Comment: 2004's fastest organic and biomolecular chemistry!

In January 2003, the Royal Society of Chemistry launched Organic & Biomolecular Chemistry (OBC)--a journal promising to provide high quality research from all aspects of synthetic, physical and biomolecular organic chemistry. The journal was set to build upon the foundations laid down by its predecessor publications (J. Chem. Soc., Perkin Trans. 1 and J. Chem. Soc., Perkin Trans. 2) as well as complement the subject coverage already published in prestigious general chemistry journals such as Chemical Communications and Chemical Society Reviews. Nearly two years on, just how is the programme developing and what can the community expect to see from the Royal Society of Chemistry (RSC)?     

Comment: 2004's fastest organic and biomolecular chemistry!

In January 2004, the Royal Society of Chemistry launched Organic & Biomolecular Chemistry (OBC) - a journal promising to provide high quality research from all aspects of synthetic, physical and biomolecular organic chemistry. The journal was set to build upon the foundations laid down by its predecessor publications (J. Chem. Soc., Perkin Trans. 1 and J. Chem. Soc., Perkin Trans. 2) as well as complement the subject coverage already published in prestigious general chemistry journals such as Chemical Communications and Chemical Society Reviews. Nearly two years on, just how is the programme developing and what can the community expect to see from the Royal Society of Chemistry (RSC)?     

Efficient anodic pyridination of poly(3-hexylthiophene) toward post-functionalization of conjugated polymers

Nucleophilic substitution reaction of poly(3-hexylthiophene) (P3HT) with pyridine derivatives as nucleophile was demonstrated in anodic oxidation process. The key reaction involves efficient nucleophilic attack of the pyridine derivatives toward thiophene rings in partly oxidized polymer, i.e., doped state, in the similar manner in which anodic pyridination of electrochemically generated pi-radical cation of a series of oligothiophene takes place in quantitative yield (Y. Li, K. Kamata, T. Kawai, J. Abe and T. Iyoda, J. Chem. Soc., Perkin Trans. 1, 2002, 1135-1140). When 1-methyl-4-(4'-pyridyl)pyridinium hexafluorophosphate (MPP+PF6-) was used as a functional nucleophile, the anodic pyridination reaction gave viologen-tailored poly(3-hexylthiophene) (P3HT), which was confirmed by electrochemical and spectroelectrochemical methods. The introduced ratio of viologen units was about 60% with respect to the polaron, i.e., one-electron oxidized state localized over five thiophene units.     

Preparation of protected syn-alpha,beta-dialkyl beta-amino acids that contain polar side chain functionality

We report the synthesis of syn-alpha,beta-dialkyl beta-amino acid derivatives suitably protected for solid-phase synthesis that give rise to residues containing positively charged lysine-like side chains. These amino acids, as well as syn-alpha,beta-dialkyl beta-amino acids that contain diverse hydrophobic side chains, are prepared in good de and ee. The key step in this route involves Davies's protocol for the conjugate addition of a chiral lithium amide to alpha,beta-unsaturated tert-butyl esters (Davies, S. G.; Ichihara, O.; Walters, I. A. S. J. Chem. Soc., Perkin Trans. 1 1994, 9, 1141). syn-alpha,beta-Dialkyl beta-amino acids are interesting building blocks because of their sheet-forming propensity and because of their presence in bioactive compounds.     

Kinetic solvent effects on proton and hydrogen atom transfers from phenols. Similarities and differences

Bimolecular rate constants for proton transfer from six phenols to the anthracene radical anion have been determined in up to eight solvents using electrochemical techniques. Effects of hydrogen bonding on measured rate constants were explored over as wide a range of phenolic hydrogen-bond donor (HBD) and solvent hydrogen-bond acceptor (HBA) activities as practical. The phenols' values ranged from 0.261 (2-MeO-phenol) to 0.728 (3,5-Cl(2)-phenol), and the solvents' values from 0.44 (MeCN) to 1.00 (HMPA), where and are Abraham's parameters describing relative HBD and HBA activities (J. Chem. Soc., Perkin Trans. 2 1989, 699; 1990, 521). Rate constants for H-atom transfer (HAT) in HBA solvents, k(S), are extremely well correlated via log k(S) = log k(0) - 8.3 , where k(0) is the rate constant in a non-HBA solvent (Snelgrove et al. J. Am. Chem. Soc. 2001, 123, 469). The same equation describes the general features of proton transfers (k(S) decreases as increases, slopes of plots of log k(S) against increase as increases). However, in some solvents, k(S) values deviate systematically from the least-squares log k(S) versus correlation line (e.g., in THF and MeCN, k(S) is always smaller and larger, respectively, than "expected"). These deviations are attributed to variations in the solvents' anion solvating abilities (THF and MeCN are poor and good anion solvators, respectively). Values of log k(S) for proton transfer, but not for HAT, give better correlations with Taft et al.'s (J. Org. Chem. 1983, 48, 2877) beta scale of solvent HBA activities than with . The beta scale, therefore, does not solely reflect solvents' HBA activities but also contains contributions from anion solvation.     

THE PHOTO-OXIDATION OF N, N-DIETHYLHYDROXYLAMINE BY ROSE BENGAL IN ACETONITRILE AND WATER

The Rose Bengal photosensitized oxidation of N,N-diethylhydroxylamine has been investigated in water and acetonitrile using the techniques of oxygen uptake, singlet oxygen phosphorescence and electron spin resonance. In both solvents H₂O₂ is the major oxidation product and diethylnitroxide is an intermediate. In water, superoxide dismutase decreases oxygen uptake suggesting involvement of superoxide anions in the oxidation process. Results indicate that in water the photo-oxidation proceeds mainly by a Type I(electron transfer) mechanism, while in acetonitrile a Type II(energy transfer) mechanism has been confirmed (Encinas et al., 1987, J. Chem. Soc. Perkin Trans. II,1125–1127).     

Conductor‐like screening model for relaxed excited states: Implementation in the semiempirical method MSINDO

Two approaches to treat solvent polarization and reorientation effects for excited states of molecules and surfaces have been implemented in the recently developed MSINDO‐sCIS method (Gadaczek, Krause, Hintze, Bredow, J. Chem. Theory Comput. 2011, 7, 3675). They allow for an efficient calculation of analytical energy gradients and hence open the opportunity to investigate fluorescence effects or photochemical reactions in solution for large molecules that are difficult to treat with high‐level methods. Both approaches are based on the conductor‐like screening model (COSMO) (Klamt and Schüürmann, J. Chem. Soc., Perkin Trans. 1993, 2, 799) in combination with the configuration interaction singles (CIS) method (Foresman, Head‐Gordon, Pople, and Frisch, J. Phys. Chem. 1992, 96, 135). The paper gives a brief outline of the theoretical background. As a first application, solvent shifts of three well‐studied, environment‐sensitive fluorescent dyes (Kucherak, Didier, Mély, and Klymchenko, J. Phys. Chem. Lett. 2010, 1, 616) have been calculated and compared with experimental results and standard time‐dependent density functional theory. A statistical evaluation of MSINDO‐COSMO‐sCIS is provided for a set of 39 molecules suggested recently by Jacquemin et al. (Jacquemin, Planchat, Adamo, and Mennucci, J. Chem. Theory Comput. 2012, 8, 2359). Calculated vertical and adiabatic excitation energies and fluorescence energies are compared to experimental data. © 2014 Wiley Periodicals, Inc.     

The role of hydrogen bonding on the h-atom-donating abilities of catechols and naphthalene diols and on a previously overlooked aspect of their infrared spectra

Catechols and 1,8-naphthalene diols contain one "free" hydroxyl and one intramolecularly H-bonded hydroxyl group. The "free" hydroxyls are strong hydrogen-bond donors (HBDs) with alpha2H values (Abraham et al. J. Chem. Soc., Perkin Trans. 2 1989, 699) ranging from 0.685 to 0.775, indicating that these compounds have similar HBD properties to those of strongly acidic phenols such as 4-chlorophenol (alpha2H = 0.670) and 3, 5-dichlorophenol (alpha2H = 0.774). Kinetic effects on H-atom abstractions from the diols in HB acceptor (HBA) solvents can be quantitatively accounted for over at least 50% of the available range of solvent HBA activities (as measured by their beta2H values; see Abraham et al. J. Chem. Soc. Perkin Trans. 2 1990, 521) on the basis of a single reactive OH group, the "free" OH. This free OH group is an outstanding H-atom donor in poor HBA solvents; e.g., in hexane rate constants for reaction with the DPPH* radical are 2.1 x 104 M-1 s-1 for 3,5-di-tert-butyl catechol and 2 x 106 M-1 s-1 for 4-methoxy-1,8-naphthalene diol, but only 7.4 x 103 M-1 s-1 for alpha-tocopherol (vitamin E). The diols are much more reactive than simple phenols because the O-H bond dissociation enthalpy of the "free" OH group is weakened by 5-9 kcal/mol by the intramolecular H-bond. The IR spectra of all the diols in CCl4 show two fairly sharp O-H stretching bands of roughly equal intensity separated by 42-138 cm-1. Addition of a low concentration of DMSO, a strong HBA, causes the band due to the intramolecularly H-bonded OH group to decrease in intensity to roughly half the extent that the "free" OH band loses intensity. The latter forms an intermolecular H-bond with the DMSO, the former does not. What has been overlooked in earlier work is that as the DMSO concentration is increased the band due to the intramolecularly H-bonded OH group first broadens and then evolves into a new, lower frequency (by 19-92 cm-1) band. The magnitude of the shift in the frequency of the intramolecular OH band caused by H-bonding of HBAs to the "free" OH group, Deltanu, increases linearly as the HBA activity of the additive increases, e.g., for 3,5-di-tert-butylcatechol, Deltanu/cm-1 = 33.8 beta2H (R 2 = 0.986). This may provide a new and simple method for determining beta2H values.     

Meet the Board of ChemistryOpen: Thomas Wirth

Thomas Wirth is Professor of organic chemistry at Cardiff University. He received the Werner Prize from the New Swiss Chemical Society in 2000, the Wolfson Research Merit Award from the Royal Society, and the Bader Award from the Royal Society of Chemistry in 2016. He is an elected fellow of The Learned Society of Wales and currently serves as Chair of the Editorial Board for ChemistryOpen.     

The Curious Story of the Chemical Society’s Missing Obituary of John Lloyd Bullock

The pharmaceutical and manufacturing chemist John Lloyd Bullock, who had joined the Chemical Society in 1842 and who played a fundamental role in the creation of the Royal College of Chemistry in 1845, did not receive an obituary when he died in 1905. Yet, nine years later on the eve of WW1, the Council of the Chemical Society suddenly commissioned an obituary from two German chemists. Although the curious circumstances of this omission and commission cannot be fully explained, their investigation provides an opportunity for an appraisal of Bullock’s role in the history of chemistry and pharmacy.     

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.     

Temperature dependence of the mean autodetachment lifetime of the p-benzoquinone molecular radical anion

Experimental data previously published from this laboratory (Asfandiarov NL, Pshenichnyuk SA, Fokin AI, Nafikova EP. Chem. Phys. 2004; 298: 263), on the temperature dependence of the mean autodetachment lifetime of the p-benzoquinone molecular radical anion, were analyzed in the framework of a simple statistical model. This model is a simplification of the well-known semiempirical approach elaborated by Christophorou et al. (Christophorou LG, Hadjiantoniou A, Carter JG. J. Chem. Soc., Faraday Trans. II 1973; 69: 1722). Evaluation of the vibrational energy storage of the target molecule and anion was made in a quantum approximation following a published procedure (Matejcik S, M?rk TD, Spanel P, Smith D, Jaffke T, Illenberger E. J. Chem. Phys. 1994; 102: 2516). The results obtained are in reasonable agreement with the experimental data.     

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.     

Vorsprung durch Chemie

The German Chemical Society (GDCh) and the Royal Society of Chemistry (RSC) have worked closely together for many years. David Giachardi, chief executive of the RSC, and Wolfram Koch, GDCh's chief executive, discuss the issues faced by the societies today.     

Explanation of the unusual peak of calorimetric heat in the adsorption of nitrogen, argon and methane on graphitized thermal carbon black

Heats of adsorption and adsorption isotherms of argon, nitrogen and methane on a perfect graphitic surface and a defective graphitic surface are studied with a Grand Canonical Monte Carlo Simulation (GCMC). For the perfect surface, the isosteric heat versus loading shows a typical pattern of adsorption of simple fluids on graphite. Depending on adsorbate, degree of graphitization and temperature, a spike in the heat curve versus loading is observed when the first layer is mostly covered with adsorbate molecules. The heat spike is observed for argon and nitrogen at 77 K while for argon at 87.3 K it is no longer present. These simulation results are consistent with the experimental data of J. Rouquerol, S. Partyka and F. Rouquerol, J. Chem. Soc., Faraday Trans. 1, 1977, 73, 306. In the case of methane we observe heat spikes at low temperatures, 84.5, 92.5 and 104 K. The heat spike shifts to higher loading with temperature and it then disappears at high temperatures. These observations are in qualitative agreement with the experimental data of A. Inaba, Y. Koga and J. A. Morrison, J. Chem. Soc., Faraday Trans. 2, 1986, 82, 1635. In all cases where heat spikes are observed, the GCMC simulation results indicate that the heat spike is associated with the squeezing of molecules into the already dense first layer, and the rearrangement of molecules to form a highly structured fluid of this layer. While this squeezing into the first layer is happening, molecules continue to adsorb onto the relatively sparse second layer.     

New insights into iron release from ferritin: direct observation of the neurotoxin 6-hydroxydopamine entering ferritin and reaching redox equilibrium with the iron core

Iron release from the iron storage protein ferritin has been studied extensively because of its important role in oxidative stress and its possible role in the progression of Parkinson's disease. For many years external indicators, notably strong iron(II) chelators, have been used to investigate this reaction. Such chelators can, however, drastically affect the electrochemical and thermodynamic properties of iron. The present study is unique in that it has been possible to follow a reaction taking place within the ferritin shell. This was made possible by our serendipitous discovery that, at physiological pHs, the oxidation product of 6-hydroxydopamine (a deprotonated quinone) acts as its own indicator (G. N. L. Jameson and W. Linert, J. Chem. Soc., Perkin Trans. 2, 2001, 563-568). The redox equilibrium data and the kinetics of the formation of this red-coloured species can only be explained on the basis that reduction of the iron(III) takes place within the ferritin shell. This is, in fact, the first time that a reaction actually taking place inside the ferritin shell has been followed. It has also been established that, at least in vitro, all eight hydrophilic channels are capable of being simultaneously involved in the reaction. It has also been possible to calculate the rate of oxidation of the 6-hydroxydopamine within the ferritin and it is demonstrated that a redox equilibrium is established within the protein. Finally, evidence is provided confirming that chelators are in fact intrinsically linked to iron removal from ferritin.     

Retraction

Retraction: [Yun-Shan Zhou, Jia Wang, Xiao-Fang Lin, Qiuhua Jiang, Jian-Nan Zhu, A new Co(II)- coordination polymer: Photocatalytic studies and treatment values on mania by reducing the ErbB4 expression on the noradrenergic neurons, J. Chin. Chem. Soc. 2021 , 68, 1478–1486 ( https://onlinelibrary.wiley.com/doi/abs/10.1002/jccs.202100020 )]. The above article, published online on 24 March 2021 in Wiley Online Library ( wileyonlinelibrary.com ), has been retracted by agreement between the authors, the journal Editor-in-Chief, Jye-Shane Yang, the Chemical Society Located in Taipei, and Wiley-VCH GmbH, Weinheim. The retraction has been agreed following an investigation based on allegations raised by a third party and a request by the authors to retract. The authors stated that there are errors in the bioactivity experiments and that these results could not be reproduced. Thus, the conclusions of the article are not considered reliable.