The construction of novel aggregation-induced emission luminogens (AIEgens) is beneficial for the derivation of new organic materials and exploration of potential application of AIEgens. Herein, a ...symmetrical AIE single-benzene derivative MeDHQB which contains two aliphatic rings without typical aromatic rotors of propeller-like AIEgens was designed. Two crystal forms were discovered by controlling the crystallization conditions. It was found that the aliphatic rings weaken the structural rigidity and promote the molecular vibration, which drastically increase the nonradiative transition in solution and can be inhibited in the aggregate states. Meanwhile, the dissimilar polymorphic physicochemical properties of MeDHQB-I and MeDHQB-II were investigated by experimental and theoretical methods. Additionally, the thermal transformation from MeDHQB-I to MeDHQB-II and the potential applications of optical waveguide and invisible ink were carefully discussed. Results presented in this work provide an efficient strategy for the construction of multifunctional AIE fluorophore based on compact single-benzene system.
A novel and efficient single benzene AIE/CIEE fluorescent scaffold with potential applications of optical waveguide and invisble ink is constructed. Display omitted
•Novel aggregation induced emission (AIE) fluorophore MeDHQB was constructed.•Two green emission polymorphs with efficient AIE and CIEE properties were discovered.•Structure-function relationship and crystal transformation were carefully studied.•The optical waveguide, invisible ink applications have been explored.
A number of researchers have performed studies on the application of chemical reaction visualization by means of computational chemistry techniques for the purpose of teaching and learning chemistry ...at secondary and higher education levels. However, on practical grounds, the presented approach thus far was generally unattainable for teachers due to the time-consuming process of finding the transition states. This research offers a less time-consuming computational chemistry technique for producing organic reaction-modelling videos upon which the students may sufficiently build their understanding of fundamental concepts of chemical reactions. The technique being proposed here consists of (1) intermediate structure modelling, (2) reactant-wise and product-wise optimizations of the intermediate structures without the search for transition states, and (3) visualizations of the optimized results. The application of this technique has managed to produce a video demonstration of an organic reaction of benzene derivatives that may serve as modelling videos in chemistry lessons at secondary education or undergraduate degree levels. REFERENCES Bode, B. M., & Gordon, M. S. (1998). Macmolplt: A graphical user interface for GAMESS. Journal of Molecular Graphics and Modelling, 16(3), 133–138. https://doi.org/10.1016/S1093-3263(99)00002-9 Carey, F. A. (2000). Organic chemistry (4th ed). McGraw-Hill. Cohlberg, J. A. (2021). Exploring Proteins and Nucleic Acids with Jmol. W. H. Freeman and Company. https://home.csulb.edu/~cohlberg/Jmolmanual.pdf Cramer, C. J. (2004). Essentials of computational chemistry: Theories and models (2nd ed). Wiley. Hanwell, M. D., Curtis, D. E., Lonie, D. C., Vandermeersch, T., Zurek, E., & Hutchison, G. R. (2012). Avogadro: An advanced semantic chemical editor, visualization, and analysis platform. Journal of Cheminformatics, 4(1), 17. https://doi.org/10.1186/1758-2946-4-17 Ikuo, A., Ikarashi, Y., Shishido, T., & Ogawa, H. (2006). User-Friendly CG Visualization with Animation of Chemical Reaction: Esterification of Acetic Acid and Ethyl Alcohol and Survey of Textbooks of High School Chemistry. Journal of Science Education Japan, 30(4), 210–215. Ikuo, A., Nagashima, H., Yoshinaga, Y., & Ogawa, H. (2009). Calculation of potential energy in the reaction of "I + H2 → HI + H" and its visualization. 6. Ikuo, A., Nagashima, H., Yoshinaga, Y., & Ogawa, H. (2011). Development of teaching material in tablet computer based on computer graphics by quantum chemistry calculation – Reaction of I + H2 → HI + H. Work-in-Progress Poster of the International Conference on Computers in Education: ICCE 2011, 31–33. Ikuo, A., & Ogawa, H. (2014). Visualization of Reaction Mechanism by CG Based on Quantum Chemical Calculation—An Approach to Electronic Laboratory Textbook -. African Journal of Chemical Education, 4(3), 22–33. Ikuo, A., Saito, K., Yoshinaga, Y., & Ogawa, H. (2013). Development of Teaching Material in Tablet PC for Experiment of Nitration of Benzene Based on Computer Graphics by Quantum Chemical Calculation. Work-in-Progress Poster of the International Conference on Computers in Education: ICCE 2013, 21–23. Koreeda, M. (2011). Chem 216 S11 Notes Lab work notes. http://websites.umich.edu/~chem216/216% 20S11-Expt%201.pdf Levine, I. N. (2009). Physical chemistry (6th ed). McGraw-Hill. Lewars, E. G. (2016). Computational Chemistry: Introduction to the Theory and Applications of Molecular and Quantum Mechanics. Springer. Mendera, I. G. (2020). Kimia: Benzena dan Turunannya. Direktorat SMA Ditjen PAUD, Dikdas, dan Dikmen Kemendikbud. Neese, F., Wennmohs, F., Becker, U., & Riplinger, C. (2020). The ORCA quantum chemistry program package. The Journal of Chemical Physics, 152(22), 224108. https://doi.org/10.1063/5.0004608 Nursanti, Y. I. (2020). Modul Tema 15: Berpadu dan Bersenyawa. Direktorat Dikmas dan Diksus Ditjen PAUD, Dikdas, dan Dikmen Kemendikbud. Omer, R., Koparir, P., Ahmed, L., & Koparir, M. (2020). Computational determination the reactivity of salbutamol and propranolol drugs. Turkish Computational and Theoretical Chemistry, 4(2), 67–75. https://doi.org/10.33435/tcandtc.768758 Polik, W. F., & Schmidt, J. R. (2022). WebMO: Web‐Based Computational Chemistry Calculations in Education and Research. WIREs Computational Molecular Science, 12(1), e1554. Putri, P. (2016). Tata Nama Senyawa dan Perhitungan Kimia—Karakteristik Peserta Didik. P4TK Bisnis dan Pariwisata Ditjen GTK Kemendikbud. Rahayu, I. (2009). Praktis Belajar Kimia untuk Kelas XII SMA/MA Program IPA. Pusat Perbukuan Depdiknas. S. Fernandes, H., Ramos, M. J., & M. F. S. A. Cerqueira, N. (2018). molUP: A VMD plugin to handle QM and ONIOM calculations using the gaussian software: A VMD Plugin to Handle QM and ONIOM Calculations. Journal of Computational Chemistry, 39(19), 1344–1353. https://doi.org/10.1002/jcc.25189 Schaftenaar, G., Vlieg, E., & Vriend, G. (2017). Molden 2.0: Quantum chemistry meets proteins. Journal of Computer-Aided Molecular Design, 31(9), 789–800. https://doi.org/10.1007/s10822-017-0042-5 Wardiyah. (2016). Kimia Organik. BPPSDMK Pusdik SDM Kesehatan Kemenkes.
This study investigated the chemical components of fine urban road dust from seven sampling sites, based on which we could predict potential human health effects. The elemental compositions, ...including the contents of metals and volatile or semivolatile organic compounds, were determined to establish comprehensive chemical profiles of solid road dust. The chemical profiles, consisting of C: H ratio, metal contents, and relative abundances of organic compounds, provided a chemical signature for road dust. To overall cytotoxicity values ranging between 7 and 58%, water extracts contributed less than 15%, and cell death mainly occurred via direct contact with solid-phase components, which possibly indicates that the selected chemical profile of solid-phase road dust components could serve as a strong predictor for BJ and WI-38 cytotoxicity. Pure metal oxides (Cr2O3, CuO, Fe2O3, MnO2, NiO, or ZnO) exhibited a positive dose-response, and the corresponding metal contents in solid road dust were well correlated with cell viability. The principal component analysis (PCA) results suggested that the metal contents were stronger predictors of cytotoxicity than the benzene derivative or hydrocarbon contents. The chemical profiles established in this study could be further utilized to identify candidate health hazard factors in road dust.
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•This study extracted potential health hazard factors from road dust compositions.•Metal content in fine road dust was strong predictor for fibroblast cytotoxicity.•Ni, Cr, or Zn content has a positive linear correlation with the cytotoxicity.•Relative abundance of benzene-derivatives was associated well with cell viability.•PCA results revealed variables in close relationship with the fibroblast cytotoxicity.
This study extracted a comprehensive set of potential health hazard factors in urban road dust.
An investigation of the solubility and loading ability (LA) of nine benzene derivative drugs with different chemical structures onto viscose substrate in supercritical carbon dioxide fluid (SCF–CO2) ...was performed, in order to construct some bases at the first time for manufacturing drug-loaded cosmetic textiles by employing an ecofriendly, sustainable supercritical methodology. Moreover, a release behavior of each of the loaded drugs from viscose substrate in a solvent of ethanol was also disclosed. The results show that a more hydrophobicity of the substituent group linked on the benzene ring readily led to a higher solubility in SCF-CO2, while an overlong aliphatic tail and its molar mass also brought some effects on its dissolving behavior. As for the isomer drugs, the locations of a methoxy group (-O-CH3) at the ortho-position to the carboxyl group (-(CO)–OH) in the benzene ring resulted in the highest solubility, while a para-position showed the lowest solubility in SCF-CO2. The loading ability (LA) for most of the tested drugs mainly depended on their solubilities in SCF-CO2, and was also affected by the interactions between the drug and viscose substrate. The investigation of drug release reveals that the LA played a predominant role in the release behaviors of the tested drugs with different substituent groups, molar mass or aliphatic chains and isomer structures. Moreover, the drug molecular size and its interaction with viscose substrate also presented effects on the subsequent release behaviors in the utilized release system and conditions.
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•Basises for ecofriendly manufacturing drug-loaded cosmetic textiles were developed in SCF-CO2.•Different dissolving and loading abilities of nine drugs on viscose in SCF-CO2 were explored.•Hydrophobicity and position of a substituent group brought effect on drug dissolving behavior in SCF-CO2.•Loading ability mainly depended on drug solubility in SCF-CO2, then the interactions with substrate.•Release behavior was notably influenced by drug loading ability, then molecular size and interactions with viscose.
Excess molar volumes of the binary mixtures against mole fraction x1 at T=303.15K for 3-chloroaniline+bromobenzene (■), 3-chloroaniline+chlorobenzene (●), 3-chloroaniline+nitrobenzene (▲) and (---) ...calculated with PFP theory using parameters. Display omitted
•Thermophysical properties of 3-chloroaniline with isomeric chlorobenzenes were studied at various temperatures.•Excess properties were correlated with Redlich–Kister equation.•The effect of temperature on density and speed of sound were discussed in term of intermolecular interactions.•Experimental VmE were successfully correlated using the PFP model.
Values of the density (ρ), speed of sound (u), and viscosity (η) are reported for binary mixtures of 3-chloroaniline with substituted benzene derivatives viz., chlorobenzene, bromobenzene and nitrobenzene over the entire composition range of mole fraction at T=(303.15–318.15)K and at atmospheric pressure 0.1MPa. The excess properties such as excess molar volume, excess isentropic compressibility and deviation in viscosity were calculated from the density, speed of sound and viscosity. Excess properties were correlated by the Redlich–Kister equation. The partial molar volumes, partial molar isentropic compressibility, excess partial molar volume and excess partial molar isentropic compressibility were calculated for all the binary systems throughout the composition range and also at infinite dilution. The VE results were analyzed in the light of the Prigogine–Flory–Patterson theory. Analysis of each of the three contributions viz. interactional, free volume and P∗ to VE show that the interactional contribution is positive for all systems, the free volume effect is negative for all the mixtures and the P∗ contribution is negative for all the mixtures except nitrobenzene which shows a positive internal pressure. The variations of these parameters with composition and temperature are discussed in terms of intermolecular interactions prevailing in these mixtures.
Potential genotoxic impurities in pharmaceuticals at trace levels are of increasing concern to both pharmaceutical industries and regulatory agencies due to their possibility for human ...carcinogenesis. Molecular functional groups that render starting materials and synthetic intermediates as reactive building blocks for small molecules may also be responsible for their genotoxicity. Determination of these genotoxic impurities at trace levels requires highly sensitive and selective analytical methodologies, which poses tremendous challenges on analytical communities in pharmaceutical research and development. Experimental guidance for the analytical determination of some important classes of genotoxic impurities is still unavailable in the literature. Therefore, the present review explores the structural alerts of commonly encountered potential genotoxic impurities, draft guidance of various regulatory authorities in order to control the level of impurities in drug substances and to assess their toxicity. This review also describes the analytical considerations for the determination of potential genotoxic impurities at trace levels and finally few case studies are also discussed for the determination of some important classes of potential genotoxic impurities. It is the authors’ intention to provide a complete strategy that helps analytical scientists for the analysis of such potential genotoxic impurities in pharmaceuticals.
The disposition and metabolism of lemborexant, a novel dual orexin receptor antagonist currently under development as a therapeutic agent for insomnia disorder, were evaluated after a single oral ...administration of
14
Clemborexant in Sprague-Dawley rats (10 mg/kg) and cynomolgus monkeys (3 mg/kg).
In both species,
14
Clemborexant was rapidly absorbed: radioactivity concentration in blood peaked at 0.83-1.8 h, and decreased with elimination half-life of 110 h. The radioactivity administered was excreted primarily into faeces, with relatively little excreted into urine.
Lemborexant was not detected in bile, urine or faeces, indicating that lemborexant administered orally was completely absorbed from the gastrointestinal tract and that the main elimination pathway was metabolism in both species.
In rats, lemborexant was found to be minor in plasma (≤5.2% of total radioactivity), and M9 (hydroxylated form) was the major circulating metabolite. In monkeys, the major circulating components were lemborexant, M4 (N-oxide metabolite), M13 (di-oxidised form), M14 (di-oxidised form) and M16 (glucuronide of mono-oxidised form).
In both species, lemborexant was metabolised to various metabolites by multiple pathways, the primary of which was oxidation of the dimethylpyrimidine or fluorophenyl moiety.
Acylphloroglucinols are well-known Eucalyptus secondary metabolites which exhibit a variety of structures and bioactivities. The investigation of a crude acetone extract of Eucalyptus camaldulensis ...leaves led to the isolation of two new acylphloroglucinols, eucalypcamals O and P (1 and 2) together with seven phloroglucinols (3-9), and a benzene derivative (10). Their chemical structures were elucidated by 1D and 2D nuclear magnetic resonance (NMR) spectroscopy and mass spectroscopy. The absolute configurations of compounds 1 and 2 were established by comparison of experimental and calculated electronic circular dichroism (ECD) data. In the putative biosynthetic pathway, eucalypcamals O and P should be derived from hetero-Diels-Alder reaction between grandinol and trans-isoeugenol.
The title compounds, C
23
H
25
Br
2
NO
2
(
1
) and C
31
H
29
BrN
2
O
4
(
2
), crystallize in the space group
P
2
1
/
n
with two (
1-A
and
1-B
) and one molecules, respectively, in the asymmetric unit ...of the cell. The molecular conformation of these compounds is stabilized by intramolecular C—H...O hydrogen bonds and C—H...N or C—H...π interactions. The crystal structure of
1
features a relatively strong Br...O=C halogen bond, which is not observed in the case of
2
. Both crystal structures are characterized by the presence of C—H...Br hydrogen bonds and numerous intermolecular C—H...O hydrogen-bonding interactions.
One new benzene derivative Diocanol(1) was isolated from the ethyl acetate soluble portion of the whole plant of Urtica dioica along with known constituents β-amyrin (2), β-sitosterol (3), ...stigmasterol (4), and oleanolic acid (5). The structures of the isolated compounds were characterized based on 1H and 13C NMR spectra, including two-dimensional NMR techniques like COSY, HMQC, and HMBC and compared with the literature data.
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