Masked alkynes for synthesis of threaded carbon chains

Polyynes are chains of sp1 carbon atoms with alternating single and triple bonds. As they become longer, they evolve towards carbyne, the 1D allotrope of carbon, and they become increasingly unstable. It has been anticipated that long polyynes could be stabilized by supramolecular encapsulation, by threading them through macrocycles to form polyrotaxanes—but, until now, polyyne polyrotaxanes with many threaded macrocycles have been synthetically inaccessible. Here we show that masked alkynes, in which the C≡C triple bond is temporarily coordinated to cobalt, can be used to synthesize polyrotaxanes, up to the C68 [5]rotaxane with 34 contiguous triple bonds and four threaded macrocycles. This is the length regime at which the electronic properties of polyynes converge to those of carbyne. Cyclocarbons constitute a related family of molecular carbon allotropes, and cobalt-masked alkynes also provide a route to [3]catenanes and [5]catenanes built around cobalt complexes of cyclo[40]carbon and cyclo[80]carbon, respectively

Aggregation of one-dimensional wires: The case of long oligoynes

We show an unexpected aggregation phenomenon of a long oligoyne (Py[16]) with 16 contiguous triple bonds and endcapped with bulky 3,5-bi(3,5-bis-tert-butylphenyl)pyridine groups. Aggregation of 1D π-conjugated oligoyne chains is rare given the minimal π–π intermolecular interactions as well as its flexibility that works against self-assembly. In dilute solutions, the reversible aggregation of Py[16] initiates at low temperature in the range of 140–180 K, and is not observed for shorter oligoynes in this series. Cryogenic UV/Vis electronic absorption spectra and vibrational Raman spectra with different laser wavelength lines tuning from in-resonance to off-resonance conditions have been used to extract the vibrational features characterizing the monomer and aggregate species. Theoretical calculations complement the spectroscopic findings.Funding for open access charge: Universidad de Málaga / CBU

Generative Pretraining in Multimodality

We present Emu, a Transformer-based multimodal foundation model, which can seamlessly generate images and texts in multimodal context. This omnivore model can take in any single-modality or multimodal data input indiscriminately (e.g., interleaved image, text and video) through a one-model-for-all autoregressive training process. First, visual signals are encoded into embeddings, and together with text tokens form an interleaved input sequence. Emu is then end-to-end trained with a unified objective of classifying the next text token or regressing the next visual embedding in the multimodal sequence. This versatile multimodality empowers the exploration of diverse pretraining data sources at scale, such as videos with interleaved frames and text, webpages with interleaved images and text, as well as web-scale image-text pairs and video-text pairs. Emu can serve as a generalist multimodal interface for both image-to-text and text-to-image tasks, and supports in-context image and text generation. Across a broad range of zero-shot/few-shot tasks including image captioning, visual question answering, video question answering and text-to-image generation, Emu demonstrates superb performance compared to state-of-the-art large multimodal models. Extended capabilities such as multimodal assistants via instruction tuning are also demonstrated with impressive performance.Comment: Code and Demo: https://github.com/baaivision/Em

The odd-number cyclo[13]carbon and its dimer, cyclo[26]carbon

Molecular rings of N carbon atoms (cyclo[N]carbons, or CN) are excellent benchmarking systems for testing quantum chemical theoretical methods and valuable precursors to other carbon-rich materials. Odd-N cyclocarbons, which have been elusive to date, are predicted to be even less stable than even-N cyclocarbons. We report the on-surface synthesis of cyclo[13]carbon, C13, by manipulation of decachlorofluorene with a scanning probe microscope tip. We elucidated the properties of C13 by experiment and theoretical modeling. C13 adopts an open-shell configuration with a triplet ground state and a kinked geometry, which shows different extents of distortion and carbene localization depending on the molecular environment. Moreover, we prepared and characterized the C13 dimer, cyclo[26]carbon, demonstrating the potential of cyclocarbons and their precursors as building blocks for carbon allotropes

On-surface synthesis of a doubly anti-aromatic carbon allotrope

Synthetic carbon allotropes such as graphene, carbon nanotubes and fullerenes have revolutionized materials science and led to new technologies. Many hypothetical carbon allotropes have been discussed, but few have been studied experimentally. Recently, unconventional synthetic strategies such as dynamic covalent chemistry and on-surface synthesis have been used to create new forms of carbon, including γ-graphyne, fullerene polymers, biphenylene networks and cyclocarbons. Cyclo[N]carbons are molecular rings consisting of N carbon atoms; the three that have been reported to date (N = 10, 14 and 18) are doubly aromatic, which prompts the question: is it possible to prepare doubly anti-aromatic versions? Here we report the synthesis and characterization of an anti-aromatic carbon allotrope, cyclo[16]carbon, by using tip-induced on-surface chemistry. In addition to structural information from atomic force microscopy, we probed its electronic structure by recording orbital density maps with scanning tunnelling microscopy. The observation of bond-length alternation in cyclo[16]carbon confirms its double anti-aromaticity, in concordance with theory. The simple structure of C16 renders it an interesting model system for studying the limits of aromaticity, and its high reactivity makes it a promising precursor to novel carbon allotropes

Advances in Polyynes to Model Carbyne

ConspectusThe formation and study of molecules that model the sp-hybridized carbon allotrope, carbyne, is a challenging field of synthetic physical organic chemistry. The target molecules, oligo- and polyynes, are often the preferred candidates as models for carbyne because they can be formed with monodisperse lengths as well as defined structures. Despite a simple linear structure, the synthesis of polyynes is often far from straightforward, due in large part to a highly conjugated framework that can render both precursors and products highly reactive, i.e., kinetically unstable. The vast majority of polyynes are formed as symmetrical products from terminal alkynes as precursors via an oxidative, acetylenic homocoupling reaction based on the Glaser, Eglinton–Galbraith, and Hay reactions. These reactions are very efficient for the synthesis of shorter polyynes (e.g., hexaynes and octaynes), but yields often drop dramatically as a function of length for longer derivatives, usually starting with the formation of decaynes. The most effective approach to circumvent unstable precursors and products has been through the incorporation of sterically demanding end groups that serve to “protect” the polyyne skeleton. This approach was arguably identified in the early 1950s by Bohlmann and co-workers with the synthesis of tBu-end-capped polyynes. During the next 50 years, a polyyne with 14 contiguous alkyne units remained the longest isolated derivative until 2010, when the record was extended to 22 alkyne units. The record length was broken again in 2020, when a polyyne consisting of 24 alkynes was isolated and characterized. Beyond polyynes, there have been several reports describing the potential synthesis of carbyne, but conclusive characterization and proof of structure have been tenuous. The sole example of synthetic carbyne arises from synthesis within carbon nanotubes, when chains of thousands of sp carbon atoms have been linked to form polydisperse samples of carbyne. Thus, model compounds for carbyne, the polyynes, remain the best means to examine and predict the experimental structure and properties of this carbon allotrope.This Account will discuss the general synthesis of polyynes using homologous series of polyynes with up to 10 alkyne units as examples (decaynes). The limited number of specific syntheses of series with longer polyynes will then be presented and discussed in more detail based on end groups. The monodisperse polyynes produced from these synthetic efforts are then examined toward providing our best extrapolations for the expected characteristics for carbyne based on 13C NMR spectroscopy, UV–vis spectroscopy, X-ray crystallography, and Raman spectroscopy

GSK3:a key target for the development of novel treatments for type 2 diabetes mellitus and Alzheimer disease

As a constitutively active kinase, glycogen synthase kinase 3 (GSK3) is a kinase which regulates body metabolism by phosphorylation of glycogen synthase (GS) and other substrates. Considerable evidence suggests that GSK3 is involved in the common pathology underlying Alzheimer's disease (AD) and type 2 diabetes mellitus (T2DM). The overexpression or overactivation of GSK3 could induce a series of pathological changes, most of which are hallmarks of AD and T2DM. Therefore, GSK3 could be a novel target to treat these two age-dependent diseases. The inhibition of this kinase can prevent the aggregation of β-amyloid (Aβ) and hyperphosphorylation of tau protein. GSK3 inhibition can also be a promising strategy to ameliorate neurodegenerative developments. Its potential association with memory formation has been shown in electrophysiological and behavioral experiments. The neuroprotective effects of novel drugs developed to treat T2DM, glucagon-like peptide 1 (GLP-1) and its long-lasting analogs, have a possible link to GSK3 modification. Recent investigations of the interaction between the phosphatidylinositol 3 kinase (PI3K) signaling pathway and the protective effect of novel GPL-1 receptor agonist geniposide on PC12 cells support this theory

New animal models of Alzheimer's disease that display insulin desensitization in the brain

Abstract Alzheimer's disease (AD) is a complex neurodegenerative disorder, which involves many underlying pathological processes. Recently, it has been demonstrated that AD also includes impairments of insulin signaling in the brain. Type 2 diabetes is a risk factor for AD, and AD and diabetes share a number of pathologies. The classical hallmarks of AD are senile plaques and neurofibrillary tangles, which consist of amyloid-β and hyperphosphorylated tau. Based on the two hallmarks, transgenic animal models of AD have been developed, which express mutant human genes of amyloid precursor protein, presenilin-1/2, and tau. It is likely that these mouse models are too limited in their pathology. In this work, we describe mouse models that model diabetes and show insulin signaling impairment as well as neurodegenerative pathologies that are similar to those seen in the brains of AD patients. The combination of traditional AD mouse models with induced insulin impairments in the brain may be a more complete model of AD. Interestingly, AD mouse models treated with drugs that have been developed to cure type 2 diabetes have shown impressive outcomes. Based on these findings, several ongoing clinical trials are testing long lasting insulin analogues or GLP-1 mimetics in patients with AD

Masked alkynes for synthesis of threaded carbon chains

Polyynes are chains of sp1 carbon atoms with alternating single and triple bonds. As they become longer, they evolve towards carbyne, the 1D allotrope of carbon, and they become increasingly unstable. It has been anticipated that long polyynes could be stabilized by supramolecular encapsulation, by threading them through macrocycles to form polyrotaxanes, but, until now, polyyne polyrotaxanes with many threaded macrocycles have been synthetically inaccessible. Here we show that masked alkynes, in which the CC triple bond is temporarily coordinated to cobalt, can be used to synthesize polyrotaxanes, up to the C68 [5]rotaxane with 34 contiguous triple bonds and four threaded macrocycles. This is the length regime at which the electronic properties of polyynes converge to those of carbyne. Cyclocarbons constitute a related family of molecular carbon allotropes, and cobalt-masked alkynes also provide a route to [3] and [5]catenanes built around cyclo[40]carbon and cyclo[80]carbon, respectively

Singlet Fission in Enantiomerically Pure Pentacene Dimers

Singlet fission (SF), that is, producing two triplet excited states (T1+T1) from a single singlet excited state (S1S0), has the potential to surpass the thermodynamic Shockley–Queisser limit for solar cells of 33 %. Of great relevance for singlet fission is the (S1S0)‐to‐1(T1T1) transformation as it is the key step in driving the efficiency of SF. In the current study, we focus on the control over intramolecular interactions in enantiomerically pure platinum linked pentacene dimers, (S,S)‐ and (R,R)‐cis‐Pt. Despite the internal heavy‐atom effect stemming from the presence of the Pt‐centered linkers, (S,S)‐ and (R,R)‐cis‐Pt undergo quantitative and solvent dependent formation of 1(T1T1). Implicit is an enantiomer‐independent SF mediation by means of a virtual CT intermediate in a superexchange mechanism. With the help of steady‐state and time‐resolved spectroscopic techniques, a kinetic model is developed to describe the entire deactivation pathway following photoexcitation of (S,S)‐ and (R,R)‐cis‐Pt