Ultrafast intramolecular charge transfer with strongly twisted aminobenzonitriles: 4-(di-tert-butylamino)benzonitrile and 3-(di-tert-butylamino)benzonitrile

The newly synthesized aminobenzonitriles with two bulky amino substituents 4-(di-tert-butylamino)benzonitrile (DTABN) and 3-(di-tert-butylamino)benzonitrile (mDTABN) have strongly twisted amino groups in the ground state. From X-ray crystal analysis it is found that the amino twist angle theta of mDTABN equals 86.5 degrees , whereas a twist angle of around 75 degrees is deduced for DTABN from the extinction coefficient of its lowest-energy absorption band in n-hexane. Because of the electronic decoupling between the amino and benzonitrile groups caused by these large twist angles, the absorption of DTABN and mDTABN is relatively weak below 40000 cm-1, with extinction coefficients around 25 times smaller than those of the planar 4-(dimethylamino)benzonitrile (DMABN). DTABN as well as mDTABN undergo efficient intramolecular charge transfer (ICT) in the singlet excited state, in nonpolar (n-hexane) as well as in polar (acetonitrile) solvents. Their fluorescence spectra consist of an ICT emission band, without evidence for locally excited (LE) fluorescence. The occurrence of efficient ICT with mDTABN is different from the findings with all other N,N-dialkylaminobenzonitriles in the literature, for which ICT only appears with the para-derivative. From solvatochromic measurements, an ICT dipole moment of 17 D is determined for DTABN as well as for mDTABN, similar to that of DMABN. The picosecond fluorescence decays of DTABN (time resolution 3 ps) are effectively single exponential. Their decay time is equal to the ICT lifetime tau'0(ICT), which increases with solvent polarity from 0.86 ns in n-hexane to 3.48 ns in MeCN at 25 degrees C. The femtosecond excited-state absorption (ESA) spectra of DTABN in n-hexane and MeCN at 22 degrees C show a decay of the LE and a corresponding rise of the ICT absorption. The ICT reaction time is 70 fs in n-hexane and 60 fs in MeCN. DTABN and mDTABN may have a strongly twisted ICT state, similar to that of 6-cyanobenzoquinuclidine but different from that of DMABN.     

A novel ethylene-bridged spiro[3.2]Hexane

3,3-Dichlorotricyclo[5.1.0.0^1,4]oct-5-en-2-one ($\text{1}$) was prepared by addition of dichloroketene to 1,3-cyclohexadiene followed by allylic bromination and dehydrobromination.     

Development of a solid‐phase microextraction LC–MS/MS method for determination of oxidative stress biomarkers in biofluids

Recently the connection between oxidative stress and various diseases, including cancer and Alzheimer's, attracts notice as a pathway suitable for diagnostic purposes. 8‐Oxo‐deoxyguanosine and 8‐oxo‐deoxyadenosine produced from the interaction of reactive oxygen species with DNA become prominent as biomarkers. Several methods have been developed for their determination in biofluids, including solid‐phase extraction and enzyme‐linked immunosorbent assays. However, still, there is a need for reliable and fast analytical methods. In this context, solid‐phase microextraction offers many advantages such as flexibility in geometry and applicable sample volume, as well as high adaptability to high‐throughput sampling. In this study, a solid‐phase microextraction method was developed for the determination of 8‐oxo‐deoxyguanosine and 8‐oxo‐deoxyadenosine in biofluids. The extractive phase of solid‐phase microextraction consisted of hydrophilic–lipophilic balanced polymeric particles. In order to develop a solid‐phase microextraction method suitable for the determination of the analytes in saliva and urine, several parameters, including desorption solvent, desorption time, sample pH, and ionic strength, were scrutinized. Analytical figures of merit indicated that the developed method provides reasonable interday and intraday precisions (<15% in both biofluids) with acceptable accuracy. The method provides a limit of quantification for both biomarkers at 5.0 and 10.0 ng/mL levels in saliva and urine matrices, respectively.     

Brownian dynamics simulations on the self-assembly behavior of AB hybrid dendritic-star copolymers

The micellization behavior of hybrid dendritic-star copolymers with solvophilic dendritic units is studied by means of Brownian dynamics simulations. The critical micelle concentration and the micelle size and shape are examined for different solvophobic/solvophilic ratios r as a function of the number of the dendritic and linear arms. Hybrid dendritic-star copolymers with one dendritic and up to three solvophobic linear branches form spherical micelles with preferential aggregation number. Those with two dendritic arms and three solvophobic branches form micelles with wide aggregation numbers only for small values of r. For hybrid dendritic-star copolymers with three dendritic arms and two or three solvophobic linear arms, micelles with wide aggregation numbers are also formed but for slightly higher values of r. Our results for the aggregation number are compared with existing results of other architectures obtained at the same temperature, and an inequality for the aggregation number is proposed.     

2020 Roadmap on Carbon Materials for Energy Storage and Conversion

Carbon is a simple, stable and popular element with many allotropes. The carbon family members include carbon dots, carbon nanotubes, carbon fibers, graphene, graphite, graphdiyne and hard carbon, etc. They can be divided into different dimensions, and their structures can be open and porous. Moreover, it is very interesting to dope them with other elements (metal or non‐metal) or hybridize them with other materials to form composites. The elemental and structural characteristics offer us to explore their applications in energy, environment, bioscience, medicine, electronics and others. Among them, energy storage and conversion are extremely attractive, as advances in this area may improve our life quality and environment. Some energy devices will be included herein, such as lithium‐ion batteries, lithium sulfur batteries, sodium‐ion batteries, potassium‐ion batteries, dual ion batteries, electrochemical capacitors, and others. Additionally, carbon‐based electrocatalysts are also studied in hydrogen evolution reaction and carbon dioxide reduction reaction. However, there are still many challenges in the design and preparation of electrode and electrocatalytic materials. The research related to carbon materials for energy storage and conversion is extremely active, and this has motivated us to contribute with a roadmap on ‘Carbon Materials in Energy Storage and Conversion’.     

Predicting retrosynthetic pathways using transformer-based models and a hyper-graph exploration strategy

We present an extension of our Molecular Transformer model combined with a hyper-graph exploration strategy for automatic retrosynthesis route planning without human intervention. The single-step retrosynthetic model sets a new state of the art for predicting reactants as well as reagents, solvents and catalysts for each retrosynthetic step. We introduce four metrics (coverage, class diversity, round-trip accuracy and Jensen–Shannon divergence) to evaluate the single-step retrosynthetic models, using the forward prediction and a reaction classification model always based on the transformer architecture. The hypergraph is constructed on the fly, and the nodes are filtered and further expanded based on a Bayesian-like probability. We critically assessed the end-to-end framework with several retrosynthesis examples from literature and academic exams. Overall, the frameworks have an excellent performance with few weaknesses related to the training data. The use of the introduced metrics opens up the possibility to optimize entire retrosynthetic frameworks by focusing on the performance of the single-step model only.

We present an extension of our Molecular Transformer model combined with a hyper-graph exploration strategy for automatic retrosynthesis route planning without human intervention.     

Electronic Structure of Rh(2)(&mgr;-CO)(CO)(2)(H(2)PCH(2)PH(2))(2). An Example of a Non-A-Frame Structure

Calculations based on density functional theory (DFT) and Hartree-Fock configuration interaction (HF-CI) methodology have been carried out to investigate the rhodium-rhodium coupling in Rh(2)(CO)(2)(dppm)(2), 1 (dppm = Ph(2)PCH(2)PPh(2)) and in Rh(2)(&mgr;-CO)(CO)(2)(dppm)(2), 2. DFT geometries, obtained with the Dgauss program, are in good agreement with those determined from X-ray, but HF geometries, calculated using the same basis sets, yield bond distances systematically too long. Calculations indicate that the rhodium atoms in 1 are linked by a single bond. The insertion of a semibridging carbonyl between the two metal atoms leads to a shortening of the rhodium-rhodium distance and also to a noticeable weakening of the metal-metal interaction. Both effects, and also the stabilization of the HOMO of 2, are related to an observed change from square planar to tetrahedral of the ligand environment of the Rh atom proximal to the inserted CO. Both MO analysis and bond characterization from the topology of the charge density confirm the existence of a bonding interaction between the semibridging carbonyl and the distal rhodium atom. The electronic structures of the dicationic complex [Rh(2)(CO)(3)(dppm)(2)](2+) and of the A-frame-like, isoelectronic system Rh(2)Br(2)(&mgr;-CO) (dppm)(2) are also discussed. The electron deformation density is derived from 2 by means of several methodological approaches, namely, HF, HF-CI, DFT, and DFT + gradient corrections. The HF deformation density obtained in the plane containing the metals and the three CO ligands is discussed, as well as the "correlation density" obtained from the difference maps DFT - HF and CI - HF.     

Optimum conditions for the water extraction of L-theanine from green tea

Theanine is a unique non-protein amino acid found in tea (Camellia sinensis). It contributes to the favourable umami taste of tea and is linked to various beneficial effects in humans. There is an increasing interest in theanine as an important component of tea, as an ingredient for novel functional foods and as a dietary supplement. Therefore, optimal conditions for extracting theanine from tea are required for the accurate quantification of theanine in tea and as an efficient first step for its purification. This study examined the effects of four different extraction conditions on the yield of theanine from green tea using water and applied response surface methodology to further optimise the extraction conditions. The results showed that temperature, extraction time, ratio of water-to-tea and tea particle sizes had significant impacts on the extraction yield of theanine. The optimal conditions for extracting theanine from green tea using water were found to be extraction at 80 °C for 30 min with a water-to-tea ratio of 20:1 mL/g and a tea particle size of 0.5-1 mm.