Copper-promoted C5-selective bromination of 8-aminoquinoline amides with alkyl bromides.

An efficient and practical method for the synthesis of C5-brominated 8-aminoquinoline amides via a copper-promoted selective bromination of 8-aminoquinoline amides with alkyl bromides was developed. The reaction proceeds smoothly in dimethyl sulfoxide (DMSO) under air, employing activated and unactivated alkyl bromides as the halogenation reagents without additional external oxidants. This method features outstanding site selectivity, broad substrate scope, and excellent yields.

The combination of skeleton-engineering and periphery-engineering: a design strategy for organic doublet emitters.

The emergence and development of radical luminescent materials is a huge breakthrough toward high-performance organic light-emitting diodes (OLEDs) without spin-statistical limits. Herein, we design a series of radicals based on tris(2,4,6-trichlorophenyl)methyl (TTM) by combining skeleton-engineering and periphery-engineering strategies, and present some insights into how different chemical modifications can modulate the chemical stability and luminescence properties of radicals by quantum chemistry methods. Firstly, through the analysis of the geometric structure changes from the lowest doublet excited state (D1) to the doublet ground state (D0) states, the emission energy differences between the BN orientation isomers are explained, and it is revealed that the radical with a smaller dihedral angle difference can more effectively suppress the geometric relaxation of the excited states and bring a higher emission energy. Meanwhile, a comparison of the excited state properties in different radicals can help us to disclose the luminescence behavior, that is, the enhanced luminescent intensity of the radical is caused by the intensity borrowing between the charge transfer (CT) state and the dark locally excited (LE) state. In addition, an efficient algorithm for calculating the internal conversion rate (kIC) is introduced and implemented, and the differences in kIC values between designed radicals are explained. More specifically, the delocalization of hole and electron wave functions can reduce nonadiabatic coupling matrix elements (NACMEs), thus hindering the non-radiative decay process. Finally, the double-regulation of chemical stability and luminescence properties was realized through the synergistic effect of skeleton-engineering and periphery-engineering, and to screen the excellent doublet emitter (BN-41-MPTTM) theoretically.

Hydrogen Migration-Triggered Diradicaloid Singlet-Fission Switch.

We present a theoretical design of the singlet-fission (SF) interconversion between two hydrogen tautomers to attract attention to electronic devices such as switches in the SF field. We develop a tuned π-electron conjugation strategy based on single-hydrogen migration to introduce diradical character and yield low-lying E(T1) levels. Specifically, these objectives could be accomplished by moving one hydrogen from a dihydrogen-substituted pyrazine-fused ring to another unsubstituted pyrazine-fused ring in tetraazatetracenes. The predicted SF efficiency would be expected to exceed 120%. To guide future SF design development, one rule of thumb regarding the S0-state and T1-state emerges from our research: In the S0-state, single-hydrogen migration is crucial for effectively localized electrons, which are the key factor in the formation of diradicals. Conversely, single-hydrogen migration induces a large area of π-electron conjugation in the T1-state, which is completely applied to the electron-hole interaction in the S0 → T1 transition, thereby providing low-lying E(T1) levels. Furthermore, a series of hydrogen tautomers of tetraazaacenes have been proposed as diradicaloid SF switches to verify the reliability of the above rule of thumb. This study will not only help researchers in the photovoltaic field to obtain the desired E(T1) in the future but also broaden the application of hydrogen migration in photovoltaic switch research and supplement the SF database.

Replication of DNA Containing Mirror-Image Thymidine in E. coli Cells.

DNA damage can occur naturally or through environmental factors, leading to mutations in DNA replication and genomic instability in cells. Normally, natural d-nucleotides were selected by DNA polymerases. The template l-thymidine (l-T) has been shown to be bypassed by several types of DNA polymerases. However, DNA replication fidelity of nucleotide incorporation opposite l-thymidine in vivo remains unknown. Here, we constructed plasmids containing a restriction enzyme (PstI) recognition site in which the l-T lesion was site-specifically located within the PstI recognition sequence (CTGCAG). Further, we assessed the efficiencies of nucleotide incorporation opposite the l-T site and l-T lesion bypass replication in vitro and in vivo. We found that recombinants containing the l-T lesion site inhibited DNA replication. In addition, A was incorporated opposite the l-T lesion by routine PCR assay, whereas preference for nucleotide incorporation opposite the l-T site was A (13%), T (22%), C (46%), and G (19%), and no nucleotide insertion and deletions were detected in E. coli cells. In particular, a novel restriction enzyme-mediated method for detection of the mutagenic properties of DNA lesion was established, which allows us to readily detect restriction-digestion of the l-T-bearing plasmids. The study provided significant insight into how mirror-image nucleosides perturb the fidelity of DNA replication in vivo and whether they elicit mutagenic effects, which may help to understand both how DNA damage interferes with the flow of genetic information during DNA replication and development of diseases caused by gene mutation.

New insight into enzymatic hydrolysis of peptides with site-specific amino acid d-isomerization.

The isomerization of l-amino acids in peptides and proteins into d-configuration under physiological conditions would affect the physiological dysfunction and caused protein conformational diseases. The presence of d-amino acids might change the higher-order structure of proteins and triggered abnormal aggregation. In order to better understand this phenomenon and promote degradation, we systematically studied the enzymatic hydrolysis of a series of peptides obtained by replacing l-amino acids in different positions of template peptide KYNETWRSED with d-amino acids under the action of Protease K. The results showed that, compared with normal peptide, isomerization of different amino acids had different effects on the anti-enzymatic hydrolysis of the peptides, especially d-tryptophan at position 6, which significantly inhibited enzymatic hydrolysis. The analysis of the peptide cleavage site revealed that the efficiency of enzymatic hydrolysis mainly depended on the isomerization of the amino acids at a specific site of the peptide cleavage. Further studies showed that the enzymatic hydrolysis of substrates could be facilitated by optimized reaction conditions such as temperature, pH, addition of metal ions, and change of buffer. In this way the accumulation of disease-associated d-amino acid containing polypeptides/proteins could be prevented.

Exploring the Influence of Halogen Coordination Effect of Stable Bimetallic MOFs on Oxygen Evolution Reaction.

The energy crisis and environmental pollution have forced scientists to explore alternative energy conversion and storage devices. The anodic reactions of these devices are all oxygen evolution reactions (OER), so the development of efficient OER electrocatalysts is of great significance. At the same time, understanding the reaction mechanism of OER is conducive to the rational design of efficient OER electrocatalysts. In general, catalytic active centers play a direct role in OER performance. In this paper, a series of stable bimetallic metal-organic frameworks (MOFs, named as Fe3 -Con -X2 , n=2, 3 and X=F, Cl, Br) with similar structure were synthesized by changing the halogen coordinated with the cobalt metal active center, aiming to investigate the influence of halogen substitution effect on OER performance. It was found that the OER activity of Fe3 -Co3 -F2 is much better than Fe3 -Co2 -Cl2 and Fe3 -Co2 -Br2 , indicating that the regulation of the electronegativity change of the coordination halogen atom can regulate the coordination electron structure of the metal active center, thereby achieving effective regulation of OER performance.

Influence of d-Amino Acids in Beer on Formation of Uric Acid.

Excessive intake of beer could increase serum uric acid levels, leading to high risk of gout, which was previously attributed to high purine content in beer. Recent reports that purine-rich vegetables and bean products do not cause higher uric acid levels do not support this theory. Why excessive intake of beer could increase a high risk of gout has been unclear. Other factors affecting the accumulation of uric acid in the blood have been explored. Beer contains relatively high levels of d-amino acids due to the racemization of l-amino acids induced by food processing. d-amino acid was catalyzed by d-amino acid oxidase to produce H2O2, which is further oxidized in the presence of Fe2+ to produce hydroxyl radicals, resulting in DNA damage and formation of a large amount of purine bases, which are oxidized to uric acid by a series of enzymes. Some food ingredients, such as vitamins and I-, prompt d-amino acids to form uric acid. d-amino acids in beer are one of the key factors responsible for the increase in uric acid levels. The biological response of d-amino acids could explain gout occurrence in beer drinkers.

Self-Assembly of a Phosphate-Centered Polyoxo-Titanium Cluster: Discovery of the Heteroatom Keggin Family.

Over the past 200 years, the most famous and important heteroatom Keggin architecture in polyoxometalates has only been synthesized with Mo, W, V, or Nb. Now, the self-assembly of two phosphate (PO4 3- )-centered polyoxo-titanium clusters (PTCs) is presented, PTi16 and PTi12 , which display classic heteroatom Keggin and its trivacant structures, respectively. Because TiIV has lower oxidate state and larger ionic radius than MoVI , WVI , VV , and NbV , additional TiIV centres in these PTCs are used to stabilize the resultant heteroatom Keggin structures, as demonstrated by the cooresponding theoretical calculation results. These photoactive PTCs can be utilized as efficient photocatalysts for highly selective CO2 -to-HCOOH conversion. This new discovery indicates that the classic heteroatom Keggin family can be assembled with Ti, thus opening a research avenue for the development of PTC chemistry.

Synthesis of Pyrrole via a Silver-Catalyzed 1,3-Dipolar Cycloaddition/Oxidative Dehydrogenative Aromatization Tandem Reaction.

Pyrroles are an important group of heterocyclic compounds with a wide range of interesting properties, which have resulted in numerous applications in a variety of fields. Despite the importance of these compounds, there have been few reports in the literature pertaining to the synthesis of pyrroles from simple alkenes using a one-pot sequential 1,3-dipolar cycloaddition/aromatization reaction sequence. Herein, we report the development of a benzoyl peroxide-mediated oxidative dehydrogenative aromatization reaction for the construction of pyrroles. We subsequently developed a one-pot tandem reaction that combined this new method with a well-defined silver-catalyzed 1,3-dipolar cycloaddition reaction, thereby providing a practical method for the synthesis of multisubstituted pyrroles from easy available alkenes. The mechanism of this oxidative dehydrogenative aromatization reaction was also examined in detail.

Naphthotetrathiophene-Based Helicene-Like Molecules: Synthesis and Photophysical Properties.

Two novel helicene-like molecules based on naphthotetrathiophene are successfully synthesized. All target molecules and intermediates are characterized by (1)H NMR, (13)C NMR, IR, and HRMS. Their electrochemical and photophysical properties are studied. The configurations of the molecules are optimized by DFT quantum calculations and UV-vis behaviors are also predicted to further understand the origin of different absorption bands. We believe the current work illustrated an efficient way for the design and synthesis of sophisticated structures with naphthotetrathiophene as building blocks.

Palladium-catalyzed enantioselective decarboxylative cycloaddition of vinylethylene carbonates with isocyanates.

An efficient method for the enantioselective construction of ß-substituted ß-vinylglycinol derivatives through palladium-catalyzed decarboxylative cycloaddition of vinylethylene carbonates with isocyanates was developed. By using a palladium complex generated in situ from [Pd2 (dba)3]⋅CHCl3 (dba=dibenzylideneacetone) and (S)-Segphos as a catalyst under mild reaction conditions, the process provided 4-substituted-4-vinyloxazolidin-2-ones in high yields with a high level of enantioselectivity. The stereochemical outcome of the reaction was explained by DFT calculations and the synthetic utility of the process was demonstrated by the gram-scale transformation and formal synthesis of MK-0731 as a kinesin spindle protein inhibitor.

Silicon Spiro Double Helicene-like Compounds Based on Dithieno[2,3-b:3',2'-d]thiophene: Syntheses and Crystal Structures.

Silicon spiro carbon-sulfur double helicene-like compounds 1 and rac-2 were synthesized from 2,5-bis-trimethylsilanyldithieno[2,3-b:3',2'-d]thiophene, with total yields of 17% and 7%, respectively. (1)H and (13)C NMR spectra and X-ray crystallographic analysis showed the predicted 4-fold symmetry for 1 and rac-2 and confirmed their spiro double helicene-like spatial configurations. The absorption behavior of compounds 1 and rac-2 was also investigated.

Aza-Wacker-type reaction between electron-deficient olefins and N-alkylsulfonamides.

A palladium-catalyzed oxidative amination protocol of electron-deficient olefins by aza-Wacker-type reaction with N-alkylsulfonamides was developed. The presence of the stoichiometric amount of methanesulfonic acid was crucial for the success of this transformation. The reactions were conducted in green solvent under mild conditions and scalable with excellent E-type stereoselectivity. In addition, a Pd(II)/Pd(0) catalytic cycle with the existence of a very strong oxidant (Selectfluor) was proposed.

Synthesis and characterization of cyclooctatetrathiophenes with different connection sequences.

Based on the selectivity of deprotonation of 5,5'-bistrimethylsilyl-2,3'-bithiophene (4) in the presence of n-BuLi, three new cyclooctatetrathiophenes (COThs), COTh-1, COTh-2, and COTh-3 have been efficiently developed via intermolecular or intramolecular cyclizations. Their crystal structures clearly show that the different connectivity sequence of the thiophene rings in the molecules. The CV data and UV-vis absorbance spectra of COThs are also described. In addition, the time-dependent density functional theory (TDDFT) calculations accurately reproduce experimental observations and afford band assignment.

Small Molecules of Cyclopentadithiophene Derivatives: Effect of Sulfur Atoms Position and Substituted Groups on Their UV-abs Properties.

Thiophene-based organic semiconductors used as the active components have received much attention. Their photoelectric properties can be easily tuned with various substitutions at different positions on molecular structures. Here, we synthesized series cyclopentadithiophene (CDT) derivatives with sulfur atoms at ortho- (o-CDT), meta- (m-CDT) and para-position (p-CDT) of the bridge carbon. These CDT derivatives were substituted by carbonyl/dicyanomethylene at the bridge position and/or by phenyl groups at α position, respectively. Due to the different conjugation extent and the variation of donor-acceptor (D-A) interaction originating from the change of sulfur atom position, diverse absorption spectra were observed. Especially for dicyanomethylene substituted o-CDT with phenyl as substitution group (DPCN-o-CDT), its absorption spectrum covers the whole region of visible light. Combining with the electrochemical behaviors and theoretical calculations, it was found that the sulfur atoms mainly contribute to the molecular conjugation in these CDT derivatives, especially for o-CDT derivatives. For phenyl groups, they primarily act as electron donor in m-CDT derivatives, and chiefly contribute to molecular conjugation in p-CDT derivatives, and simultaneously work as electron donor and conjugation component in o-CDT derivatives, respectively.

Palladium-catalyzed decarboxylative cycloaddition of vinylethylene carbonates with formaldehyde: enantioselective construction of tertiary vinylglycols.

An efficient method for the enantioselective construction of tertiary vinylglycols through a palladium-catalyzed asymmetric decarboxylative cycloaddition of vinylethylene carbonates with formaldehyde was developed. By using a palladium complex generated in situ from [Pd2(dba)3]⋅CHCl3 and a phosphoramidite ligand as a catalyst under mild reaction conditions, the process allows conversion of racemic 4-substituted 4-vinyl-1,3-dioxolan-2-ones into the corresponding 1,3-dioxolanes, as methylene acetal protected tertiary vinylglycols, in high yields with good to excellent enantioselectivities.

After the electronic field: structure, bonding, and the first hyperpolarizability of HArF.

In this work, we add different strength of external electric field (E(ext)) along molecule axis (Z-axis) to investigate the electric field induced effect on HArF structure. The H-Ar bond is the shortest at E(ext) = -189 × 10(-4) and the Ar-F bond show shortest value at E(ext) = 185 × 10(-4) au. Furthermore, the wiberg bond index analyses show that with the variation of HArF structure, the covalent bond H-Ar shows downtrend (ranging from 0.79 to 0.69) and ionic bond Ar-F shows uptrend (ranging from 0.04 to 0.17). Interestingly, the natural bond orbital analyses show that the charges of F atom range from -0.961 to -0.771 and the charges of H atoms range from 0.402 to 0.246. Due to weakened charge transfer, the first hyperpolarizability (ß(tot)) can be modulated from 4078 to 1087 au. On the other hand, make our results more useful to experimentalists, the frequency-dependent first hyperpolarizabilities were investigated by the coupled perturbed Hartree-Fork method. We hope that this work may offer a new idea for application of noble-gas hydrides.

Theoretical insights into [PMo12O40](3-) grafted on single-walled carbon nanotubes.

Nano-hybrid materials based on a combination of polyoxometalate (POM) clusters and single-walled carbon nanotubes (SWNT) exhibit a great interesting application in molecular cluster batteries. The interactions between POM and SWNT and their detailed electronic properties have been investigated by employing first-principles calculations. Various models were constructed to study the geometries, interactions (binding sites and energies), and charge transfer behavior. Analysis of charge distributions reveals two different charge transfer characteristic depending on the type of POM interaction with SWNT. The simulation provides insight into the optimal structures in lieu of interfacial stability. Finally, the implications of these results for understanding the properties of molecular cluster batteries are discussed.

Quantum chemical characterization and design of host materials based on phosphine oxide-substituted (triphenylamine) fluorene for (deep) blue phosphors in OLEDs.

We studied the electronic structures of a series of fluorene derivatives (p/mPODPFs and p/mPOAPFs) using density functional theory calculations and investigated their performances as host materials in organic light-emitting diodes from three aspects, i.e. triplet energy, ability of charge injection from neighboring organic layer or electrode, and match of the hosts and the reference guests (FIrpic and FCNIr) for efficient energy transfer (EF). Especially for the last aspect, the singlet/triplet (S(1)/T(1)) energies as well as the simulated host emission and guest absorption spectra are investigated to predict the possible emission mechanisms in the host-guest system and therefore to pursue the most suitable host for (deep) blue guest. From the investigated results, we deduced that pPODPF and pPOAPF are suitable for sky-blue FIrpic due to feasible Förster/Dexter energy transfers from pPODPF/pPOAPF to FIrpic, which agrees well with the experimental results. Furthermore, the higher external quantum efficiency (20.6%) of the pPOAPF-based device than that of the pPODPF-based device (13.2%) in experiments was inferred to be attributed to the matching S(1) energies between pPOAPF and FIrpic as well as good hole/electron injection abilities of pPOAPF in spite of a smaller overlap between the pPOAPF emission and FIrpic absorption spectra. By contrast, mPOAPF and mPODPF, designed in the work, may match with deep-blue FCNIr. In particular, mPOAPF may exhibit good performance as a host material for deep blue FCNIr as a consequence of its own balanced hole/electron injection ability and the matching S(1)/T(1) energies between mPOAPF and FCNIr.