Engineering digital polymer based on thiol–maleimide Michael coupling toward effective writing and reading

Liu, Baolei; Shi, Qiunan; Hu, Lihua; Huang, Zhihao; Zhu, Xiulin; Zhang, Zhengbiao

doi:10.1039/c9py01939a

Cited by 39 publications

(45 citation statements)

References 47 publications

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“…To address this issue, the chemical structure of monomers can be optimized to decrease their MS/MS reactivity and hence lower the number of dissociation pathways per repeating unit. [ 13,14 ] Using this strategy, the longest chain read so far by MS/MS alone is a 77‐mer. [ 4 ] Increasing the number of encoded bits per monomer is another efficient strategy to enhance the storage capacity of a single chain.…”

Section: Introductionmentioning

confidence: 99%

Desorption Electrospray Ionization (DESI) of Digital Polymers: Direct Tandem Mass Spectrometry Decoding and Imaging from Materials Surfaces

Amalian

Mondal

Konishcheva

et al. 2021

Adv Materials Technologies

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Sequence‐defined synthetic polymers have recently emerged as an attractive medium to store information at the molecular level, where comonomers of the chains are defined as letters of an alphabet. The main read‐out methodology employed to retrieve such molecularly encoded information is tandem mass spectrometry (MS/MS), but a major current limitation remains the low storage capacity of readable chains. Ordering short oligomers at discrete locations onto surfaces to compose long messages is an attractive alternative to the difficult synthesis of long coded polymers. Yet, such surface storage requires a reliable sampling technique to be coupled on‐line with MS/MS. Because it combines fast surface extraction with efficient analyte ionization in ambient conditions, desorption electrospray ionization (DESI) is shown here to be perfectly suited to envisage bidimensional data storage. The present study demonstrates performances of DESI‐MS/MS at mapping oligomers used to write letters of a word, extracting digital labels from materials tagged for anticounterfeiting purposes, and imaging text written with coded polymeric inks.

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Section: Introductionmentioning

confidence: 99%

Desorption Electrospray Ionization (DESI) of Digital Polymers: Direct Tandem Mass Spectrometry Decoding and Imaging from Materials Surfaces

Amalian

Mondal

Konishcheva

et al. 2021

Adv Materials Technologies

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“…Such structural designs always aim at reducing the number of dissociation routes, in order to avoid signal dilution when dealing with long chains, while still enabling full sequence coverage. For this purpose, different strategies have been reported: removing reactive functions, [14] controlling the oxidation degree of specific atoms, [15] or introducing linkages of low dissociation energy to make any other bonds MS/MS silent [16] . The latter approach was successfully employed to decipher large amounts of information stored in sequence‐defined poly(phosphodiester)s using a routine mass spectrometer [17] .…”

Section: Introductionmentioning

confidence: 99%

Precise Alkoxyamine Design to Enable Automated Tandem Mass Spectrometry Sequencing of Digital Poly(phosphodiester)s

et al. 2020

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A major step towards reliable reading of information coded in the sequence of long poly(phosphodiester)s was previously achieved by introducing an alkoxyamine spacer between information sub‐segments. However, MS/MS decoding had to be performed manually to safely identify useful fragments of low abundance compared to side‐products from the amide‐based alkoxyamine used. Here, alternative alkoxyamines were designed to prevent side‐reactions and enable automated MS/MS sequencing. Different styryl‐TEMPO spacers were prepared to increase radical delocalization and stiffness of the structure. Their dissociation behavior was investigated by EPR and best results were obtained with spacers containing in‐chain benzyl ring, with no side‐reaction during synthesis or sequencing. Automated decoding of these polymers was performed using the MS‐DECODER software, which interprets fragmentation data recorded for each sub‐segment and re‐align them in their original order based on location tags.

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“…In order to capitalize on the robustness of the phosphoramidite used in the automated synthesis of long poly(phosphodiester)s, specific reagents were prepared to include alkoxyamine linkages in the final chains, the low bond dissociation energy of which makes all phosphate bonds MS/MS‐silent, lowering the number of product ion series from eight to two and hence ensuring full sequence coverage of long chains 15 . Similarly, Zhang and co‐workers recently showed that controlling the oxidation degree of sulfur atoms in the backbone of poly(succinimide thioester)s drastically enhances dissociation selectivity 16 . In addition to re‐engineering structures, fragmentation of synthetic polymers can also be manipulated by appropriate adjustments of experimental parameters in the ionization step.…”

Section: Introductionmentioning

confidence: 99%

Optimal conditions for tandem mass spectrometric sequencing of information‐containing nitrogen‐substituted polyurethanes

Charles

Mondal

Greff

et al. 2020

Rapid Comm Mass Spectrometry

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Rationale To prevent solubility issues faced with sequence‐defined polyurethanes, a new family of digital polyurethanes was conceived with the alkyl coding chain held by the carbamate nitrogen (N) atom and CH3 instead of OH as the ϖ termination. This led to different dissociation mechanisms that were explored prior to optimizing tandem mass spectrometric (MS/MS) sequencing. Methods N‐Substituted polyurethanes (N–R PUs) were dissolved in methanol and subjected to collision‐induced dissociation (CID) as deprotonated chains in the negative ion mode, and as ammonium and sodium adducts in the positive ion mode, using electrospray ionization (ESI) as the ionization technique. Their dissociation behavior was thoroughly investigated using a quadrupole time‐of‐flight (QTOF) instrument in order to provide accurate mass measurements to support proposed fragmentation mechanisms. Results While O–(CO) bonds were broken in N–H PUs, the CH2–O linkage between repeating units was cleaved upon CID of N–R PUs. This main process occurred either from deprotonated molecules or from cationized chains but was followed by different rearrangements, producing up to four product ion series. Yet, MS/MS spectra could be drastically simplified for precursor ions having their acidic α group methylated, as was found to spontaneously occur upon storage in methanol. Conclusions Using experimental conditions aimed at avoiding any reactive proton in precursor ions (no acidic end‐groups and alkali adduction), full coverage sequence of N–R PUs was successfully achieved with the single ion series observed in MS/MS, opening a promising perspective for reading large amounts of information stored in these dyad‐encoded polymers.

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Engineering digital polymer based on thiol–maleimide Michael coupling toward effective writing and reading

Abstract: Based on thiol–maleimide Michael coupling, a digital polymer allowing efficient message writing and reading was rationally designed.

Cited by 39 publications

References 47 publications

Desorption Electrospray Ionization (DESI) of Digital Polymers: Direct Tandem Mass Spectrometry Decoding and Imaging from Materials Surfaces

Desorption Electrospray Ionization (DESI) of Digital Polymers: Direct Tandem Mass Spectrometry Decoding and Imaging from Materials Surfaces

Precise Alkoxyamine Design to Enable Automated Tandem Mass Spectrometry Sequencing of Digital Poly(phosphodiester)s

Optimal conditions for tandem mass spectrometric sequencing of information‐containing nitrogen‐substituted polyurethanes

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