Bioinspired Underwater Adhesives by Using the Supramolecular Toolbox

Nature has developed protein-based adhesives whose underwater performance has attracted much research attention over the last few decades. The adhesive proteins are rich in catechols combined with amphiphilic and ionic features. This combination of features constitutes a supramolecular toolbox, to provide stimuli-responsive processing of the adhesive, to secure strong adhesion to a variety of surfaces, and to control the cohesive properties of the material. Here, the versatile interactions used in adhesives secreted by sandcastle worms and mussels are explored. These biological principles are then put in a broader perspective, and synthetic adhesive systems that are based on different types of supramolecular interactions are summarized. The variety and combinations of interactions that can be used in the design of new adhesive systems are highlighted

Temperature-Responsive Polyelectrolyte Complexes for Bio-Inspired Underwater Adhesives

Adhesive proteins of marine organisms contain significant amounts of hydrophobic amino acids. Therefore, inter- and intramolecular hydrophobic interactions are expected to play an important role in both adhesion and cohesion. Here, we mimic the hydrophobicity of adhesive proteins by using temperature-responsive polyelectrolyte complexes (TERPOCs) with a high poly(N-isopropylacrylamide) (PNIPAM) content. Upon mixing aqueous solutions of PNIPAM-b-poly(acrylic acid)-b-PNIPAM and poly(2-(dimethylamino) ethyl methacrylate) (PDMAEMA), complexation between the oppositely charged polyelectrolytes occurs. At low temperatures, complex coacervate core micelles (C3Ms) with a PNIPAM corona are formed, and upon a temperature increase, the solution turns into a hydrogel by the formation of a network of hydrophobic PNIPAM domains. Consequently, an abrupt increase in viscosity is observed upon heating which facilitates injectability of the adhesive. The gelation temperature, Tgel, and (adhesive) strength of the TERPOC can be adjusted by altering the salt and polymer concentration, which changes the balance between the electrostatic and hydrophobic interactions. Despite the importance of hydrophobic groups in strong underwater adhesives, we conclude that TERPOCs with a high PNIPAM content (70 wt%) are unstable due to water release. Consequently, there is a limited amount of hydrophobic groups that can be inserted in this type of systems. Nevertheless, TERPOCs show promising and tunable properties for application as injectable underwater adhesives, for example in biomedical applications

Rapid and Quantitative De-tert-butylation for Poly(acrylic acid) Block Copolymers and Influence on Relaxation of Thermoassociated Transient Networks

The synthesis of charged polymers often requires the polymerization of protected monomers, followed by a polymer-analogous reaction to the polyelectrolyte product. We present a mild, facile method to cleave tert-butyl groups from poly(tert-butyl acrylate) blocks that yields poly(acrylic acid) (pAA) blocks free of traces of the ester. The reaction utilizes a slight excess of HCl in hexafluoroisopropanol (HFIP) at room temperature and runs to completion within 4 h. We compare deprotection in HFIP with the common TFA/DCM method and show that the latter does not yield clean pAA. We show the effect of complete tert-butyl cleavage on a ABA triblock copolymer, where poly(N-isopropylacrylamide) (pNIPAM) is A and pAA is B, by means of viscosimetry, DLS, and SAXS on solutions above overlap. The pNIPAM blocks dehydrate, and their increased self-affinity above the lower critical solution temperature (LCST) results in network formation by the triblocks. This manifests itself as an increase in viscosity and a slowing down of the first-order correlation function in light scattering. However, this stickering effect manifests itself exclusively when the pAA block is tert-butyl-free. Additionally, SAXS shows that the conformational properties of tert-butyl-free pAA copolymers are markedly different from those with residual esters. Thus, we illustrate a surprising effect of hydrophobic impurities that act across blocks and assert the usefulness of HCl/HFIP in pAA synthesis

Molecular characteristics of carbapenemase-producing Enterobacterales in the Netherlands; results of the 2014–2018 national laboratory surveillance

Objectives: Carbapenem resistance mediated by mobile genetic elements has emerged worldwide and has become a major public health threat. To gain insight into the molecular epidemiology of carbapenem resistance in The Netherlands, Dutch medical microbiology laboratories are requested to submit suspected carbapenemase-producing Enterobacterales (CPE) to the National Institute for Public Health and the Environment as part of a national surveillance system. Methods: Meropenem MICs and species identification were confirmed by E-test and MALDI-TOF and carbapenemase production was assessed by the Carbapenem Inactivation Method. Of all submitted CPE, one species/carbapenemase gene combination per person per year was subjected to next-generation sequencing (NGS). Results: In total, 1838 unique isolates were received between 2014 and 2018, of which 892 were unique CPE isolates with NGS data available. The predominant CPE species were Klebsiella pneumoniae (n = 388, 43%), Escherichia coli (n = 264, 30%) and Enterobacter cloacae complex (n = 116, 13%). Various carbapenemase alleles of the same carbapenemase gene resulted in different susceptibilities to meropenem and this effect varied between species. Analyses of NGS data showed variation of prevalence of carbapenemase alleles over time with blaOXA-48 being predominant (38%, 336/892), followed by blaNDM-1 (16%, 145/892). For the first time in the Netherlands, blaOXA-181, blaOXA-232 and blaVIM-4 were detected. The genetic background of K. pneumoniae and E. coli isolates was highly diverse. Conclusions: The CPE population in the Netherlands is diverse, suggesting multiple introductions. The predominant carbapenemase alleles are blaOXA-48 and blaNDM-1. There was a clear association between species, carbapenemase allele and susceptibility to meropenem

National laboratory-based surveillance system for antimicrobial resistance: a successful tool to support the control of antimicrobial resistance in the Netherlands

An important cornerstone in the control of antimicrobial resistance (AMR) is a well-designed quantitative system for the surveillance of spread and temporal trends in AMR. Since 2008, the Dutch national AMR surveillance system, based on routine data from medical microbiological laboratories (MMLs), has developed into a successful tool to support the control of AMR in the Netherlands. It provides background information for policy making in public health and healthcare services, supports development of empirical antibiotic therapy guidelines and facilitates in-depth research. In addition, participation of the MMLs in the national AMR surveillance network has contributed to sharing of knowledge and quality improvement. A future improvement will be the implementation of a new semantic standard together with standardised data transfer, which will reduce errors in data handling and enable a more real-time surveillance. Furthermore, the

Bioinspired Underwater Adhesives by Using the Supramolecular Toolbox

Nature has developed protein-based adhesives whose underwater performance has attracted much research attention over the last few decades. The adhesive proteins are rich in catechols combined with amphiphilic and ionic features. This combination of features constitutes a supramolecular toolbox, to provide stimuli-responsive processing of the adhesive, to secure strong adhesion to a variety of surfaces, and to control the cohesive properties of the material. Here, the versatile interactions used in adhesives secreted by sandcastle worms and mussels are explored. These biological principles are then put in a broader perspective, and synthetic adhesive systems that are based on different types of supramolecular interactions are summarized. The variety and combinations of interactions that can be used in the design of new adhesive systems are highlighted

Rapid and quantitative de- tert-butylation for poly(acrylic acid) block copolymers and influence on relaxation of thermoassociated transient networks

\u3cp\u3eThe synthesis of charged polymers often requires the polymerization of protected monomers, followed by a polymer-analogous reaction to the polyelectrolyte product. We present a mild, facile method to cleave tert-butyl groups from poly(tert-butyl acrylate) blocks that yields poly(acrylic acid) (pAA) blocks free of traces of the ester. The reaction utilizes a slight excess of HCl in hexafluoroisopropanol (HFIP) at room temperature and runs to completion within 4 h. We compare deprotection in HFIP with the common TFA/DCM method and show that the latter does not yield clean pAA. We show the effect of complete tert-butyl cleavage on a ABA triblock copolymer, where poly(N-isopropylacrylamide) (pNIPAM) is A and pAA is B, by means of viscosimetry, DLS, and SAXS on solutions above overlap. The pNIPAM blocks dehydrate, and their increased self-affinity above the lower critical solution temperature (LCST) results in network formation by the triblocks. This manifests itself as an increase in viscosity and a slowing down of the first-order correlation function in light scattering. However, this stickering effect manifests itself exclusively when the pAA block is tert-butyl-free. Additionally, SAXS shows that the conformational properties of tert-butyl-free pAA copolymers are markedly different from those with residual esters. Thus, we illustrate a surprising effect of hydrophobic impurities that act across blocks and assert the usefulness of HCl/HFIP in pAA synthesis.\u3c/p\u3

In-flight calibration and monitoring of the Tropospheric Monitoring Instrument (TROPOMI) short-wave infrared (SWIR) module

During its first year in operation the shortwave infrared (SWIR) Tropospheric Monitoring Instrument (TROPOMI) was calibrated in-flight and its performance was monitored. In this paper we present the results of the in-flight calibration and the ongoing instrument monitoring. This includes the determination of the background signals, noise performance, instrument spectral response function (ISRF) stability, and stray-light stability. From these results, the number of incurred dead and bad pixels due to cosmic-ray impacts is determined. The light-path transmission is checked by monitoring internal lamp and diffuser stabilities. Due to its high sensitivity to Earth radiation on the eclipse side, the calibration strategy for the background (i.e. dark current and offset) monitoring was adjusted. Trends over the first full year of nominal operations reveal a very stable SWIR module. The number of newly incurred dead and bad pixels is less than 0.1% over nearly a full year since the start of operations. Assuming linear degradation of various components, the SWIR module is expected to keep performing within expected parameters for the full operational lifetime

Rapid and Quantitative De- tert-butylation for Poly(acrylic acid) Block Copolymers and Influence on Relaxation of Thermoassociated Transient Networks

The synthesis of charged polymers often requires the polymerization of protected monomers, followed by a polymer-analogous reaction to the polyelectrolyte product. We present a mild, facile method to cleave tert-butyl groups from poly(tert-butyl acrylate) blocks that yields poly(acrylic acid) (pAA) blocks free of traces of the ester. The reaction utilizes a slight excess of HCl in hexafluoroisopropanol (HFIP) at room temperature and runs to completion within 4 h. We compare deprotection in HFIP with the common TFA/DCM method and show that the latter does not yield clean pAA. We show the effect of complete tert-butyl cleavage on a ABA triblock copolymer, where poly(N-isopropylacrylamide) (pNIPAM) is A and pAA is B, by means of viscosimetry, DLS, and SAXS on solutions above overlap. The pNIPAM blocks dehydrate, and their increased self-affinity above the lower critical solution temperature (LCST) results in network formation by the triblocks. This manifests itself as an increase in viscosity and a slowing down of the first-order correlation function in light scattering. However, this stickering effect manifests itself exclusively when the pAA block is tert-butyl-free. Additionally, SAXS shows that the conformational properties of tert-butyl-free pAA copolymers are markedly different from those with residual esters. Thus, we illustrate a surprising effect of hydrophobic impurities that act across blocks and assert the usefulness of HCl/HFIP in pAA synthesis.</p

Self-assembly of oppositely charged polyelectrolyte block copolymers containing short thermoresponsive blocks

\u3cp\u3eThe assembly of oppositely charged block copolymers, containing small thermoresponsive moieties, was investigated as a function of salt concentration and temperature. Aqueous solutions of poly-[N-isopropylacrylamide]-b-poly[dimethylaminoethyl methacrylate] (NIPAM\u3csub\u3e44\u3c/sub\u3e-b-DMAEMA\u3csub\u3e216\u3c/sub\u3e) and PNIPAM-b-poly[acrylic acid]-b-PNIPAM (NIPAM\u3csub\u3e35\u3c/sub\u3e-b-AA\u3csub\u3e200\u3c/sub\u3e-b-NIPAM\u3csub\u3e35\u3c/sub\u3e) were mixed in equal charge stoichiometry, and analysed by light scattering (LS), NMR spectroscopy and small angle X-ray scattering (SAXS). At room temperature, two different micelle morphologies were found at different salt concentrations. At NaCl concentrations below 0.75 M, complex coacervate core micelles (C3M) with a PNIPAM corona were formed as a result of interpolyelectrolyte complexation. At NaCl concentrations exceeding 0.75 M, the C3M micelles inverted into PNIPAM cored micelles (PCM), containing a water soluble polyelectrolyte corona. This behavior is ascribed to the salt concentration dependence of both the lower critical solution temperature (LCST) of PNIPAM, and the complex coacervation. Above 0.75 M NaCl, the PNIPAM blocks are insoluble in water at room temperature, while complexation between the polyelectrolytes is prevented because of charge screening by the salt. Upon increasing the temperature, both types of micelles display a cloud point temperature (T\u3csub\u3ecp\u3c/sub\u3e), despite the small thermoresponsive blocks, and aggregate into hydrogels. These hydrogels consist of a complexed polyelectrolyte matrix with microphase separated PNIPAM domains. Controlling the morphology and aggregation of temperature sensitive polyelectrolytes can be an important tool for drug delivery systems, or the application and hardening of underwater glues.\u3c/p\u3