The structural evolution of ubiquitin after transfer into the gas phase was studied by electron capture dissociation. Site-specific fragment yields show that ubiquitin's solution fold is overall unstable in the gas phase, but unfolding caused by loss of solvent is slowest in regions stabilized by salt bridges.

A spiro-linked hyperbranched architecture has been incorporated into electrophosphorescent conjugated polymers for the first time, aiming at simultaneously tailoring the intra- and intermolecular triplet energy back transfer from the phosphorescent guest to the conjugated polymer host. Based on a prototype with this unique structure, slower decay of triplet excitons, and ...

The nature of the chemical bond in conjugated hydrocarbons is analyzed through the generalized product function energy partitioning (GPF-EP) method, which allows the calculation of the quantum-mechanical interference and quasi-classical contributions to the energy. The method is applied to investigate the differences between the chemical bonding in conjugated and non-conjugated ...

Nonlinear excitations associated with dopant states play fundamental roles for charge transport in conjugated polymers. Here we report on real-space visualization of individual dopant states in single conjugated oligomers of poly-para-phenylene using cryogenic scanning tunneling microscopy and spectroscopy. We have found that these states exhibit a typical spatial extension of ...

Two-dimensional π-systems are of current interest in the design of functional organic molecules, exhibiting unique behavior for applications in organic electronics, single-molecule devices, and sensing. Here we describe the synthesis and characterization of "push-pull macrocycles": electron-rich and electron-poor moieties linked by a pair of (matched) conjugated bridges. We have developed ...

An anaerobic microbial community was enriched in a chemostat that was operated for more than 8 years with benzene and nitrate as electron acceptor. The coexistence of multiple species in the chemostat and the presence of a biofilm, led to the hypothesis that benzene-degrading species coexist in a syntrophic interaction, ...

The effective conjugation of ortho and ortho-alt-para-arylene ethynylenes, with appropriately positioned pyridine and pyrazine heterocycles, increases upon binding to Ag(I) and Pd(II) cations. Significant bathochromic shifts in the electronic spectra, witnessed upon introduction of these metal bridges, are consistent with enhanced electron delocalization in the unsaturated backbone. Control studies suggest ...

We have firstly demonstrated the dual facet of gold(iii) in the reaction between gold(iii) and porphyrins, which could be tuned through changing the counter ions, ligands and the electronic effect of the substituents of the porphyrins.

The metal coordination polymer of hypocrellin A bearing tryptamine motif (M-DTrpHA) can include fullerene via two-point interaction, involving π-π stacking and electron donor-acceptor interaction. The 1:1 host-guest system M-DTrpHA/fullerene exhibits moderate association constant Ka (6.62×104~6.46×105 M-1). Both the metal ions in M-DTrpHA and the substituents connected to the fullerene core ...

Energy and electron transfer from frameworks of nanoporous or mesostructured materials to guest species in the nanochannels have been attracting much attention due to their increasing availability for the design and construction of solid photofunctional systems, such as luminescent materials, photovoltaic devices, and photocatalysts. In the present study, energy and ...

Understanding the effects of substituents on the spectra of chlorophylls is essential for gaining a deep understanding of photosynthetic processes. Chlorophyll a and b differ solely in the nature of the 7-substituent (methyl versus formyl) whereas chlorophyll a and d differ solely in the 3-substituent (vinyl versus formyl), yet have ...

The electronic structure of modified chalcopyrite CuInS2 has been analyzed from first-principles within the density functional theory. The host chalcopyrite has been modified by introducing atomic impurities M at substitutional sites of the lattice host with M=C, Si, Ge, Sn, Ti, V, Cr, Fe, Co, Ni, Rh, and Ir. Both ...

The titanium dioxide (TiO(2)) photoassisted degradation of herbicide dinoseb has been examined in aqueous suspensions under UV light irradiation. The degradation kinetics were studied under various conditions such as substrate concentration, type of catalyst, catalyst dosage, pH, and light intensity as well as in presence of electron acceptors such as ...

The photodissociation of molecules often produces atomic fragments with polarized electronic angular momentum, and the atomic alignment, for example, can provide valuable information on the dynamical pathways of chemical reactions unavailable by other means. In this work, we demonstrate for the first time that orbital polarization in chemical reactions can ...

Chiral recognition abilities of the title host for (R)- and (S)-α-methyl-4-nitrobenzylamine were examined in the ground and excited states to give a relative affinity (K(R)/K(S)) of 2.16 by spectral titration and a relative rate constant (k(R)/k(S)) of 2.23 by fluorescence quenching, revealing that the quenching process is static and not ...

We show that gated bilayer graphene hosts a strong topological insulator (TI) phase in the presence of Rashba spin-orbit (SO) coupling. We find that gated bilayer graphene under preserved time-reversal symmetry is a quantum valley Hall insulator for small Rashba SO coupling λ_{R}, and transitions to a strong TI when ...

We report efficient host-guest solid-state light-emitting electrochemical cells (LECs) utilizing a cationic terfluorene derivative as the host and a red-emitting cationic transition metal complex as the guest. Carrier trapping induced by the energy offset in the lowest unoccupied molecular orbital (LUMO) levels between the host and the guest impedes electron ...

Magnetic-sensitive radical-ion-pair reactions are understood to underlie the biochemical magnetic compass used by avian species for navigation. Recent experiments have provided growing evidence for the radical-ion-pair magnetoreception mechanism, while recent theoretical advances have unravelled the quantum nature of radical-ion-pair reactions, which were shown to manifest a host of quantum-information-science concepts ...

Domino reactions of 2-methyl substituted chromones containing an electron withdrawing group at the 3-position with chromone-fused dienes synthesized a diverse range of benzo[a]xanthones and complicated chromone derivatives. These multiple-step reactions result in either two or three new C-C bonds without a transition metal catalyst or an inert atmosphere.

The gas-phase reaction of LiH(+) (X(2)Σ) with He((1)S) atoms, yielding Li(+)He with a small endothermicity for the rotovibrational ground state of the reagents, is analysed using the quantum reactive approach that employs the Negative Imaginary Potential (NIP) scheme discussed earlier in the literature. The dependence of low-T rates on the ...

Trypanosoma cruzi is a hemoflagellate protozoan that causes Chagas' disease. The life cycle of T. cruzi is complex and involves different evolutive forms that have to encounter different environmental conditions provided by the host. Herein, we performed a functional assessment of mitochondrial metabolism in the following two distinct evolutive forms ...

Density functional theory (DFT) calculations were carried out to investigate the electronic structures of representative ambipolar hosts for blue electroluminescence, based on two carbazole end-groups and meta-terphenyl-like bridges. The bridge molecular segments include meta-terphenyl, 2,6-bisphenylpyridine, 3,5-bisphenylpyridine, and 2,6-bisphenylpyrimidine. While the ionization potentials and electron affinities of these molecules are mainly ...

This article describes the preparation and the physico-chemical characterization of a new host-guest system consisting of zeolite beta nanoparticles as host and mitoxantrone as guest. The resulting host-guest system mitoxantrone@beta is characterized in terms of morphology (transmission electron microscopy, dynamic light scattering), structure (powder wide-angle X-ray diffraction, nitrogen sorption), surface ...

Anoplistes halodendri halodendri (Pallas, 1776) and Anoplistes halodendri ephippium (Stevens and Dalman, 1817) are two subspecies of the longicorn beetle A. halodendri (Coleoptera, Cerambycidae). In the recent years, these subspecies have been spreading rapidly in Hippophae rhamnoides and Hedysarum scoparium shrubberies in the Chinese provinces of Shanxi and Kingie, causing ...

The reduction of the three imines, N-benzylidene aniline (BAI), N-benzylidenemethylamine (BMI) and benzophenone imine (BPI) with SmI2 gives the reduced as well as coupled products. The reactions were found to be autocatalytic due to the formation of the tri-valent samarium in the course of the reaction. When pre-prepared SmI3, was ...

A new hexaazatriphenylene (HAT) derivative formed by the fusion of three HAT units has been prepared and its electronic and molecular structures have been fully characterized by optical and vibrational Raman spectroscopy, electrochemistry, solid-state UV and inverse photoemission spectroscopy (UPS and IPES), and by quantum-chemical calculations. A comparative HAT versus ...

Li-Yb co-doped nano-crystalline ZnO has been synthesized by a method of thermal growth from the salt mixtures. X-ray diffraction, transmission electron microscopy, atomic absorption spectroscopy and optical spectroscopy confirm the doping and indicate that the dopants may form Li-Li and Yb³⁺-Li based nanoclusters. When pumped into the conduction and exciton ...

The mean reaction force is introduced as the negative derivative of the free energy along a predefined reaction path. In analogy to the reaction force, this descriptor allows detailed characterization of different processes of the reaction mechanism and the assignment of electronic and structural free energy contributions to activation barriers. ...

In contrast to the bright success in thermal asymmetric synthesis, the precise stereocontrol remains a great challenge in chiral photochemistry, owing to the lack of effective tools and methodologies to control the short-lived, weakly interacting and highly reactive electronically excited species. In this study, we have achieved this ultimate goal ...

Viruses hijack host cell functions and optimize them for viral replication causing a severe threat to human health. However, viruses are also tools to understand cell biology and they may be effective reagents in nano-medicine. Studies from the molecular to cellular levels are aimed at understanding the details of viral ...

The future of organic light-emitting devices (OLEDs) is drifting from electrofluorescence toward electrophosphorescence due to the feasibility of realizing 100% internal quantum efficiency. There is limited availability of transition metals (TMs) such as Ir, Os, and Pt, which are used for color-tunable phosphorescent emitters, and the use of the host-guest ...

The low-temperature absorption and excitation spectra of interconfigurational 4f-5d transitions of Tb(3+) in a cubic fluoride host demonstrate the appearance of a first-order linear Jahn-Teller effect for the high-spin excited states of the excited electronic configuration 4f(7)5d involving 5d t(2g) orbitals. The τ(2g) mode is observed to be responsible for ...

We report a Pd-catalyzed direct cross-coupling of electron-deficient polyfluoroarenes with heteroaromatic tosylates. The notable features of this reaction are its high reaction efficiency, excellent chemoselectivity, operational simplicity, and mild reaction conditions. We have applied this protocol to prepare the semiconducting materials in a highly efficient manner.

We study the dynamical behavior of the unstable periodic orbit (NHIM) associated to the non-return transition state (TS) of the H(2) + H collinear exchange reaction and their effects on the reaction probability. By means of the normal form of the Hamiltonian in the vicinity of the phase space saddle ...

The electron density versus NICS(zz) (the out-of-plane component of nucleus-independent chemical shifts (NICS)) scan for assessing magnetic aromaticity among similar molecules with different ring sizes is improved by scanning the Laplacian of electron density versus NICS(zz) to include molecules containing different types of atoms. It is demonstrated that the new ...

Deep-blue organic light-emitting diodes (OLEDs) with nearly 5% external quantum efficiency were demonstrated using a 1,4-(dinaphthalen-2-yl)-naphthalene (DNN) host. The 4,4'-bis(9-ethyl-3-carbazovinylene)-1,1'-biphenyl (BCzVBi) dopant that was used in this experiment effectively accepted energy from the DNN host via Förster energy transfer because the photoluminescence spectrum of the DNN host showed better spectra ...

Sn-based SBA-15 was prepared by reacting di-n-butyldimethoxystannane with SBA-15 pretreated with trimethylchlorosilane (TMCS) to cap the external hydroxyl groups. Small-angle X-ray diffraction (SXRD), infrared spectroscopy (IR), nitrogen adsorption/desorption, transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and inductively coupled plasma atomic emission (ICP-AES) measurements allow us to propose that the organotin ...

A macrocyclic exTTF host for fullerenes offers control over the electronic coupling between an electron donor and an acceptor, and stabilizes the charge separated state lifetimes into the range of 500 ps.

Apanteles cypris is an endoparasitoid of rice pest Cnaphalocrocis medinalis. To better understand its host location mechanism, we examined the external morphology of antennal sensilla of A. cypris via scanning electron microscopy. The antennae of male and female A. cypris were filiform in shape, which consist of scape, pedicel, and ...

Sparidae are economically important fishes to both, fisheries and aquaculture in the Mediterranean. Species diversification is an important strategy for the development of Mediterranean aquaculture. One of the species recently introduced is the sharpsnout seabream Diplodus puntazzo (Walbaum, 1792). During a parasitological study of fish from the Gulf of Valencia ...

Quantum state-to-state dynamics for the H + HBr(υ(i) = 0,j(i) =0) reaction was studied on an accurate ab intio potential energy surface for the electronic ground state of BrH(2). Both the H + HBr → H(2) + Br abstraction reaction and the H(') + HBr → H(')Br + H exchange ...

Much of what is known regarding Riftia pachyptila physiology is based on the wealth of studies of tubeworms living at diffuse flows along the fast-spreading, basalt-hosted East Pacific Rise (EPR). These studies have collectively suggested that Riftia pachyptila and its chemoautotrophic symbionts are physiologically specialized, highly productive associations relying on ...

ABSTRACT: The electronic properties of multi-walled carbon nanotubes (MWCNTs) depend on the positions of their walls with respect to neighboring shells. This fact can enable several applications of MWCNTs as nano-electromechanical systems (NEMS). In this article, we report the findings of a first-principles study on the stability and dynamics of ...

A basic N,N-dimethylaminoazobenzene-fullerene (C(60)) dyad molecular skeleton is modelled and synthesized. In spite of the myriad use of azobenzene as a photo- and electrochromic moiety, the idea presented herein is to adopt a conceptually different path by using it as a bridge in a donor-bridge-acceptor single-molecular skeleton, connecting the electron ...

Free energy profiles for the proton transfer reactions in hydrogen-bonded complex of phenol with trimethylamine in methyl chloride solvent are studied with the reference interaction site model self-consistent field method. The reactions in both the electronic ground and excited states are considered. The second-order Møller-Plesset perturbation (MP) theory or the ...

A new type of the π-electron polycyclic organic superbases is proposed exhibiting very high proton affinities in the gas phase spanning the range from 280 to 323 kcal mol(-1) and the pK(a) up to 41.4 units in the MeCN solutions. Their salient feature is formation of the (H(+))-bridge upon protonation ...

The vibrationally resolved electronic spectra of isolated protonated polycyclic aromatic hydrocarbons (PAHs)-naphthalene, anthracene, and tetracene-have been recorded via neutral photofragment spectroscopy. The S(1)←S(0) transitions are all in the visible region and do not show a monotonic red shift as a function of the molecular size, as observed for the neutral ...

Cytochrome c3 from Desulfovibrio desulfuricans ATCC 27774 appears to be capable of receiving two protons and two electrons from hydrogenase for transport to the membrane, and converting electronic energy into proton motive force. Detailed studies of the mechanism require control both of the redox state and of the protonation state ...

The excited-state proton transfer and geminate recombination of 6-hydroxyquinoline (6HQ) encaged in catalytic Na(+)-exchanged faujasite zeolites X (NaX) and Y (NaY) have been explored by measuring steady-state and picosecond time-resolved spectra. The pathways and rate constants of proton transfer of excited 6HQ are determined by the microscopic environment of zeolitic ...

The indirect vicinal proton-proton coupling constants for pyrrole, furan, thiophene and 15 related heteroaromatic compounds were calculated using the Khon-Sham approximation. An analysis of the four Ramsey contributions to the coupling constants was carried out showing that the Fermi contact term is always positive and dominant, although the remaining contributions ...