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71.
V. V. Ivanovskaya A. N. Enyashin A. L. Ivanovskii 《Journal of Structural Chemistry》2004,45(1):151-155
Quantum-chemical modeling of electronic structure and interatomic interaction parameters has been performed for a series of fullerenelike cage molecules based on the isoelectronic TiO2, SnO2, and SnS2. The above characteristics are analyzed in relation to the type of atomic configuration, as well as the size and chemical composition of a nanostructure. 相似文献
72.
The molecular intrinsic characteristic contour (MICC) is defined as the set of all the classical turning points of electron movement in a molecule. Studies on the MICCs of some medium organic molecules, such as dimethylether, acetone, and some homologues of alkanes, alkenes, and alkynes, as well as the electron density distributions on the MICCs, are shown for the first time. Results show that the MICC is an intrinsic approach to shape and size of a molecule. Unlike the van der Waals hard-sphere model, the MICC is a smooth contour, and it has a clear physical meaning. Detailed investigations on the cross-sections of MICCs have provided a kind of important information about atomic size changing in the process of forming molecules. Studies on electron density distribution on the MICC not only provide a new insight into molecular shape, but also show that the electron density distribution on the boundary surface relates closely with molecular properties and reactivities. For the homologues of alkanes, Rout(H), Dmin, and Dmax (the minimum and maximum of electron density on the MICC), all have very good linear relationships with minus of the molecular ionization potential. This work may serve as a basis for exploring a new reactivity indicator of chemical reactions and for studying molecular shape properties of large organic and biological molecules. 相似文献
73.
The molecular intrinsic characteristic contour (MICC) is defined based on the classical turning point of electron movement in a molecule. Three typical organic molecules, I.e. Methane, methanol and formic acid, were employed as examples for detailed introduction of our method. Investigations on the cross-sections of MICC provide important information about atomic size changing in the process of forming molecules. The electron density distributions on the MICCs of these molecules were calculated and shown for the first time. Results showed that the electron density distribution on the MICC correlates closely with molecular chemical properties, and it provides a new insight into molecular boundary. 相似文献
74.
Homogeneity and structure of organically modified polysiloxane networks prepared by sol-gel co-condensation, as well as location and nature of water molecules and silanol groups were studied by 1D and 2D solid-state NMR. 1H–29Si and 1H–1H interatomic distances were estimated from variable contact-time CP/MAS experiments, 1H NMR chemical shifts and off-resonance WISE NMR. A structure model of these networks is proposed and discussed. The fraction of proton-inaccessible units Q4 in the networks decreases with increasing amounts of dimethylsiloxane (D) and methylsiloxane (T) units. In contrast to systems prepared by co-condensation of tetraethoxysilane (TEOS) with dimethyl(diethoxy)silane (DMDEOS), proton-inaccessible units form essential fraction in networks prepared by co-condensation of TEOS with methyl(triethoxy)silane (MTEOS). The proton-accessible part of the networks with high O/Si ratios is nano-heterogeneous phase, which is composed of water containing Q
i
particles separated by copolymer domains. The overall homogeneity and uniformity of binding sites around silanol groups increases by co-condensation TEOS with DMDEOS or MTEOS, while the amount of physisorbed water as well as the hydrogen bond strength decreases, as compared with neat silica gel prepared by polycondensation of TEOS. 相似文献
75.
Jan Franz 《International journal of quantum chemistry》2006,106(4):773-786
This work presents multi‐state multi‐reference Møller–Plesset second‐order perturbation theory as a variant of multi‐reference perturbation theory to treat electron correlation in molecules. An effective Hamiltonian is constructed from the first‐order wave operator to treat several strongly interacting electronic states simultaneously. The wave operator is obtained by solving the generalized Bloch equation within the first‐order interaction space using a multi‐partitioning of the Hamiltonian based on multi‐reference Møller–Plesset second‐order perturbation theory. The corresponding zeroth‐order Hamiltonians are nondiagonal. To reduce the computational effort that arises from the nondiagonal generalized Fock operator, a selection procedure is used that divides the configurations of the first‐order interaction space into two sets based on the strength of the interaction with the reference space. In the weaker interacting set, only the projected diagonal part of the zeroth‐order Hamiltonian is taken into account. The justification of the approach is demonstrated in two examples: the mixing of valence Rydberg states in ethylene, and the avoided crossing of neutral and ionic potential curves in LiF. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006 相似文献
76.
Twenty-two isomers/conformers of C3H6S+√ radical cations have been identified and their heats of formation (ΔHf) at 0 and 298 K have been calculated using the Gaussian-3 (G3) method. Seven of these isomers are known and their ΔHf data are available in the literature for comparison. The least energy isomer is found to be the thioacetone radical cation (4+) with C2v symmetry. In contrast, the least energy C3H6O+√ isomer is the 1-propen-2-ol radical cation. The G3 ΔHf298 of 4+ is calculated to be 859.4 kJ mol−1, ca. 38 kJ mol−1 higher than the literature value, ≤821 kJ mol−1. For allyl mercaptan radical cation (7+), the G3 ΔHf298 is calculated to be 927.8 kJ mol−1, also not in good agreement with the experimental estimate, 956 kJ mol−1. Upon examining the experimental data and carrying out further calculations, it is shown that the G3 ΔHf298 values for 4+ and 7+ should be more reliable than the compiled values. For the five remaining cations with available experimental thermal data, the agreement between the experimental and G3 results ranges from fair to excellent.
Cation CH3CHSCH2+√ (10+) has the least energy among the eleven distonic radical cations identified. Their ΔHf298 values range from 918 to 1151 kJ mol−1. Nevertheless, only one of them, CH2=SCH2CH2+√ (12+), has been observed. Its G3 ΔHf298 value is 980.9 kJ mol−1, in fair agreement with the experimental result, 990 kJ mol−1.
A couple of reactions involving C3H6S+√ isomers CH2=SCH2CH2+√ (12+) and trimethylene sulfide radical cation (13+) have also been studied with the G3 method and the results are consistent with experimental findings. 相似文献
77.
Fahadul Islam Saikat Mitra Talha Bin Emran Zidan Khan Nikhil Nath Rajib Das Rohit Sharma Ahmed Abdullah Al Awadh Moon Nyeo Park Bonglee Kim 《Molecules (Basel, Switzerland)》2022,27(17)
Gastric cancer is one of the most common cancers of the gastrointestinal tract. Although surgery is the primary treatment, serious maladies that dissipate to other parts of the body may require chemotherapy. As there is no effective procedure to treat stomach cancer, natural small molecules are a current focus of research interest for the development of better therapeutics. Chemotherapy is usually used as a last resort for people with advanced stomach cancer. Anti-colon cancer chemotherapy has become increasingly effective due to drug resistance and sensitivity across a wide spectrum of drugs. Naturally-occurring substances have been widely acknowledged as an important project for discovering innovative medications, and many therapeutic pharmaceuticals are made from natural small molecules. Although the beneficial effects of natural products are as yet unknown, emerging data suggest that several natural small molecules could suppress the progression of stomach cancer. Therefore, the underlying mechanism of natural small molecules for pathways that are directly involved in the pathogenesis of cancerous diseases is reviewed in this article. Chemotherapy and molecularly-targeted drugs can provide hope to colon cancer patients. New discoveries could help in the fight against cancer, and future stomach cancer therapies will probably include molecularly formulated drugs. 相似文献
78.
Jelver A. Sierra Katherine Gilchrist Jorge H. Tabares-Guevara Liliana Betancur-Galvis Jose R. Ramirez-Pineda Miguel A. Gonzlez-Cardenete 《Molecules (Basel, Switzerland)》2022,27(19)
Abietic acid (AA), dehydroabietic acid (DHA) and triptoquinones (TQs) are bioactive abietane-type diterpenoids, which are present in many edible vegetables and medicinal herbs with health-promoting properties. Evidence suggests that beneficial effects of diterpenes operate, at least in part, through effects on cells in the immune system. Dendritic cells (DCs) are a key type of leukocyte involved in the initiation and regulation of the immune/inflammatory response and natural or synthetic compounds that modulate DC functions could be potential anti-inflammatory/immunomodulatory agents. Herein, we report the screening of 23 known semisynthetic AA and DHA derivatives, and TQs, synthesized previously by us, in a multi-analyte DC-based assay that detects inhibition of pro-inflammatory cytokine production. Based on the magnitude of the inhibitory effect observed and the number of cytokines inhibited, a variety of activities among compounds were observed, ranging from inactive/weak to very potent inhibitors. Structurally, either alcohol or methyl ester substituents on ring A along with the introduction of aromaticity and oxidation in ring C in the abietane skeleton were found in compounds with higher inhibitory properties. Two DHA derivatives and two TQs exhibited a significant inhibition in all pro-inflammatory cytokines tested and were further investigated. The results confirmed their ability to inhibit, dose dependently, LPS-stimulated expression of the co-stimulatory molecules CD40 and/or CD86 and the production of the pro-inflammatory cytokines IL-1β, IL-6, IL-12 and TNFα. Our results demonstrate that DC maturation process can be targeted by semisynthetic DHA derivatives and TQ epimers and indicate the potential of these compounds as optimizable anti-inflammatory/immunomodulatory agents. 相似文献
79.
Mattia Russo Kirsty E. McGhee Tersilla Virgili David G. Lidzey Giulio Cerullo Margherita Maiuri 《Molecules (Basel, Switzerland)》2022,27(20)
Molecular dyes are finding more and more applications in photonics and quantum technologies, such as polaritonic optical microcavities, organic quantum batteries and single-photon emitters for quantum sensing and metrology. For all these applications, it is of crucial importance to characterize the dephasing mechanisms. In this work we use two-dimensional electronic spectroscopy (2DES) to study the temperature dependent dephasing processes in the prototypical organic dye Lumogen-F orange. We model the 2DES maps using the Bloch equations for a two-level system and obtain a dephasing time T2 = 53 fs at room temperature, which increases to T2 = 94 fs at 86 K. Furthermore, spectral diffusion processes are observed and modeled by a combination of underdamped and overdamped Brownian oscillators. Our results provide useful design parameters for advanced optoelectronic and photonic devices incorporating dye molecules. 相似文献
80.
Elizaveta Konstantinova Timofey Savchuk Olga Pinchuk Ekaterina Kytina Elizaveta Ivanova Lidiya Volkova Vladimir Zaitsev Alexander Pavlikov Elena Elizarova 《Molecules (Basel, Switzerland)》2022,27(22)
Titania is very famous photocatalyst for decomposition of organic pollutants. Its photocatalytic properties significantly depend on the morphology and chemical composition of the samples. Herein, the TiO2 nanotubes/CuxO nanoheterostructures have been synthesized and the effect of heat treatment performed in molecular atmospheres of air and argon on their photoelectrochemical and photocatalytic properties has been studied. The prepared samples have a higher reaction rate constant compared to TiO2 nanotubes in the decomposition reaction of methylene blue molecules. It is established that in argon treated nanoheterostructures, the copper oxide is present in two phases, CuO and Cu2O, while in air treated ones there is only CuO. In the TiO2 nanotubes/CuxO samples, Cu2+ ions and molecular O2− radicals were detected while in TiO2 nanotubes only carbon dangling bond defects are present. The dynamics of O2− radicals under illumination are discussed. It was shown that the TiO2 nanotubes do not exhibit photocatalytic activity under visible light. The mechanism of the photocatalytic reaction on the surface of the TiO2 nanotubes/CuxO samples was proposed. It is assumed that a photocatalytic decomposition of organic molecules under visible light at the surface of the nanoheterostructures under investigation is realized mainly by the reaction of these molecules with photogenerated O2− radicals. The results obtained are completely original and indicate the high promise of the prepared photocatalysts. 相似文献