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Abstract Background Efavirenz is the preferred non-nucleoside reverse transcriptase inhibitor for first-line antiretroviral treatment in many countries. For women of childbearing potential, advantages of efavirenz are balanced by concerns that it is teratogenic. This paper reviews evidence of efavirenz teratogenicity and considers implications in common clinical scenarios. Findings Concerns of efavirenz-induced fetal effects stem from animal studies, although the predictive value of animal data for humans is unknown. Four retrospective cases of central nervous system birth defects in infants with first trimester exposure to efavirenz have been interpreted as being consistent with animal data. In a prospective pregnancy registry, which is subject to fewer potential biases, no increase was detected in overall risk of birth defects following exposure to efavirenz in the first-trimester. Discussion For women planning a pregnancy or not using contraception, efavirenz should be avoided if alternatives are available. According to WHO guidelines for resource-constrained settings, benefits of efavirenz are likely to outweigh risks for women using contraception. Women who become pregnant while receiving efavirenz often consider drug substitution or temporarily suspending treatment. Both options have substantial risks for maternal and fetal health which, we argue, appear unjustified after the critical period of organogenesis (3–8 weeks post-conception). Efavirenz-based triple regimens, initiated after the first trimester of pregnancy and discontinued after childbirth, are potentially an important alternative for reducing mother-to-child transmission in pregnant women who do not yet require antiretroviral treatment. Conclusion Current recommendations for care for women who become pregnant while receiving efavirenz may need to be re-considered, particularly in settings with limited alternative drugs and laboratory monitoring. With current data limitations, additional adequately powered prospective studies are needed.

In the present work, we have used classical molecular dynamics and quantum mechanical density functional theory modeling to investigate the grain size-dependent thermal expansion coefficient (CTE) of nanocrystalline Cu. We find that the CTE increases by up to 20% with a gradually decreasing grain size. This behavior emerges as a result of the increased population of occupied anti-bonding states and bond order variation in the grain boundary regions, which contribute to the reduced resistance against thermally-induced bond stretching and dictate the thermal expansion behavior in the small grain size limit. As a part of the present work, we have established a procedure to produce ab initio thermal expansion maps that can be used for the prediction of the grain size-dependent CTE. This can serve as a modeling tool, e.g., to explore the impact of grain boundary impurity segregation on the CTE.

A new class of perylene bisimide (PBI) derivatives is introduced by bridging 1,12- and 1,6,7,12-hydroxy functionalized bay positions with oxygen-carbon-oxygen linker(s). This functionalization rigidifies the inherently twisted bay-substituted perylene core to afford dyes of high stability and solubility that are characterized by vibronically well-resolved absorption and fluorescence spectra and intense yellow emission with quantum yields close to 100%.

Dye arrays from dimers up to larger oligomers constitute the functional units of natural light harvesting systems as well as organic photonic and photovoltaic materials. Whilst in the past decades many photophysical studies were devoted to molecular dimers for deriving structure-property relationship to unravel the design principles for ideal optoelectronic materials, they fail to accomplish the subsequent processes of charge carrier generation or the detachment of two triplet species in singlet fission (SF). Here, we present a slip-stacked perylene bisimide trimer, which constitutes a bridge between hitherto studied dimer and solid-state materials, to investigate SF mechanisms. This work showcases multiple pathways towards the multiexciton state through direct or excimer-mediated mechanisms by depending upon interchromophoric interaction. These results suggest the comprehensive role of the exciton coupling, exciton delocalization, and excimer state to facilitate the SF process. In this regard, our observations expand the fundamental understanding the structure-property relationship in dye arrays., (© 2022. The Author(s).)

A series of donor-acceptor (D-A) macrocyclic dyads consisting of an electron-poor perylene bisimide (PBI) π-scaffold bridged with electron-rich α-oligothiophenes bearing four, five, six and seven thiophene units between the two phenyl-imide substituents has been synthesized and characterized by steady-state UV/Vis absorption and fluorescence spectroscopy, cyclic and differential pulse voltammetry as well as transient absorption spectroscopy. Tying the oligothiophene strands in a conformationally fixed macrocyclic arrangement leads to a more rigid π-scaffold with vibronic fine structure in the respective absorption spectra. Electrochemical analysis disclosed charged state properties in solution which are strongly dependent on the degree of rigidification within the individual macrocycle. Investigation of the excited state dynamics revealed an oligothiophene bridge size-dependent fast charge transfer process for the macrocyclic dyads upon PBI subunit excitation., (© 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Enantioselective molecular recognition of chiral molecules that lack specific interaction sites for hydrogen bonding or Lewis acid-base interactions remains challenging. Here we introduce the concept of tailored chiral π-surfaces toward the maximization of shape complementarity. As we demonstrate for helicenes it is indeed possible by pure van-der-Waals interactions (π-π interactions and CH-π interactions) to accomplish enantioselective binding. This is shown for a novel benzo[ghi]perylene trisimide (BPTI) receptor whose π-scaffold is contorted into a chiral plane by functionalization with 1,1'-bi-2-naphthol (BINOL). Complexation experiments of enantiopure (P)-BPTI with (P)- and (M)-[6]helicene afforded binding constants of 10 700 M -1 and 550 M -1 , respectively, thereby demonstrating the pronounced enantiodifferentiation by the homochiral π-scaffold of the BPTI host. The enantioselective recognition is even observable by the naked eye due to a specific exciplex-type emission originating from the interacting homochiral π-scaffolds of electron-rich [6]helicene and electron-poor BPTI., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Deracemization describes the conversion of a racemic mixture of a chiral molecule into an enantioenriched mixture or an enantiopure compound without structural modifications. Herein, we report an inherently chiral perylene bisimide (PBI) cyclophane whose chiral pocket is capable of transforming a racemic mixture of [5]-helicene into an enantioenriched mixture with an enantiomeric excess of 66 %. UV/Vis and fluorescence titration studies reveal this cyclophane host composed of two helically twisted PBI dyes has high binding affinities for the respective homochiral carbohelicene guests, with outstanding binding constants of up to 3.9×10 10  m -1 for [4]-helicene. 2D NMR studies and single-crystal X-ray analysis demonstrate that the observed strong and enantioselective binding of homochiral carbohelicenes and the successful template-catalyzed deracemization of [5]-helicene can be explained by the enzyme-like perfect shape complementarity of the macrocyclic supramolecular host., (© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

A highly sensitive short-wave infrared (SWIR, λ > 1000 nm) organic photodiode (OPD) is described based on a well-organized nanocrystalline bulk-heterojunction (BHJ) active layer composed of a dicyanovinyl-functionalized squaraine dye (SQ-H) donor material in combination with PC 61 BM. Through thermal annealing, dipolar SQ-H chromophores self-assemble in a nanoscale structure with intermolecular charge transfer mediated coupling, resulting in a redshifted and narrow absorption band at 1040 nm as well as enhanced charge carrier mobility. The optimized OPD exhibits an external quantum efficiency (EQE) of 12.3% and a full-width at half-maximum of only 85 nm (815 cm -1 ) at 1050 nm under 0 V, which is the first efficient SWIR OPD based on J-type aggregates. Photoplethysmography application for heart-rate monitoring is successfully demonstrated on flexible substrates without applying reverse bias, indicating the potential of OPDs based on short-range coupled dye aggregates for low-power operating wearable applications., (© 2021 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Purpose of Review: This review focuses on the foundational evidence from the last two decades of lipid genetics research and describes the current status of data-driven approaches for transethnic GWAS, fine-mapping, transcriptome informed fine-mapping, and disease prediction., Recent Findings: Current lipid genetics research aims to understand the association mechanisms and clinical relevance of lipid loci as well as to capture population specific associations found in global ancestries. Recent genome-wide trans-ethnic association meta-analyses have identified 118 novel lipid loci reaching genome-wide significance. Gene-based burden tests of whole exome sequencing data have identified three genes-PCSK9, LDLR, and APOB-with significant rare variant burden associated with familial dyslipidemia. Transcriptome-wide association studies discovered five previously unreported lipid-associated loci. Additionally, the predictive power of genome-wide genetic risk scores amalgamating the polygenic determinants of lipid levels can potentially be used to increase the accuracy of coronary artery disease prediction., Conclusions: Lipids are one of the most successful group of traits in the era of genome-wide genetic discovery for identification of novel loci and plausible drug targets. However, a substantial fraction of lipid trait heritability remains unexplained. Further analysis of diverse ancestries and state of the art methods for association locus refinement could potentially reveal some of this missing heritability and increase the clinical application of the genomic association results.

Two types of helically chiral compounds bearing one and two boron atoms were synthesized by a modular approach. Formation of the helical scaffolds was executed by the introduction of boron to flexible biaryl and triaryl derived from small achiral building blocks. All-ortho-fused azabora[7]helicenes feature exceptional configurational stability, blue or green fluorescence with quantum yields (Φ fl ) of 18-24 % in solution, green or yellow solid-state emission (Φ fl up to 23 %), and strong chiroptical response with large dissymmetry factors of up to 1.12×10 -2 . Azabora[9]helicenes consisting of angularly and linearly fused rings are blue emitters exhibiting Φ fl of up to 47 % in CH 2 Cl 2 and 25 % in the solid state. As revealed by the DFT calculations, their P-M interconversion pathway is more complex than that of H1. Single-crystal X-ray analysis shows clear differences in the packing arrangement of methyl and phenyl derivatives. These molecules are proposed as primary structures of extended helices., (© 2020 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Open shell organic molecules bearing π-cores are of great interest for optical, electronic, and magnetic applications but frequently suffer fast decomposition or lack synthetic accessibility. In this regard, nitronyl nitroxides are promising candidates for stable (bi-)radicals due to their high degree of spin delocalization along the O-N-C-N-O pentad unit. Unfortunately, they are limited to electron-rich systems so far. To overcome this limitation, we developed a synthetic procedure for the twofold spin decoration of electron-poor chromophores ( E red = -1158 mV) with nitronyl nitroxide radical moieties via selective deprotection/oxidation of the respective silylated precursors with boron fluoride and subsequent quenching with tetraethyl orthosilicate. Nitronyl nitroxide biradicals PBI-NN, IIn-NN, PhDPP-NN, ThDPP-NN, and FuDPP-NN bridged by perylene bisimide (PBI), isoindigo (IIn), and diketopyrrolopyrrole (DPP) pigment colorants were finally obtained as bench stable compounds after periodate oxidation with yields of 60-81%. The absorption spectral signatures of the chromophores remain preserved in the open shell state and match the ones of the pristine parent compounds, which allowed an a priori prediction of their optical properties. Consequently, we achieved twofold spin labeling while keeping the intrinsic properties of the electron deficient chromophores intact.

The interactions between auxochromic groups in π-conjugated functional molecules dictate their electronic properties. From the standpoint of potential applications, understanding and control of such interactions is a vital requirement for the material design. In this communication, we describe the design, synthesis, and functional properties of a novel class of helically chiral diimide molecules, namely, [ n ]HDI-OMe ( n  = 5, 6, and 7), in which two imide units are connected via an [ n ]helicene skeleton. The experimental results supported by quantum chemical calculations reveal that the helical backbone in these molecules offers not only through-bond but also through-space conjugation between imide groups, which leads to distinct optical and electrochemical properties when compared to the related [ n ]helicenes and rylene diimides.

A series of four indolenine squaraines bearing a chiral center at the 3-position of the indolenine moiety, with either an n -propyl or a phenyl group alongside a methyl group, were synthesized and obtained in a high purity of ≥98% for the desired stereoisomer. The indolenine precursors with a phenyl group attached at the chiral center were asymmetrically synthesized using a pericyclic-reaction cascade and obtained in a high ee of 98%, whereas the ones with an n -propyl group were prepared by kinetic resolution through asymmetric hydrogenation, resulting in an ee of up to 98%. X-ray crystallography revealed a slightly twisted geometry for the phenyl-substituted cisoid squaraine derivative, whereas the n -propyl-substituted derivative possessed the expected planar geometry. Variation of the substitution also influenced the optical properties, where the introduction of phenyl groups caused a progressive red-shift and reduction in squared transition moments, as well as reduced fluorescence quantum yields, Stokes shifts, and fluorescence lifetimes. All of the investigated compounds exhibited strong ECD signals, with Δε values of up to 24 M -1 cm -1 for the HOMO-LUMO transition. DFT calculations indicated that this was due to both large electric and magnetic transition moments, although the two vectors were mutually almost orthogonal.

Future simulation and motivation are two strategies that might help children improve their induced-state episodic foresight. In Study 1, 3- to 5-year-old children ( N = 96) consumed pretzels (to induce thirst) and were asked what they would prefer the next day, pretzels or water. Children were randomly assigned to an experimental condition: (1) a standard thirsty condition, (2) an episodic simulation condition where they imagined being hungry the next day, (3) a motivation condition where children chose between a cupcake and water, or (4) a control condition (thirst was not induced). Future preferences did not differ by age and children were less likely to choose water (vs. a cupcake) in the motivation condition compared to the standard thirsty condition. Study 2 found that 3- to 5-year-old children ( N = 22) were also less likely to choose water for right now versus a cupcake when thirst was induced., (© 2020 Elsevier Inc. All rights reserved.)

The one-step reaction of a dicyanovinyl-functionalized squaric acid with Fischer bases afforded C2v symmetric squaraine dyes with rigid planar structures due to intramolecular N-HO hydrogen bonds. Dense molecular packing, decrease of HOMO level, and sufficient thermal stability for sublimation enabled vacuum-processed OTFTs with hole mobility up to 0.32 cm2 V-1 s-1 and current on/off ratio of 106.

We report the direct imidization of naphthalene and perylene dicarboxylic anhydrides/esters with bulky ortho,ortho-diaryl- and ortho,ortho-dialkynylaniline derivatives. This imidization method uses n-butyllithium as a strong base to increase the reactivity of bulky amine derivatives, proceeds under mild reaction conditions, requires only stoichiometric amounts of reactants and gives straightforward access to new sterically crowded rylene dicarboximides. Mechanistic investigations suggest an isoimide as intermediary product, which was converted to the corresponding imide upon addition of an aqueous base. Single-crystal X-ray diffraction analyses reveal dimeric packing motifs for monoimides, while two-side shielded bisimides crystallize in isolated molecules without close π-π-interactions. Spectroscopic investigations disclose the influence of the bulky substituents on the optical properties in the solid state., (© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

A trigonal-bipyramidal covalent organic cage compound serves as an efficient host to form stable 1 : 1-complexes with C 60 and C 70 . Fullerene encapsulation has been comprehensively studied by NMR and UV/Vis spectroscopy, mass spectrometry as well as single-crystal X-ray diffraction. Exohedral functionalization of encapsulated C 60 via threefold Prato reaction revealed high selectivity for the symmetry-matched all- trans -3 addition pattern., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Herein we report a broad series of new trinuclear supramolecular Ru(bda) macrocycles bearing different substituents at the axial or equatorial ligands which enabled investigation of substituent effects on the catalytic activities in chemical and photocatalytic water oxidation. Our detailed investigations revealed that the activities of these functionalized macrocycles in water oxidation are significantly affected by the position at which the substituents were introduced. Interestingly, this effect could not be explained based on the redox properties of the catalysts since these are not markedly influenced by the functionalization of the ligands. Instead, detailed investigations by X-ray crystal structure analysis and theoretical simulations showed that conformational changes imparted by the substituents are responsible for the variation of catalytic activities of the Ru macrocycles. For the first time, macrocyclic structure of this class of water oxidation catalysts is unequivocally confirmed and experimental indication for a hydrogen-bonded water network present in the cavity of the macrocycles is provided by crystal structure analysis. We ascribe the high catalytic efficiency of our Ru(bda) macrocycles to cooperative proton abstractions facilitated by such a network of preorganized water molecules in their cavity, which is reminiscent of catalytic activities of enzymes at active sites., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Herein, we have synthesized an enantiomerically pure propeller-shaped PAH, C 90 H 48 , possessing three [7]helicene and three [5]helicene subunits. This compound can be obtained in gram quantities in a straightforward manner. The photophysical and chiroptical properties were investigated using UV/Vis absorption and emission, optical rotation and circular dichroism spectroscopy, supported by DFT calculations. The nonlinear optical properties were investigated by two-photon absorption measurements using linearly and circularly polarized light. The extremely twisted structure and packing of the homochiral compound were investigated by single-crystal X-ray diffraction analysis., (© 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

Boron-doping has long been recognized as a promising LUMO energy-lowering modification of graphene and related polycyclic aromatic hydrocarbons (PAHs). Unfortunately, synthetic difficulties have been a significant bottleneck for the understanding, optimization, and application of precisely boron-doped PAHs for optoelectronic purposes. Herein, a facile one-pot hydroboration electrophilic borylation cascade/dehydrogenation approach from simple alkene precursors is coupled with postsynthetic B-substitution to give access to ten ambient-stable core- and periphery-tuned boron-doped PAHs. These include large hitherto unknown doubly boron-doped analogues of anthanthrene and triangulene. Crystallographic, optical, electrochemical, and computational studies were performed to clarify the effect of boron-doped PAH shape, size, and structure on optoelectronic properties. Our molecular tuning allowed the synthesis of molecules exhibiting visible-range absorption, near-unity fluorescence quantum yields, and, to our knowledge, the most facile electrochemical reductions of any reported ambient-stable boron-doped PAHs (corresponding to LUMO energy levels as low as fullerenes). Finally, our study describes the first implementation of a precise three-coordinate boron-substituted PAH as an acceptor material in organic solar cells with power conversion efficiencies (PCEs) of up to 3%.

A key issue for the application of π-conjugated organic molecules as thin film solid-state materials is the packing structure, which drastically affects optical and electronic properties due to intermolecular coupling. In this regard, merocyanine dyes usually pack in H-coupled antiparallel arrangements while structures with more interesting J-type coupling have been rarely reported. Here we show that for three highly dipolar merocyanine dyes, which exhibit the same π-scaffold and accordingly equal properties as monomers in solution, the solid-state packing can be changed by a simple variation of aliphatic substituents to afford narrow and intense absorption bands with huge hypsochromic (H) or bathochromic (J) shifts for their thin films and nanocrystals. Time-dependent density functional theory calculations show that the energetic offset of almost 1 eV magnitude results from distinct packing motifs within the crystal structures that comply with the archetype H- or J-aggregate structures as described by Kasha's exciton theory.

[60]Fullerene hexakisadducts possessing 12 carboxylic acid side chains form crystalline hydrogen-bonding frameworks in the solid state. Depending on the length of the linker between the reactive sites and the malonate units, the distance of the [60]fullerene nodes and thereby the spacing of the frameworks can be controlled and for the most elongated derivative, continuous channels are obtained within the structure. Stability, structural integrity and porosity of the material were investigated by powder X-ray diffraction, thermogravimetry and sorption measurements.

The introduction of one alkyne moiety at the central carbon atom of the tripodal tribenzotriquinacene scaffold allows easy access to a great variety of apically functionalized derivatives. The spatially well-separated arrangement of different functional units on the convex face and outer rim was further proven by single-crystal X-ray studies. Subsequent modifications that feature a general protecting group-free strategy for the demethylation of protected catechols in the presence of a terminal alkyne group, an azide-alkyne Huisgen cycloaddition, and Sonogashira cross-coupling reactions showcase the high synthetic potential of this modular approach for tribenzotriquinacene derivatization., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Modern spectroscopic techniques such as time-resolved second-harmonic-generation spectroscopy allow molecules to be examined selectively directly at phase interfaces. Two-phase systems formed by glycerol/water and alkane layers have previously been studied by time-resolved second-harmonic-generation spectroscopic measurements. In this molecular dynamics study, a triphenylmethane dye was inserted at the glycerol/water-alkane interface and was used as a probe for local properties such as viscosity. We now show how extensive simulations over a wide range of concentrations can be used to obtain a detailed view of the molecular structure at the glycerol/water-alkane interface. Glycerol is accumulated in a double layer adjacent to the alkane interface, which results in increased viscosity of the glycerol/water phase in the direct vicinity of the interface. We also show that conformational ensembles created by classical molecular-dynamics simulations can serve as input for QM/MM calculations, yielding further information such as transition dipoles, which can be compared with spectroscopic measurements.

The syntheses and comprehensive characterization of 14 organic semiconductors based on perylene bisimide (PBI) dyes that are equipped with up to four halogen substituents in the bay area of the perylene core and five different highly fluorinated imide substituents are described. The influence of the substituents on the LUMO level and the solid state packing of PBIs was examined by cyclic voltammetry and single crystal structure analyses of seven PBI derivatives, respectively. Top-contact/bottom-gate organic thin film transistor (OTFT) devices were constructed by vacuum deposition of these PBIs on SiO(2) gate dielectrics that had been pretreated with n-octadecyl triethoxysilane in vapor phase (OTS-V) or solution phase (OTS-S). The electrical characterization of all devices was accomplished in a nitrogen atmosphere as well as in air, and the structural features of thin films were explored by grazing incidence X-ray diffraction (GIXD) and atomic force microscopy (AFM). Several of those PBIs that bear only hydrogen or up to two fluorine substitutents at the concomitantly flat PBI core afforded excellent n-channel transistors, in particular, on OTS-S substrate and even in air (mu > 0.5 cm(2) V(-1) s(-1); I(on)/I(off) > 10(6)). The best OTFTs were obtained for 2,2,3,3,4,4,4-heptafluorobutyl-substituted PBI 1a ("PTCDI-C4F7") on OTS-S with n-channel field effect mobilities consistently >1 cm(2) V(-1) s(-1) and on-to-off current rations of 10(6) in a nitrogen atmosphere and in air. For distorted core-tetrahalogenated (fluorine, chlorine, or bromine) PBIs, less advantageous solid state packing properties were found and high performance OTFTs were obtained from only one tetrachlorinated derivative (2d on OTS-S). The excellent on-to-off current modulation combined with high mobility in air makes these PBIs suitable for a wide range of practical applications.