletin of the Chemical Society of Japan, 10.1246/bcsj.74.883, 74, 5, 883-888, 2001.05, A benzocrown-appended lanthanum(III) porphyrin double decker has been synthesized which is capable of binding simple K+ in a cooperative, allosteric fashion to form a 1:4 complex. Analysis of this system by means of the Hill equation gave an overall binding constant (Kb) of 1.0 × 1014 (mol dm-3)-4 and a Hill coefficient of 4.0. This same system, however, binds Na+ in a conventional, linear fashion. These results indicate that the novel allosteric binding occurs as the result of 1:2 sandwich complexes between K+ and appended crown ether moieties of the two joined porphyrins. The suitability of lanthanum(III) over cerium(IV) for preparing this highly crowded double decker porphyrin is also noted..
9. Andrew Robertson, Takahiro Matsumoto, Seiji Ogo, The development of aqueous transfer hydrogenation catalysts, Dalton Transactions, 10.1039/c1dt10544b, 40, 40, 10304-10310, 2011.10, This review discusses the development of aqueous phase, homogeneous, transfer hydrogenation catalysis. Transfer hydrogenation catalysts, based on Ru, Ir and Rh, reduce organic substrates in water by assisting the transfer of hydrogen from simple donor species. These catalysts are expected to have significant benefits when compared with organic phase catalysts, including greater activity, greater selectivity and smaller environmental impact. They will therefore be expected to make a significant contribution to homogeneous catalysis and 'green chemistry'. Here, we comprehensively examine these catalysts, paying special attention to structural features..
10. Kyoungmok Kim, Takahiro Matsumoto, Andrew Robertson, Hidetaka Nakai, Seiji Ogo, Simple ligand effects switch a hydrogenase mimic between H 2 and O 2 activation, Chemistry - An Asian Journal, 10.1002/asia.201101020, 7, 6, 1394-1400, 2012.06, Herein, we report a [NiRu] biomimetic system for O 2-tolerant [NiFe]hydrogenases and demonstrate that electron donation to the [NiRu] center can switch the system between the activation of H 2 and O 2 through simple ligand effects by using hexamethylbenzene and pentamethylcyclopentadienyl ligands, respectively. Furthermore, we present the synthesis and direct observations of a [NiRu]-peroxo species, which was formed by the oxygenation of a Ni-SIa model [NiRu] complex, that we propose as a biomimetic analogue of O 2-bound species (OBS) of O 2-tolerant [NiFe]hydrogenases. The [NiRu]-peroxo complex was fully characterized by X-ray analysis, X-ray photoelectron spectroscopy (XPS), mass spectrometry, and 1H NMR spectroscopy. The OBS analogue was capable of oxidizing p-hydroquinone and sodium borohydride to turn back into the Ni-SIa model complex..
11. Takeshi Yatabe, Mitsuhiro Kikkawa, Takahiro Matsumoto, Keishi Urabe, Andrew Robertson, Hidetaka Nakai, Seiji Ogo, An fe-based model for metabolism linking between O2-reduction and H2O-oxidation, Chemistry Letters, 10.1246/cl.150468, 44, 9, 1263-1265, 2015.01, Here, we report the first Fe-based model for metabolism linking between the dioxygen reduction of respiration and the water oxidation of photosynthesis. The reaction mechanism was investigated by X-ray analysis, UV-vis spectroscopy, and mass spectrometry..
12. Koji Yoshimoto, Takeshi Yatabe, Takahiro Matsumoto, Andrew Robertson, Hidetaka Nakai, Hiromasa Tanaka, Takashi Kamachi, Yoshihito Shiota, Kazunari Yoshizawa, Koichiro Asazawa, Hirohisa Tanaka, Seiji Ogo, Synthesis and structure of a water-soluble μ-η1
η1-N2 dinuclear RuII complex with a polyamine ligand, Chemistry Letters, 10.1246/cl.151004, 45, 2, 149-151, 2016.01, We report the first example of a μ-η11-N2 dinuclear RuII complex with a polyamine ligand and elucidate the structure by means of X-ray analysis. The N=N stretching vibration has been observed at 1994 cm-1 by Raman spectroscopy, which is the lowest value of all the known N2-coordinated RuII complexes. This low value strongly suggests the N=N bond is primed for activation..
13. Koji Yoshimoto, Takeshi Yatabe, Takahiro Matsumoto, Viet Ha Tran, Andrew Robertson, Hidetaka Nakai, Koichiro Asazawa, Hirohisa Tanaka, Seiji Ogo, Inorganic clusters with a [Fe2MoOS3] core - A functional model for acetylene reduction by nitrogenases, Dalton Transactions, 10.1039/c6dt01655c, 45, 37, 14620-14627, 2016.01, We report the first example of a wholly inorganic mimic of a part of the FeMoco active centre of nitrogenases. We detail the synthesis, characterisation and reactivity of two related, transient hydride-containing inorganic clusters, a dihydride complex and a vinyl monohydride complex, which bear the [Fe2MoOS3] portion of FeMoco. The dihydride complex is capable of reducing acetylene to ethylene via the vinyl monohydride complex. In the reaction cycle, a transient low-valent complex was generated by the reductive elimination of H2 or ethylene from dihydride or vinyl monohydride complexes, respectively..
14. Mohammed Djemai, Hakim Saibi, Mohamed Mesbah, Andrew Robertson, Spatio-temporal evolution of the physico-chemical water characteristics of the Sebaou river valley (Great Kabylia, Algeria), Journal of Hydrology: Regional Studies, 10.1016/j.ejrh.2017.04.002, 12, 33-49, 2017.08, The Sebaou river valley (SRV) is located in the northern Tell region of Algeria, and is a significant source of ground and surface waters because of its geographical context within the northern Algerian Tell region. The water resources from the study area are important for both local people and environmental scientists since the area is undergoing significant industrial development. Therefore a quantitative and qualitative study of the surface and groundwater can help us to establish the current physico-chemical variables of the water resources, allowing comparisons with future studies. In this study we present the most comprehensive survey of the hydrogeological properties of this region reported to date, including the spatio-temporal variation of physico-chemical variables as studied by principal component analysis. This method allowed us to confirm the principal chemical facies and to differentiate the waters of the middle and upper Sebaou river from the waters of river tributaries, specifically the Aissi and Bougdoura rivers. The quality of these water resources is declining as a result of local development and so this study is expected to provide a valuable resource for future water management strategies in the region..
15. ROBERTSON, A., A Total Project Approach to Academic Courses, 2017.01.
16. DJEMAI, M., SAIBI, H., MESBAH, M., ROBERTSON, A., Spatio-temporal evolution of the physico-chemical water characteristics of the Sebaou river valley (Great Kabylia, Algeria), 2019.08.
17. YOSHIMOTO, K., YATABE, T., MATSUMOTO, T., TRAN, V.-H., ROBERTSON, A., NAKAI, H., ASAZAWA, K., TANAKA, H., OGO, S., Inorganic clusters with a [Fe2MoOS3] core - A functional model for acetylene reduction by nitrogenases, 2019.08.
18. YOSHIMOTO, K., YATABE, T., MATSUMOTO, T., ROBERTSON, A., NAKAI, H., TANAKA, H., KAMACHI, T., SHIOTA, Y., YOSHIZAWA, K., ASAZAWA, K., TANAKA, H., OGO, S., Synthesis and structure of a water-soluble μ-η1:η1-N2 dinuclear RuII complex with a polyamine ligand, 2019.08.
19. YATABE, T., KIKKAWA, M., MATSUMOTO, T., URABE, K., ROBERTSON, A., NAKAI, H., OGO, S., An Fe-based model for metabolism linking between O2-reduction and H2O-oxidation, 2019.08.
20. KIM, K., MATSUMOTO, T., ROBERTSON, A., NAKAI, H., OGO, S., Simple ligand effects switch a hydrogenase mimic between H2 and O2 activation, 2019.08.
21. ROBERTSON, A., IKEDA, M., TAKEUCHI, M., SHINKAI, S., Allosteric binding of K+ to crown ether macrocycles appended to a lanthanum double decker system, 2019.08.
22. IKEDA, M., TAKEUCHI, M., SUGASAKI, A., ROBERTSON, A., IMADA, T., SHINKAI, S., Strong Positive Allosterism which Appears in Molecular Recognition with Cerium(IV) Double Decker Porphyrins: 'Correlation between the Number of Binding Sites and Hill Coefficients, 2019.08.
23. SUGASAKI, A., IKEDA, M., TAKEUCHI, M., ROBERTSON, A., SHINKAI, S., Efficient chirality transcription utilizing a cerium(IV) double decker porphyrin: A prototype for development of a molecular memory system, 2019.08.
24. KIJIMA, H., TAKEUCHI, M., ROBERTSON, A., SHINKAI, S., COOPER, C., JAMES, T.D., Exploitation of a novel 'on-off' photoinduced electron-transfer (PET) sensor against conventional 'off-on' PET sensors, 2019.08.
25. ROBERTSON, A., PHILP, D., SPENCER, N., Recognition-induced control of a Diels-Alder cycloaddition, 1999.08.
26. PHILP, D., ROBERTSON, A., Recognition-induced control of a Diels-Alder reaction, 1998.08.