Solid-State Glass Nanopipette: Modification and Application
Chemistry. 2024 Mar 20:e202400281. doi: 10.1002/chem.202400281. Online ahead of print.ABSTRACTSolid-state glass nanopipettes provide a promising confined space that offers several advantages such as controllable size, simple preparation, low cost, good mechanical stability, and good thermal stability. These advantages make them an ideal choice for various applications such as biosensors, DNA sequencing, and drug delivery. In this review, we first delve into the functionalized nanopipettes for sensing various analytes and the methods used to develop detection means with them. Next, we provide an in-depth overview of the adv...
Source: Chemistry - March 20, 2024 Category: Chemistry Authors: Hao Wang Haoran Tang Xia Qiu Yongxin Li Source Type: research

Tandem Electrochemical Oxidation of Polycyclic Aromatic Amines Towards Carbazoles and Phenazine-based Aza-helicenes
Chemistry. 2024 Mar 20:e202400614. doi: 10.1002/chem.202400614. Online ahead of print.ABSTRACTExperimental and theoretical study of the regioselectivity and mechanism of polycyclic aromatic amine (PAA) electrochemical oxidation is important for designing nitrogen doped large π-conjugated functional molecules. Herein, we used binary-, ternary-, and quaternary-fused PAAs as electro-oxidative reaction substrates to investigate the yield changes of carbazole and phenazine based aza-helicene other than oligomers, which were obtained through pyrrole and pyrazine annulation pathways. Combined with the restrained electrostatic po...
Source: Chemistry - March 20, 2024 Category: Chemistry Authors: Boning Yan Ming Lei Zefeng Tang Hengyi Liao Kang Xu Source Type: research

64 Cu tumor labeling with hexadentate picolinic acid-based bispidine immunoconjugates
Chemistry. 2024 Mar 20:e202400366. doi: 10.1002/chem.202400366. Online ahead of print.ABSTRACTDiscussed are two picolinate appended bispidine ligands (3,7-diazabicyclo[3.3.1]nonane derivatives) in comparison with an earlier described bis-pyridine derivative, which are all known to strongly bind CuII. The radiopharmacological characterization of the two isomeric bispidine complexes includes quantitative labeling with 64CuII at ambient conditions with high radiochemical purities and yields (molar activities > 200 MBq/nmol). Challenge experiments in presence of EDTA, cyclam, human serum and SOD demonstrate high stability a...
Source: Chemistry - March 20, 2024 Category: Chemistry Authors: Manja Kubeil Christin Neuber Miriam Starke Claudia Arndt Liliana R Loureiro Lydia Hoffmann Anja Feldmann Michael Bachmann Jens Pietzsch Peter Comba Holger Stephan Source Type: research

A pH-Sensitive Double Chromophore Fluorescent Dye for  Live-Tracking of Lipophagy
In this study, we describe the development of a lipophilic dye containing two fluorophores, one of which is pH-sensitive and the other pH-stable. We further demonstrate that this "Lipo-Fluddy" can be used to visualize and quantify lipophagy in living cells, in an easily applicable and protein label-free approach. After estimating the ability of compound candidates to penetrate LDs, we synthesized several BODIPY and (pH-switchable) rhodol dyes, whose fluorescence properties (incl. their photophysical compatibility) were analyzed. Of three Lipo-Fluddy dyes synthesized, one exhibited the desired properties and allowed observa...
Source: Chemistry - March 20, 2024 Category: Chemistry Authors: Pascal M Engelhardt Matteo Veronese Alpay A Eryigit Anushka Das Alexander T Kaczmarek Elena I Rugarli Hans-G ünther Schmalz Source Type: research

Fingerprints of Chalcogen Bonding Revealed Through 77Se-NMR
Chemistry. 2024 Mar 20:e202400385. doi: 10.1002/chem.202400385. Online ahead of print.ABSTRACT77Se-NMR is used to characterise several chalcogen bonded complexes of derivatives of the organoselenium drug ebselen, exploring a range of electron demand. NMR titration experiments support the intuitive understanding that chalcogen bond donors bearing more electron withdrawing substituents give rise stronger chalcogen bonds. The chemical shift of the selenium nucleus is also shown to move upfield as it participates in a chalcogen bond. Solid-state NMR is used to explore chalcogen bonding in co-crystals. Due to the lack of molec...
Source: Chemistry - March 20, 2024 Category: Chemistry Authors: Thomas Fellowes Marc Antoine Sani Jonathan White Source Type: research

Predisposition in Dynamic Covalent Chemistry: The Role of Non-Covalent Interactions in the Assembly of Tetrahedral Boronate Cages
This study explores these challenges by synthesizing boronic acid tripods with varied oxygen positions at the tripodal feet and investigating their role in assembling tetrahedral boronate MOCs. Our results reveal substantial differences in the assembly efficiency among tripods. While the building blocks with oxygen in the benzylic position relative to the central aromatic ring form the MOCs in high yields, those with the oxygen atom directly bound to the central aromatic ring, only yield traces. Through X-ray crystallography and DFT analyses, we elucidate how intramolecular interactions profoundly influence the geometry of...
Source: Chemistry - March 20, 2024 Category: Chemistry Authors: Manuel Rondelli Jorge Pas án Israel Fern ández Tom ás Martín Source Type: research

Scaffold-Oriented Asymmetric Catalysis: Conformational Modulation of Transition State Multivalency during a Catalyst-Controlled Assembly of a Pharmaceutically Relevant Atropisomer
Chemistry. 2024 Mar 20:e202401109. doi: 10.1002/chem.202401109. Online ahead of print.ABSTRACTA new class of superbasic, bifunctional peptidyl guanidine catalysts is presented, which enables the organocatalytic, atroposelective synthesis of axially chiral quinazolinediones. Computational modeling unveiled the conformational modulation of the catalyst by a novel phenyl urea N-cap, that preorganizes the structure into the active, folded state. A previously unanticipated noncovalent interaction involving a difluoroacetamide acting as a hybrid mono- or bidentate hydrogen bond donor emerged as a decisive control element inducin...
Source: Chemistry - March 20, 2024 Category: Chemistry Authors: Nicol ò Tampellini Brandon Mercado Scott J Miller Source Type: research

Solid-State Glass Nanopipette: Modification and Application
Chemistry. 2024 Mar 20:e202400281. doi: 10.1002/chem.202400281. Online ahead of print.ABSTRACTSolid-state glass nanopipettes provide a promising confined space that offers several advantages such as controllable size, simple preparation, low cost, good mechanical stability, and good thermal stability. These advantages make them an ideal choice for various applications such as biosensors, DNA sequencing, and drug delivery. In this review, we first delve into the functionalized nanopipettes for sensing various analytes and the methods used to develop detection means with them. Next, we provide an in-depth overview of the adv...
Source: Chemistry - March 20, 2024 Category: Chemistry Authors: Hao Wang Haoran Tang Xia Qiu Yongxin Li Source Type: research

Unravelling the Role of Free Radicals in Photocatalysis
Chemistry. 2024 Mar 19:e202400001. doi: 10.1002/chem.202400001. Online ahead of print.ABSTRACTFree radicals are increasingly recognized as active intermediate reactive species that can participate in various redox processes, significantly influencing the mechanistic pathways of reactions. Numerous researchers have investigated the generation of one or more distinct photogenerated radicals, proposing various hypotheses to explain the reaction mechanisms. Notably, recent research has demonstrated the emergence of photogenerated radicals in innovative processes, including organic chemical reactions and the photocatalytic diss...
Source: Chemistry - March 19, 2024 Category: Chemistry Authors: Yao Chen Shuyang Xu Chun Fang Wen Hanyun Zhang Ting Zhang Fujian Lv Yinghong Yue Zhenfeng Bian Source Type: research

From Criegee to Breslow: How π-Donors Steer the Route of Olefin Ozonolysis
Chemistry. 2024 Mar 19:e202400026. doi: 10.1002/chem.202400026. Online ahead of print.ABSTRACTWhile π-bonds typically undergo cycloaddition with ozone, resulting in the release of much-noticed carbonyl O-oxide Criegee intermediates, lone-pairs of electrons tend to selectively accept a single oxygen atom from O3, producing singlet dioxygen. We questioned whether the introduction of potent electron-donating groups, akin to N-heterocyclic olefins, could influence the reactivity of double bonds - shifting from cycloaddition to oxygen atom transfer or generating lesser-known, yet stabilized, donor-substituted Criegee intermedi...
Source: Chemistry - March 19, 2024 Category: Chemistry Authors: Serhii Medvedko Jan Philipp Wagner Source Type: research

Bimodal glycosyl donors as an emerging approach towards a general glycosylation strategy
Chemistry. 2024 Mar 19:e202400399. doi: 10.1002/chem.202400399. Online ahead of print.ABSTRACTOrganic synthesis provides an accessible route to preparative scale biological glycans, although schemes to access these complex structures are often complicated by preparation of multiple monosaccharide building blocks. Bimodal glycosyl donors capable of forming both α- and β-anomers selectively, are an emerging tactic to reduce the required number of individual synthetic components in glycan construction. This review discusses examples of bimodal donors in the literature, and how they achieve their stereocontrol for both anome...
Source: Chemistry - March 19, 2024 Category: Chemistry Authors: Matthew E Warnes Martin Anthony Fascione Source Type: research

Interfacial Bonding Induced Charge Transfer in Two-dimensional Amorphous MoO3-x/Graphdiyne Oxide Non-van der Waals Heterostructures for Dominant SERS Enhancement
Chemistry. 2024 Mar 19:e202400227. doi: 10.1002/chem.202400227. Online ahead of print.ABSTRACTTwo-dimensional semiconductor-based nanomaterials have shown to be an effective substrate for Surface-enhanced Raman Scattering (SERS) spectroscopy. However, the enhancement factor (EF) tends to be relatively weak compared to that of noble metals and does not allow for trace detection of molecules. In this work, we report the successful preparation of two-dimensional (2D) amorphous non-van der Waals heterostructures MoO3-x/GDYO nanomaterials using supercritical CO2. Due to the synergistic effect of the localized surface plasmon re...
Source: Chemistry - March 19, 2024 Category: Chemistry Authors: Jian Yang Pengfei Yan Zongwei Chen Wei Liu Zhaoxi Liu Zijian Ma Qun Xu Source Type: research

Synthesis of Superbulky Amide Ligands by Addition of Polar Reagents to Sila-Imine
Chemistry. 2024 Mar 19:e202400715. doi: 10.1002/chem.202400715. Online ahead of print.ABSTRACTThe chemistry of extremely bulky amide ligands is troubled by difficulties in deprotonation of the parent amine. As an alternative route to superbulky amide reagents, the addition of polar reagents to a sila-imine has been investigated. Attempts to synthesize the superbulky amide anion (tBu3Si)2N- by addition of tBuLi to tBu2Si=N(SitBu3) failed and gave tBu3Si(tBu2HSi)NLi and isobutene. Reaction of the sila-imine with KOtBu successfully led to tBu3Si[tBu2(tBuO)Si]NK which crystallized as a separated ion-pair. Reaction with the sli...
Source: Chemistry - March 19, 2024 Category: Chemistry Authors: Christian Kn üpfer Lukas Klerner Michael Raucheisen Jens Langer Sjoerd Harder Source Type: research

The divalent lanthanoid triflates Ln(CF3SO3)2(CH3CN) (Ln = Sm, Eu): Structure, luminescence, and magnetism
Chemistry. 2024 Mar 19:e202400462. doi: 10.1002/chem.202400462. Online ahead of print.ABSTRACTThe reaction of the trivalent lanthanide triflates Ln(OTf)3 (Ln = Sm, Eu; OTf = CF3SO3-) with the respective metals in acetonitrile leads to the Ln(II)-triflates Eu(OTf)2(CH3CN) (monoclinic, P21/n, Z = 4, a = 1053.54(1), b = 610.28(5), c = 1946.92(2) pm, b = 98.611(4)) and Sm(OTf)2(CH3CN) (monoclinic, P21/n, Z = 4, a = 1054.41(4), b = 612.16(2), c = 1952.65(7) pm, b = 98.524(2)). The isotypic strontium compound Sr(OTf)2(CH3CN) (monoclinic, P21/n, Z = 4, a = 1056.39(5), b = 610.05(3), c = 1950.1(1) pm, b = 98.900(2)°) has been obt...
Source: Chemistry - March 19, 2024 Category: Chemistry Authors: Niko Flosbach Bertold Rasche Leonhard Rochels Sabrina Disch Claudia Wickleder Matthias Adlung Pia Fischer Mathias Wickleder Source Type: research

Genetically Fusing Order-Promoting and Thermoresponsive Building Blocks to Design Hybrid Biomaterials
Chemistry. 2024 Mar 19:e202400582. doi: 10.1002/chem.202400582. Online ahead of print.ABSTRACTThe unique biophysical and biochemical properties of intrinsically disordered proteins (IDPs) and their recombinant derivatives, intrinsically disordered protein polymers (IDPPs) offer opportunities for producing multistimuli-responsive materials; their sequence-encoded disorder and tendency for phase separation facilitate the development of multifunctional materials. This review highlights the strategies for enhancing the structural diversity of elastin-like polypeptides (ELPs) and resilin-like polypeptides (RLPs), and their self...
Source: Chemistry - March 19, 2024 Category: Chemistry Authors: Sai S Patkar Bin Wang Ana Maria Mosquera Kristi L Kiick Source Type: research