An improved synthesis of ‘octa-acid’ deep-cavity cavitand

An improved synthesis of a water-soluble deep-cavity cavitand (octa-acid, 1) is presented. Previously (Gibb, C.L.D.; Gibb, B.C. J. Am. Chem. Soc. 2004, 126, 11408–11409), we documented access to host 1 in eight (non-linear) steps starting from resorcinol; a synthesis that required four steps involving chromatographic purification. Here, we reveal a modified synthesis of host 1. Consisting of seven (non-linear) steps, this new synthesis involves only one chromatographic step, and avoids a minor impurity observed in the original approach. This improved synthesis is therefore useful for the laboratories that are investigating the properties of these types of host.     

Understanding the Role of Water in Aqueous Ruthenium‐Catalyzed Transfer Hydrogenation of Ketones.

We report an accurate computational study of the role of water in transfer hydrogenation of formaldehyde with a ruthenium‐based catalyst using a water‐specific model. Our results suggest that the reaction mechanism in aqueous solution is significantly different from that in the gas phase or in methanol solution. Previous theoretical studies have shown a concerted hydride and proton transfer in the gas phase (M. Yamakawa, H. Ito, R. Noyori, J. Am. Chem. Soc. 2000 , 122, 1466–1478;J.‐W. Handgraaf, J. N. H. Reek, E. J. Meijer, Organometallics 2003 , 22, 3150–3157; D. A. Alonso, P. Brandt, S. J. M. Nordin, P. G. Andersson, J. Am. Chem. Soc. 1999 , 121, 9580–9588; D. G. I. Petra, J. N. H. Reek, J.‐W. Handgraaf, E. J. Meijer, P. Dierkes, P. C. J. Kamer, J. Brussee, H. E. Schoemaker, P. W. N. M. van Leeuwen, Chem. Eur. J. 2000 , 6, 2818–2829), whereas a delayed, solvent‐mediated proton transfer has been observed in methanol solution (J.‐W. Handgraaf, E. J. Meijer, J. Am. Chem. Soc. 2007 , 129, 3099–3103). In aqueous solution, a concerted transition state is observed, as in the previous studies. However, only the hydride is transferred at that point, whereas the proton is transferred later by a water molecule instead of the catalyst.     

Kinetics for tautomerizations and dissociations of triglycine radical cations

Fragmentations of tautomers of the α-centered radical triglycine radical cation, [GGG^•]⁺, [GG^•G]⁺, and [G^•GG]⁺, are charge-driven, giving b-type ions; these are processes that are facilitated by a mobile proton, as in the fragmentation of protonated triglycine (Rodriquez, C. F. et al. J. Am. Chem. Soc. 2001, 123, 3006–3012). By contrast, radical centers are less mobile. Two mechanisms have been examined theoretically utilizing density functional theory and Rice-Ramsperger-Kassel-Marcus modeling: (1) a direct hydrogen-atom migration between two α-carbons, and (2) a two-step proton migration involving canonical [GGG]^•+ as an intermediate. Predictions employing the latter mechanism are in good agreement with results of recent CID experiments (Chu, I. K. et al. J. Am. Chem. Soc. 2008, 130, 7862–7872).     

Kinetics of the Effect of Some Bidentate Amino Acid Ligands in the Oxidation of Lactic Acid by Chromium(VI)1

The oxidation of lactic acid by Cr(VI) under acidic conditions is catalyzed by bidentate amino acid ligands such as glycine, alanine, aspartic acid and hydroxyproline. Catalysis is a function of [L]/[Cr(VI)] ratio and acidity. Pyruvic acid and acetaldehyde in a ratio of 2 : 1 are obtained as oxidation products in both uncatalyzed and catalyzed oxidation. This supports the previous understanding of the oxidation of -substituted carboxylic acids. Cromium(V) and chromium(VI) behave similarly in a C–H bond rupture (Rocek, J. and Radkowsky, A.E., J. Am. Chem. Soc., 1973, vol. 95, p. 7123), whereas Cr(IV) is responsible for C–C bond cleavage products (Wiberg, K.B. and Schafer, H., J. Am. Chem. Soc., 1969, vol. 91, p. 927).     

Ethylene spacer-linked bis-acetamidopyridine for dicarboxylic acid recognition and polymeric new wave-like anti-perpendicular arrangement of a host–guest in the solid state

In this paper, 1,2-bis(2-acetamido-6-pyridyl)ethane, receptor 1, having an ethylene spacer is reported to recognise dicarboxylic acids. The binding study in the solution phase is carried out using ¹H NMR (1:1) and UV–vis experiments and in the solid phase by single-crystal X-ray analysis. In ¹H NMR, the downfield shifts of specific amide protons of receptor 1 in 1:1 complexes of receptor and guest diacids, and in the UV–vis experiment, the appearance of an isosbestic point as well as significant binding constants are observed, which thus unambiguously support the complexation of receptor 1 with dicarboxylic acids in solution. Receptor 2, simple 2-acetamido-6-methylpyridine, has lower binding constants than receptor 1 due to cooperative binding of two pyridine amide groups with two acid groups of diacids. In the solid phase, the ditopic receptor 1 shows a grid-like polymeric hydrogen-bonded network that changes to a polymeric wave-like 1:1 anti-perpendicular network instead of the syn–syn polymeric 1:1 (Goswami, S.; Dey, S.; Fun, H.-K.; Anjum, S.; Rahman, A.-U. Tetrahedron Lett. 2005 (a) Goswami, S., Ghosh, K. and Dasgupta, S. 2000. J. Org. Chem., 65: 1907–1914. (b) Goswami, S.; Ghosh, K.; Mukherjee, R. Tetrahedron2001, 57, 4987–4993. (c) Goswami, S.; Ghosh, K.; Halder, M. Tetrahedron Lett.1999, 40, 1735–1738. (d) Goswami, S.; Dey, S.; Fun, H.-K.; Anjum, S.; Rahman, A.-U. Tetrahedron Lett.2005, 46, 7187–7191. (e) Goswami, S.; Jana, S.; Dey, S.; Razak, I.A.; Fun, H.-K. Supramol. Chem.2006, 18, 571–574. (f) Goswami, S.; Jana, S.; Fun, H.-K. Cryst. Eng. Comm.2008, 10, 507–517. (g) Goswami, S.; Jana, S.; Dey, S.; Sen, D.; Fun, H.-K.; Chantrapromma, S. Tetrahedron2008,64, 6426–6433. (h) Goswami, S.; Dey, S.; Jana, S. Tetrahedron2008, 64, 6358–6363 [Google Scholar], 46, 7187–7191), anti–anti polymeric 1:1 (Goswami, S.; Jana, S.; Dey, S.; Razak, I.A.; Fun, H.-K. Supramol. Chem. 2006 (a) Goswami, S., Ghosh, K. and Dasgupta, S. 2000. J. Org. Chem., 65: 1907–1914. (b) Goswami, S.; Ghosh, K.; Mukherjee, R. Tetrahedron2001, 57, 4987–4993. (c) Goswami, S.; Ghosh, K.; Halder, M. Tetrahedron Lett.1999, 40, 1735–1738. (d) Goswami, S.; Dey, S.; Fun, H.-K.; Anjum, S.; Rahman, A.-U. Tetrahedron Lett.2005, 46, 7187–7191. (e) Goswami, S.; Jana, S.; Dey, S.; Razak, I.A.; Fun, H.-K. Supramol. Chem.2006, 18, 571–574. (f) Goswami, S.; Jana, S.; Fun, H.-K. Cryst. Eng. Comm.2008, 10, 507–517. (g) Goswami, S.; Jana, S.; Dey, S.; Sen, D.; Fun, H.-K.; Chantrapromma, S. Tetrahedron2008,64, 6426–6433. (h) Goswami, S.; Dey, S.; Jana, S. Tetrahedron2008, 64, 6358–6363 [Google Scholar], 18, 571–574; Goswami, S.; Jana, S.; Fun, H.-K. Cryst. Eng. Comm. 2008, 10, 507–517; Goswami, S.; Jana, S.; Dey, S.; Sen, D.; Fun, H.-K.; Chantrapromma, S. Tetrahedron 2008, 64, 6426–6433), syn–syn 2:2 (Karle, I.L.; Ranganathan, D.; Haridas, V. J. Am. Chem. Soc. 1997 (a) Garcia-Tellado, F., Goswami, S., Chang, S.K., Geib, S.J. and Hamilton, A.D. 1990. J. Am. Chem. Soc., 112: 7393–7394. (b) Geib, S.J.; Vicent, C.; Fan, E.; Hamilton, A.D. Angew. Chem. Int. Ed. Engl.1993, 32, 119–121. (c) Garcia-Tellado, F.; Geib, S.J.; Goswami, S.; Hamilton, A.D. J. Am. Chem. Soc.1991, 113, 9265–9269. (d) Karle, I.L.; Ranganathan, D.; Haridas, V. J. Am. Chem. Soc.1997, 119, 2777–2783. (e) Moore, G.; Papamicaël, C.; Levacher, V.; Bourguignon, J.; Dupas, G. Tetrahedron2004, 60, 4197–4204. (f) Korendovych, I.V.; Cho, M.; Makhlynets, O.V.; Butler, P.L.; Staples, R.J.; Rybak-Akimova, E.V. J. Org. Chem.2008, 73, 4771–4782. (g) Ghosh, K.; Masanta, G.; Fröhlich, R.; Petsalakis, I.D.; Theodorakopoulos, G. J. Phys. Chem. B2009, 113, 7800–7809 [Google Scholar], 119, 2777–2783) or top–bottom-bound 1:1 (Garcia-Tellado, F.; Goswami, S.; Chang, S.K.; Geib, S.J.; Hamilton, A.D. J. Am. Chem. Soc. 1990 (a) Goswami, S., Ghosh, K. and Dasgupta, S. 2000. J. Org. Chem., 65: 1907–1914. (b) Goswami, S.; Ghosh, K.; Mukherjee, R. Tetrahedron2001, 57, 4987–4993. (c) Goswami, S.; Ghosh, K.; Halder, M. Tetrahedron Lett.1999, 40, 1735–1738. (d) Goswami, S.; Dey, S.; Fun, H.-K.; Anjum, S.; Rahman, A.-U. Tetrahedron Lett.2005, 46, 7187–7191. (e) Goswami, S.; Jana, S.; Dey, S.; Razak, I.A.; Fun, H.-K. Supramol. Chem.2006, 18, 571–574. (f) Goswami, S.; Jana, S.; Fun, H.-K. Cryst. Eng. Comm.2008, 10, 507–517. (g) Goswami, S.; Jana, S.; Dey, S.; Sen, D.; Fun, H.-K.; Chantrapromma, S. Tetrahedron2008,64, 6426–6433. (h) Goswami, S.; Dey, S.; Jana, S. Tetrahedron2008, 64, 6358–6363 [Google Scholar], 112, 7393–7394) co-crystals.

     

The Conquest of Taxol

Much has been written about taxol, one of the newest weapons against cancer, and its producer, the Pacific Yew tree (Taxus brevifolia).

1 K. C. Nicolaou, W.-M. Dai, R. K. Guy, Angew. Chem. 1994, 106, 38–69; Angew. Chem. Int. Ed. Engl. 1994, 33, 15–44.

In this article, the authors give a frank and behind-the-scenes account of their encounter with this well-known molecule, which they and their collaborators faced as a synthetic target.

2 K. C. Nicolaou, Z. Yang, J.-J. Liu, H. Ueno, P. G. Nantermet, R. K. Guy, C. F. Claiborne, J. Renaud, E. A. Couladouros, K. Paulvannan, E. J. Sorensen, Nature (London) 1994, 367, 630–634.

3 K. C. Nicolaou, J.-J. Liu, Z. Yang, H. Ueno, R. K. Guy, E. A. Couladouros, E. J. Sorensen, J. Am. Chem. Soc. 1995, 117, 624–633.

4 K. C. Nicolaou, J.-J. Liu, Z. Yang, H. Ueno, E. J. Sorensen, C. F. Claiborne, R. K. Guy, C.-K. Hwang, M. Nakada, P. G. Nantermet, J. Am. Chem. Soc. 1995, 117, 634–644.

5 K. C. Nicolaou, Z. Yang, J.-J. Liu, P. G. Nantermet, C. F. Claiborne, J. Renaud, R. K. Guy, K. Shibayama, J. Am. Chem. Soc. 1995, 117, 645–652.

6 K. C. Nicolaou, H. Ueno, J.-J. Liu, P. G. Nantermet, Z. Yang, J. Renaud, K. Paulvannan, R. Chadha, J. Am. Chem. Soc. 1995, 117, 653–659.

Once again total synthesis is found to offer excellent opportunities for developing new synthetic strategies and novel reactions. The team of chemists who took up this challenge emerged with valuable experience and confidence in their skills.     

Die chemische Analyse durch Hochfreqnenzmethoden

Ohne Zusammenfassung Blaedel, W. J., T. S. Burkhalter, D. G. Flom, G. Hare und F. W. Jensen: Analyt. Chemistry : 4, 198 (1952). Digest of round-table discussion at 119. Meeting, Amer. Chem. Soc., Div. of Anal. Chem., Cleveland, Ohio.     

Enantiopure cryptophane-129Xe nuclear magnetic resonance biosensors targeting carbonic anhydrase

The (+) and ( ? ) enantiomers for a cryptophane-7-bond-linker-benzenesulfonamide biosensor (C7B) were synthesised and their chirality was confirmed by electronic circular dichroism spectroscopy. Biosensor binding to carbonic anhydrase II (CAII) was characterised for both enantiomers by hyperpolarised (HP) ¹²⁹Xe NMR spectroscopy. Our previous study of the racemic ( ± ) C7B biosensor–CAII complex [Chambers, J.M.; Hill, P.A.; Aaron, J.A.; Han, Z.H.; Christianson, D.W.; Kuzma, N.N.; Dmochowski, I.J. J. Am. Chem. Soc.2009, 131, 563–569] identified two ‘bound’ ¹²⁹Xe@C7B peaks by HP ¹²⁹Xe NMR (at 71 and 67 ppm, relative to ‘free’ biosensor at 64 ppm), which led to the initial hypothesis that (+) and ( ? ) enantiomers produce diastereomeric peaks when coordinated to Zn²⁺ at the chiral CAII active site. Unexpectedly, the single enantiomers complexed with CAII also identified two ‘bound’ ¹²⁹Xe@C7B peaks: (+) 72, 68 ppm and ( ? ) 68, 67 ppm. These results are consistent with X-ray crystallographic evidence for benzenesulfonamide inhibitors occupying a second site near the CAII surface. As illustrated by our studies of this model protein–ligand interaction, HP ¹²⁹Xe NMR spectroscopy can be useful for identifying supramolecular assemblies in solution.     

Re-evaluation of the Activity Coefficients of Aqueous Hydrochloric Acid Solutions up to a Molality of 16.0 mol·kg<Superscript>−1</Superscript> Using the Hückel and Pitzer Equations at Temperatures from 0 to 50 °C

The simple three-parameter Pitzer and extended Hückel equations were used for calculation of activity coefficients of aqueous hydrochloric acid at various temperatures from 0 to 50 °C up to a molality of 5.0 mol·kg^?1. A more complex Hückel equation was also used at these temperatures up to a HCl molality of 16 mol·kg^?1. The literature data measured by Harned and Ehlers J. Am. Chem. Soc. 54, 1350–1357 (1932) and 55, 2179–2193 (1933) and by Åkerlöf and Teare [J. Am. Chem. Soc. 59, 1855–1868 (1937)] on galvanic cells without a liquid junction were used in the parameter estimations for these equations. The latter data consist of sets of measurements in the temperature range 0 to 50 °C at intervals of 10 °C, and data at these temperatures were used in all of these estimations. It was observed that the estimated parameters follow very simple equations with respect to temperature. They are either constant or depend linearly on the temperature. The values for the activity coefficient parameters calculated by using these simple equations are recommended here. The suggested new parameter values were tested with all reliable cell potential and vapor pressure data available in literature for concentrated HCl solutions. New Harned cell data at 5, 15, 25, 35, and 45 °C up to a molality of 6.5 mol·kg^?1 are reported and were also used in the tests. The activity coefficients obtained from the new equations were compared to those calculated by using the Pitzer equations of Holmes et al. [J. Chem. Thermodyn. 19, 863–890 (1987)] and of Saluja et al. [Can. J. Chem. 64, 1328–1335 (1986)] at various temperatures, and by using the extended Hückel equation of Hamer and Wu [J. Phys. Chem. Ref. Data 1, 1047–1099 (1972)] at 25 °C.     

The structure of dehydrated zeolite 3A (Si/Al = 1.01) by neutron profile refinement

A neutron powder diffraction study of a dehydrated commercially available potassium exchanged zeolite A (Linde 3A) has shown that the diffraction pattern can be indexed in cubic space group $\text{Fm}\text{3}\text{c}$. For this sample there is 63% exchange of potassium for sodium (K⁺/Na⁺ = 1.69). Data collected at a neutron wavelength of 2.98 Å shows no evidence of rhombohedral distortion and suggests that the assignment of space group $\text{Fm}\text{3}\text{c}$ is correct. The final structural model is closely analogous to that found for dehydrated sodium zeolite A (J. M. Adams, D. A. Haselden, and A. W. Hewat, J. Solid State Chem.44, 245 (1982); J. J. Pluth and J. V. Smith, J. Amer. Chem. Soc.102, 4074 (1980). Unusual features of previous refinements of potassium containing zeolite A samples, i.e., “zero coordinate” cations (P. C. W. Leung, M. B. Kunz, K. Seff, and I. E. Maxwell, J. Phys. Chem.83, 741 (1979)) or potassium inside the β-cage (J. J. Pluth and J. V. Smith, J. Phys. Chem.83, 741 (1979)) have not been found. Refinements using the same 1.9 Å neutron powder diffraction data were also obtained with the models of Leung et al. and Pluth and Smith (1979) as starting points (denoted LKSM and PS, respectively) and comparison is made with these. The final R factors for the three refinements were R_pw (A. K. Cheetham and J. C. Taylor, J. Solid State Chem.21, 253 (1977)) = 10.24% for the model presented here, R_pw = 10.38% (PS model), and R_pw = 10.61% (LKSM model).     

Pyramidalized Alkenes: Theory and Experiment

Structural X-ray data on highly strained anti-Bredt olefins (see, for instance, J. Am. Chem. Soc. 1990 1128627) prompted us to perform model ab initio calculations with the 6-31G* basis set for ethylene and its simple derivatives. A variety of modes of distortion for ethylene were examined: deformations in plane, pyramidalization, and twist. Olefinic atoms are found to be spontaneously pyramidalized either (1) under the influence of certain substituents that break the original symmetry of a molecule, or (2) when a distortion is introduced in a molecule that simulates the cyclization. Furthermore, pyramidalization is enhanced when a bond angle deformation takes place. The stereochemistry of C=C and Si=Si is briefly compared and discussed.     

Condensation of o-aminophenol and α-dicarbonyl compounds. Part 1. Benzoxazines

By condensation with o-aminophenol of a series of phenylglyoxal derivatives two species of products were obtained, namely 2-hydroxy-(2H)-1,4-benzoxazines (I) and 2′ -aryl-2,2′ -dibenzoxa-zolines (II). The structure of compounds I was investigated by ir, uv and pmr spectroscopy and a reaction mechanism was proposed. J. Chem. Soc., 14, 997 (1977)     

Determinants of cyanuric acid and melamine assembly in water

While the recognition of cyanuric acid (CA) by melamine (M) and their derivatives has been known to occur in both water and organic solvents for some time, analysis of CA/M assembly in water has not been reported (Ranganathan, A.; Pedireddi, V. R.; Rao, C. N. R. J. Am. Chem. Soc.1999, 121, 1752-1753; Mathias, J. P.; Simanek, E. E.; Seto, C. T.; Whitesides, G. M. Macromol. Symp.1994, 77, 157-166; Zerkowski, J. A.; MacDonald, J. C.; Seto, C. T.; Wierda, D. A.; Whitesides, G. M. J. Am. Chem. Soc.1994, 116, 2382-2391; Mathias, J. P.; Seto, C. T.; Whitesides, G. M. Polym. Prepr.1993, 34, 92-93; Seto, C. T.; Whitesides, G. M. J. Am. Chem. Soc.1993, 115, 905-916; Zerkowski, J. A.; Seto, C. T.; Whitesides, G. M. J. Am. Chem. Soc.1992, 114, 5473-5475; Seto, C. T.; Whitesides, G. M. J. Am. Chem. Soc.1990, 112, 6409-6411; Wang, Y.; Wei, B.; Wang, Q. J. Chem. Cryst.1990, 20, 79-84; ten Cate, M. G. J.; Huskens, J.; Crego-Calama, M.; Reinhoudt, D. N. Chem.-Eur. J.2004, 10, 3632-3639). We have examined assembly of CA/M, as well as assembly of soluble trivalent CA and M derivatives (TCA/TM), in aqueous solvent, using a combination of solution phase NMR, isothermal titration and differential scanning calorimetry (ITC/DSC), cryo-transmission electron microscopy (cryo-TEM), and synthetic chemistry. While the parent heterocycles coprecipitate in water, the trivalent system displays more controlled and cooperative assembly that occurs at lower concentrations than the parent and yields a stable nanoparticle suspension. The assembly of both parent and trivalent systems is rigorously 1:1 and proceeds as an exothermic, proton-transfer coupled process in neutral pH water. Though CA and M are considered canonical hydrogen-bonding motifs in organic solvents, we find that their assembly in water is driven in large part by enthalpically favorable surface-area burial, similar to what is observed with nucleic acid recognition. There are currently few synthetic systems capable of robust molecular recognition in water that do not rely on native recognition motifs, possibly due to an incomplete understanding of recognition processes in water. This study establishes a detailed conceptual framework for considering CA/M heterocycle recognition in water which enables the future design of molecular recognition systems that function in water.     

Rational groups and integer-valued characters of Thompson group <Emphasis Type="Italic">Th</Emphasis>

According to the main result of W. Feit and G. M. Seitz (Illinois J Math 33(1):103–131, 1988), the Thompson group Th is non-rational or unmatured group (S. Fujita in Bull Chem Soc Jpn 71:2071–2080, 1998). Using the concept of markaracter tables proposed by S. Fujita (Bull Chem Soc Jpn 71:1587–1596, 1998), we are able to obtain tables of integer-valued characters for finite unmatured groups. In this paper, the integer-valued character for Thompson group is successfully derived for the first time.     

Metal complexes as indicators of solvent structures. Part IV. The effect of solvation on the interaction between tris-1,2-diaminoethanecobalt(III) and anions in aqueous solution

Summary Changes in the circular dichroism of (+)tris-1,2-diaminoethanecobalt(III) in the presence of sulphate ion can be attributed to changes in the cybotactic solvation of the complex ion as well as to the formation of discrete ion-pairs.Parts 1, 2 and 3: R. D. Gillard and H. M. Sutton,J. Chem. Soc., A, (1970) 1309, 2172 and 2175 respectively.     

Structure of azomesobilirubin isomers

The structure of azomesobilirubin isomers as their methyl esters were determined using nmr and Eu(fod)₃ as a shift reagent. J. Chem. Soc., 14, 1101 (1977)     

4-Methylisocamphenilansäure und 4-(3,3,4-Trimethyl-2-exo-norbornyl)-3-buten-2-on

The synthesis of 4-methylisocamphenilanic acid (7) and of the unsaturated ketone 4-(3,3,4-trimethyl-2-exo-norbornyl)-3-buten-2-one (2), an analogue of -irone (1), are described. The preparation of2 has been accomplished by: catalyzedDiels—Alder reaction of methylcyclopentadiene and mesityl oxide, hydrogenation and isomerization of the resulting ketone mixture to theexo-ketone6, oxidation of6 to the acid7, reduction of7 to the corresponding aldehyde8 and aldol reaction of8 with acetone. The structure of the key intermediate6 was established by mass, 100 MHz¹H-NMR and¹³C-NMR spectra. The odour of2 is discussed briefly.

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Teil der Diplomarbeit vonI. Schmidmayer.

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9. Mitt.,G. Buchbauer undM. Wiltschko. J. Soc. Cosmet. Chem., im Druck.

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8. Mitt.,G. Buchbauer undE. Klissenbauer, Mh. Chem.109, 499 (1978).     

Driving the Future with Photocatalytic Solar Fuels

Tierui Zhang is a full Professor in Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, and the director of Key Laboratory of Photochemical Conversion and Optoelectronic Materials, CAS. He is associate editor of Science Bulletin and also serves as an editorial board member for several peer-reviewed journals including Advanced Energy Materials, ChemPhysChem, Scientific Reports, and Solar RRL. He has published more than 200 papers in refereed SCI journals, including Nat. Commun., Chem. Soc. Rev., Adv. Mater., Angew. Chem. Int. Ed., and J. Am. Chem. Soc., with total number of citations >14000 and a h-index of 64. He was named in the annual Highly Cited Researchers 2018/2019 List by Clarivate Analytics. He was supported by an Alexander von Humboldt Fellowship, Royal Society-Newton Advanced Fellowship, National High-Level Talents Special Support Program, “Outstanding Young Scholars” of the National Science Fund, and so on. He is the recipient of numerous awards including 2019 “Nano Research Young Innovators Award” in NanoEnergy and Outstanding Young Scientist in Photochemistry and Photocatalysis. He was named a fellow of the Royal Society of Chemistry (FRSC) in 2017.     

The structural phase transitions of aminoguanidinium(1+) dihydrogen phosphate—study of crystal structures, vibrational spectra and thermal behavior

Aminoguanidinium(1+) dihydrogen phosphate was prepared by crystallization from aqueous solution. On the basis of the results of DSC measurements, X-ray structural analysis was carried out at temperatures of 160, 215 and 293 K for three aminoguanidinium(1+) dihydrogen phosphate phases ( |Z=2|non-ferroic |melting point 408 K; II |201-222 K|(2) |Z=2|non-ferroic|-; III |<201 K|(2)|Z=4|non-ferroic|-). The triclinic unit cell dimensions (a=6.8220(2), b=7.1000(2), c=7.4500(2) Å, α=86.925(2)°, β=80.731(2)°, γ=79.630(2)°, V=350.21(2) Å³—phase I) are similar for all three structural phases with the exception of phase III, where doubling of the c-axis length leads to an increase in the volume to 692.34(3) Å³. The crystal structure of all three modifications consists of parallel layers of dihydrogen phosphate anions that are interconnected by aminoguanidinium(1+) cations through hydrogen bonds of the N-H…O type. The planar aminoguanidinium(1+) cations are oriented almost parallel to each other and are perpendicular to the anion layers. The primary differences amongst phases I, II and III lie in the location of the H atom in the short O-H…O bonds connecting the dihydrogen phosphate anions in layers. The FTIR and FT Raman spectra of natural and deuterated compounds were recorded and interpreted. The FTIR spectra were studied down to a temperature of 90 K.     

An Improved Synthesis of 4-Cycloheptene-1-Carboxylic Acid

Modification of the method of Stork and Landesman (J. Am. Chem. Soc. 1956, 78, 5129) permitted the synthesis of the title acid (1) in 58% yield from a cyclopentanone enamine. Acid 1 is a useful intermediate for the preparation of 4-substituted cycloheptenes in good yields.