Benchmarking of Density Functionals for the Description of Optical Properties of Newly Synthesized π-Conjugated TADF Blue Emitters

Computational modeling of the optical characteristics of organic molecules with potential for thermally activated delayed fluorescence (TADF) may assist markedly the development of more efficient emitting materials for organic light-emitting diodes. Recent theoretical studies in this area employ mostly methods from density functional theory (DFT). In order to obtain accurate predictions within this approach, the choice of a proper functional is crucial. In the current study, we focus on testing the performance of a set of DFT functionals for estimation of the excitation and emission energy and the excited singlet-triplet energy gap of three newly synthesized compounds with capacity for TADF. The emitters are designed specifically to enable charge transfer by π-electron conjugation, at the same time possessing high-energy excited triplet states. The functionals chosen for testing are from various groups ranging from gradient-corrected through global hybrids to range-separated ones. The results show that the monitored optical properties are especially sensitive to how the long-range part of the exchange energy is treated within the functional. The accurate functional should also be able to provide well balanced distribution of the π-electrons among the molecular fragments. Global hybrids with moderate (less than 0.4) share of exact exchange (B3LYP, PBE0) and the meta-GGA HSE06 are outlined as the best performing methods for the systems under study. They can predict all important optical parameters correctly, both qualitatively and quantitatively.     

2-Methyltetrahydrofuran (2-MeTHF) as a versatile green solvent for the synthesis of amphiphilic copolymers via ROP,FRP, and RAFT tandem polymerizations

2-methyltetrahydrofuran (2-MeTHF) is a readily available, inexpensive, neoteric, bio-based solvent. It has been adopted across a wide range of chemical processes including the batch manufacture of fine chemicals, enzymatic polycondensations and ring opening polymerizations. To reduce the environmental burden related to the synthesis of pharmaceutical-grade polymers based on lactide and caprolactone, we envisaged the use of 2-MeTHF. For the first time, we combined a series of metal-free and enzymatic ROPs with free radical and controlled RAFT polymerizations (carried out separately and in tandem) in 2-MeTHF, in order to easily tune the chemistry and the architecture of the final polymers. After a simple purification, the amphiphilic polymers were formulated into nanoparticles and tested for their cytocompatibility in three model cell lines, to assess their application as potential polymeric excipients for nanomedicines.     

Zwitterionic Polymeric Sulfur Ylides with Minimal Charge Separation Open a New Generation of Antifouling and Bactericidal Materials**

Zwitterionic polymers are widely employed hydrophilic building blocks for antifouling coatings with numerous applications across a wide range of fields, including but not limited to biomedical science, drug delivery and nanotechnology. Zwitterionic polymers are considered as an attractive alternative to polyethylene glycol because of their biocompatibility and effectiveness to prevent formation of biofilms. To this end, zwitterionic polymers are classified in two categories, namely polybetaines and polyampholytes. Yet, despite a fundamental interest to drive the development of new antifouling materials, the chemical composition of zwitterionic polymer remains severely limited. Here, we show that poly(sulfur ylides) that belong to the largely overlooked class of poly(ylides), effectively prevent the formation of biofilms from pathogenic bacteria. While surface energy analysis reveals strong hydrogen-bond acceptor capabilities of poly(sulfur ylide), membrane damage of pathogenic bacteria induced by poly(sulfur ylides) indicates toxicity towards bacteria while not affecting eucaryotic cells. Such synergistic effect of poly(sulfur ylides) offers distinct advantages over polyethylene glycol when designing new antifouling materials. We expect that our findings will pave the way for the development of a range of ylide-based materials with antifouling properties that have yet to be explored, opening up new directions at the interface of chemistry, biology, and material science.     

Synthesis of 2D Germanane (GeH): a New,Fast, and Facile Approach

Germanane (GeH), a germanium analogue of graphane, has recently attracted considerable interest because its remarkable combination of properties makes it an extremely suitable candidate to be used as 2D material for field effect devices, photovoltaics, and photocatalysis. Up to now, the synthesis of GeH has been conducted by substituting Ca by H in a β‐CaGe₂ layered Zintl phase through topochemical deintercalation in aqueous HCl. This reaction is generally slow and takes place over 6 to 14 days. The new and facile protocol presented here allows to synthesize GeH at room temperature in a significantly shorter time (a few minutes), which renders this method highly attractive for technological applications. The GeH produced with this method is highly pure and has a band gap (E_g) close to 1.4 eV, a lower value than that reported for germanane synthesized using HCl, which is promising for incorporation of GeH in solar cells.     

Controlling the Surface Functionalization of Ultrasmall Gold Nanoparticles by Sequence-Defined Macromolecules

Ultrasmall gold nanoparticles (diameter about 2 nm) were surface-functionalized with cysteine-carrying precision macromolecules. These consisted of sequence-defined oligo(amidoamine)s (OAAs) with either two or six cysteine molecules for binding to the gold surface and either with or without a PEG chain (3400 Da). They were characterized by ¹H NMR spectroscopy, ¹H NMR diffusion-ordered spectroscopy (DOSY), small-angle X-ray scattering (SAXS), and high-resolution transmission electron microscopy. The number of precision macromolecules per nanoparticle was determined after fluorescent labeling by UV spectroscopy and also by quantitative ¹H NMR spectroscopy. Each nanoparticle carried between 40 and 100 OAA ligands, depending on the number of cysteine units per OAA. The footprint of each ligand was about 0.074 nm² per cysteine molecule. OAAs are well suited to stabilize ultrasmall gold nanoparticles by selective surface conjugation and can be used to selectively cover their surface. The presence of the PEG chain considerably increased the hydrodynamic diameter of both dissolved macromolecules and macromolecule-conjugated gold nanoparticles.     

Polypyridyl-Based Copper Phenanthrene Complexes: Combining Stability with Enhanced DNA Recognition

We report a series of copper(II) artificial metallo-nucleases (AMNs) and demonstrate their DNA damaging properties and in-vitro cytotoxicity against human-derived pancreatic cancer cells. The compounds combine a tris-chelating polypyridyl ligand, di-(2-pycolyl)amine (DPA), and a DNA intercalating phenanthrene unit. Their general formula is Cu-DPA-N,N' (where N,N'=1,10-phenanthroline (Phen), dipyridoquinoxaline (DPQ) or dipyridophenazine (DPPZ)). Characterisation was achieved by X-ray crystallography and continuous-wave EPR (cw-EPR), hyperfine sublevel correlation (HYSCORE) and Davies electron-nuclear double resonance (ENDOR) spectroscopies. The presence of the DPA ligand enhances solution stability and facilitates enhanced DNA recognition with apparent binding constants (K_app) rising from 10⁵ to 10⁷ m ⁻¹ with increasing extent of planar phenanthrene. Cu-DPA-DPPZ, the complex with greatest DNA binding and intercalation effects, recognises the minor groove of guanine–cytosine (G-C) rich sequences. Oxidative DNA damage also occurs in the minor groove and can be inhibited by superoxide and hydroxyl radical trapping agents. The complexes, particularly Cu-DPA-DPPZ, display promising anticancer activity against human pancreatic tumour cells with in-vitro results surpassing the clinical platinum(II) drug oxaliplatin.     

Structural Characterization of Graphene Nanosheets for Miniaturization of Potentiometric Urea Lipid Film Based Biosensors

The present article describes a miniaturized potentiometric urea lipid film based biosensor on graphene nanosheets. Structural characterization of graphene nanosheets for miniaturization of potentiometric urea lipid film based biosensors have been studied through atomic force microscopy (AFM) and transmission electron microscopy (TEM) measurements. UV‐Vis and Fourrier transform IR (FTIR) spectroscopy have been utilized to study the pre‐ and postconjugated surfaces of graphene nanosheets. The presented potentiometric urea biosensor exhibits good reproducibility, reusability, selectivity, rapid response times (～4 s), long shelf life and high sensitivity of ca. 70 mV/decade over the urea logarithmic concentration range from 1×10^?6 M to 1×10^?3 M.     

Efficient Synthesis of 2‐Aminothiazole‐4‐phenyl‐5‐acetamides via the Open Chain Tautomers of γ‐Keto Amides

A simple and efficient method is described for the synthesis of new functionalized 2‐aminothiazoles, the 2‐aminothiazole‐4‐phenyl‐5‐acetamides 5, in 67–96% yields based on an application of the Hantzsch synthesis. The method involves the reaction of thiourea with 3‐benzoyl‐3‐bromo‐propionamides 4 prepared from the corresponding 3‐benzoylpropionamides 3. The tautomeric structure of the γ‐keto amides 3 and 6 is directly related to the present study, because 2‐aminothiazoles 5 are readily obtained from the corresponding open chain γ‐keto amides 3.