Abstract Glycosaminoglycans are highly anionic functional polysaccharides with information content in their structure that plays a major role the communication between cell and extracellular environment. The study presented here reports label-free detection analysis of glycosaminoglycan molecules at single molecule level using sensing by biological nanopore, thus addressing need to decipher structural oligo- polysaccharide sequences, which remains challenge for glycoscience. We demonstrate...

Abstract Sequence‐defined oligourethanes were tested as in vivo taggants for implant identification. The oligomers prepared an orthogonal solid‐phase iterative approach and thus contained a coded monomer sequence that can be unequivocally identified by tandem mass spectrometry (MS/MS). then included small amounts (1 wt %) square‐centimeter‐sized crosslinked poly(vinyl alcohol) (PVA) model films, which intramuscularly subcutaneously implanted the abdomen of rats. After one week, month, or...

Abstract A three‐step post‐polymerization modification method was developed for the design of digitally encoded poly(phosphodiester)s with controllable side groups. Sequence‐defined precursors were synthesized, either manually on polystyrene resins or automatically controlled pore glass supports, using two phosphoramidite monomers containing terminal alkynes triisopropylsilyl (TIPS) protected alkyne Afterwards, these polymers modified by stepwise copper‐catalyzed azide–alkyne cycloaddition...

The shape of the spectral features in arrival time distributions (ATDs) recorded by ion mobility spectrometry (IMS) can often be interpreted terms coexistence different isomeric species. Interconversion between such species is also acknowledged to influence ATD, even if no general quantitative description this effect available. We present an analytical model that allows simulating ATDs resulting from interconverting This used reproduce experimental data obtained on a bistable system and...

We report a molecular design and concept using π-system elongation steric effects from helicenes surrounding triphenylene core toward stable chiral polycyclic aromatic hydrocarbons (PAHs) with maximal π-distortion to tackle their aromaticity, supramolecular properties. The selective syntheses, the structural, conformational chiroptical properties of two diastereomeric large multi-helicenes formula C90 H48 having embedding three [5]helicene units on inner edges [7]helicene at periphery are...

Digital polymers are uniform macromolecules that store monomer-based binary sequences. Molecularly stored information is usually extracted from the polymer by a tandem mass spectrometry (MS/MS) measurement, in which coded chains fragmented to reveal each bit (i.e. basic monomer unit) of sequence. Here, we show data-extraction can be greatly simplified favoring formation MS/MS fragments containing two bits instead one. In order do so, digital poly(alkoxyamine phosphodiester)s, dyads repeat...

Abstract Mixtures of uniform sequence‐defined oligourethanes are evaluated as 2D molecular barcodes for labeling three different commodity polymers, namely polystyrene, polyvinylchloride and polyethylene terephthalate. Six synthesized by solid‐phase iterative synthesis coded using a binary monomer alphabet. High‐resolution mass spectrometry studies indicate that all oligomers sequence‐defined. However, instead them individual chains, with chain‐length, sequence mixed into intentionally...

Digital polymers are monodisperse chains with a controlled sequence of co‐monomers, defined as letters an alphabet, and used to store information at the molecular level. Reading such messages is hence sequencing task that can be efficiently achieved by tandem mass spectrometry. To improve their readability, structure sequence‐controlled synthetic optimized, based on considerations regarding fragmentation behavior. This strategy described here for poly(phosphodiester)s, which were synthesized...

Microorganisms associated with termites are an original resource for identifying new chemical scaffolds or active metabolites. A molecular network was generated from a collection of strain extracts analyzed by liquid chromatography coupled to tandem high-resolution mass spectrometry, generated, and activities against the human pathogens methicillin-resistant Staphylococcus aureus, Candida albicans Trichophyton rubrum were mapped, leading selection single extract Penicillium sclerotiorum...

The aim of this work was to develop a reliable and efficient analytical method characterise differentiate saxitoxin analogues (STX), including sulphated (gonyautoxins, GTX) non-sulphated analogues. For purpose, hydrophilic interaction liquid chromatography (HILIC) used separate We also resorted ion mobility spectrometry the STX because technique adds new dimension separation based on gas phase conformation. Positive negative ionisation modes were for gonyautoxins while positive mode...

The use of sequence-defined polymers is an interesting emerging solution for materials identification and traceability. Indeed, a very large amount sequences can be created using limited alphabet coded monomers. However, in all reported studies, taggants are usually included host material by noncovalent adsorption or entrapment, which may lead to leakage, aggregation, degradation. To avoid these problems, covalently attached the present work mesh model materials, namely acrylamide hydrogels....

Chondroitin sulfate (CS) glycosaminoglycans are bioactive sulfated polysaccharides comprising repeating units of uronic acid and N-acetyl galactose at various positions. The optimal length sulfation pattern the CS sequences remain elusive so that structure-activity relationships cannot be easily established. Development efficient analytical methods allowing differentiation patterns is therefore particular importance to correlate their biological functions pattern.Discrimination different...

Abstract Für das Design informationstragender Polyphosphodiester mit kontrollierbar einzuführenden Seitenketten wurde eine dreistufige polymeranaloge Syntheseroute entwickelt. Durch Phosphoramidit‐Synthese wurden dazu entweder manuell auf Polystyrolharz oder automatisiert einer CPG‐Festphase Sequenzen definierter Primärstruktur als Vorstufe erhalten. Verwendet dabei zwei Monomere, die terminale Alkine analog Triisopropylsilyl (TIPS) geschützten Substituenten aufweisen. Derlei Polymere sind...

Abstract Digital polymers are uniform macromolecules that store monomer‐based binary sequences. Molecularly stored information is usually extracted from the polymer by a tandem mass spectrometry (MS/MS) measurement, in which coded chains fragmented to reveal each bit (i.e. basic monomer unit) of sequence. Here, we show data‐extraction can be greatly simplified favoring formation MS/MS fragments containing two bits instead one. In order do so, digital poly(alkoxyamine phosphodiester)s, dyads...

Abstract A photoregulated phosphoramidite iterative process is studied for the synthesis of non‐natural, digitally encoded oligo(phosphodiester)s. The oligomers are prepared using two reactive monomers containing a 2‐(2‐nitrophenyl)propoxycarbonyl (NPPOC) protected OH group. stepwise performed on an OH‐functional soluble polystyrene support, which allows recycling by precipitation in nonsolvent. Repeating cycles involving coupling, oxidation phosphite to phosphate, and NPPOC deprotection...

Abstract Sequence‐defined oligourethanes were tested as in vivo taggants for implant identification. The oligomers prepared an orthogonal solid‐phase iterative approach and thus contained a coded monomer sequence that can be unequivocally identified by tandem mass spectrometry (MS/MS). then included small amounts (1 wt %) square‐centimeter‐sized crosslinked poly(vinyl alcohol) (PVA) model films, which intramuscularly subcutaneously implanted the abdomen of rats. After one week, month, or...

Annonaceous acetogenins are natural products held responsible for atypical Parkinsonism due to chronic consumption in traditional medicine or as food, leading the development of analytical strategies their complete chemical characterization complex mixtures. Characterization by tandem mass spectrometry (MS/MS) using collision-induced dissociation from lithium adducts provides additional structural information compared protonated sodiated species such ketone location on acetogenin backbone....

Sequence-defined oligourethanes were transformed into ATRP initiators and used for the synthesis of precision macromolecular architectures.

Abstract The formation and characterization of K + Cs complexes originating from the cooperativity three non‐covalent interactions is explored. tridimensional preorganization naphthothiophene platform displays a favorable well‐defined bay region combining π fragment carbonyl moiety flanking central sulfur atom. A joint theoretical experimental infrared multiple photon dissociation (IRMPD) study allowed deciphering key contribution orthogonal phenyl to elaboration alkali metal complexes. In...

Abstract Kendrick mass defect (KMD) analysis is shown here to be a convenient method read binary messages encoded in the structure of two types sequence‐defined synthetic polymers, namely, polyurethanes and poly(alkoxyamine phosphodiester)s. KMD allows graphical ranking data obtained for species containing repeating units. This performed on MS/MS which distribution fragments reveals comonomer sequence digital macromolecules. Choosing one coding monomer as base unit, computation leads...

Liquid chromatography with UV detection and ion mobility-mass spectrometry are evaluated to study the <italic>E</italic> → <italic>Z</italic> thermal back relaxation kinetics of azobenzenes.