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Bio‐inspired approaches in materials science and systems chemistry are yielding a variety of stimuli‐responsive and dynamic materials that are gradually changing our everyday life. However, the ability to chemically program these materials to exhibit macroscopic higher‐order behaviours such as self‐assembly, contractility, swarming, taxis, chemical communication, or predator‐prey dynamics remains an ongoing challenge. While still in its infancy, the successful fabrication of bio‐inspired materials displaying higher‐order behaviours not only will help bridging the gap between living and non‐living matter, but it will also contribute to the development of advanced materials for potential applications ranging from tissue engineering and biotechnology, to soft robotics and regenerative medicine. Our Mini‐Review will systematically discuss the higher‐order behaviours developed thus far in bio‐inspired systems, namely (i) polymer networks (ii) microbots, (iii) protocells, and (iv) prototissues. For each system it will provide key examples and highlight how the emergent behaviour could be chemically programmed. [ABSTRACT FROM AUTHOR]

The achievement of light‐responsive behaviours is an important target for protocell engineering to allow control of fundamental protocellular processes such as communication via diffusible chemical signals, shape changes or even motility at the flick of a switch. As a step towards this ambitious goal, here we describe the synthesis of a novel poly(ethylene glycol)‐based crosslinker, reactive towards nucleophiles, that effectively degrades with UV light (405 nm). We demonstrate its utility for the fabrication of the first protocell membranes capable of light‐induced disassembly, for the photo‐generation of patterns of protocells, and for the modulation of protocell membrane permeability. Overall, our results not only open up new avenues towards the engineering of spatially organised, communicating networks of protocells, and of micro‐compartmentalised systems for information storage and release, but also have important implications for other research fields such as drug delivery and soft materials chemistry. [ABSTRACT FROM AUTHOR]

The bottom‐up fabrication of synthetic cells (protocells) from molecules and materials, is a major challenge of modern chemistry. A significant breakthrough has been the engineering of protocells capable of chemical communication using bio‐derived molecules and ex situ stabilised cell machineries. These, however, suffer from short shelf‐lives, high costs, and require mild aqueous conditions. In this Concept Article we analyse the chemistry at the heart of protocell communication to highlight new opportunities for synthetic chemists in protocell engineering. Specifically, we (i) categorise the main bio‐derived chemical communication machineries in enzyme cascades, DNA strand displacement, and gene‐mediated communication; (ii) review the chemistries of these signal transduction machineries; and (iii) introduce new types of bio‐inspired, fully synthetic artificial enzymes to replace their natural counterparts. Developing protocells that incorporate synthetic analogues of bio‐derived signal transduction machineries will improve the robustness, stability, and versatility of protocells, and broaden their applications to highly strategic fields such as photocatalysis and fine chemicals production. [ABSTRACT FROM AUTHOR]

Photocatalysis is an emerging field that exploits light‐absorbing catalysts to yield transformations not even achievable in the dark. Considering the drawbacks of metal‐based photocatalysts, Carbon Dots (CDs) recently emerged as suitable green alternatives for different photocatalytic reactions. These carbon nanoparticles are easy to prepare, non‐toxic and potentially recyclable. Moreover, CDs usually display core‐shell structures which are highly tunable via synthetic and post‐synthetic strategies. This Concept Article focuses on the recent advancements in the CD‐based photocatalysis, highlighting the link between their superficial and core composition and their resulting photo‐redox abilities, and giving future perspectives on their application in cutting‐edge areas. [ABSTRACT FROM AUTHOR]

Bundles of single-walled carbon nanotubes (SWCNTs) prepared by plasma torch method and further purified, are deposited over a glass coverslip to estimate the spatial resolution of tip-enhanced Raman spectroscopy measurements. For this purpose, near-field Raman maps and spectra of isolated bundles of carbon nanotubes are collected using optimized experimental conditions such as a tightly focused beam using a 1.4 numerical aperture oil immersion microscope objective and a gold coated atomic force microscope probe illuminated by a radially polarized 632.8 nm wavelength to selectively excite the localized surface plasmon confined at the extremity of the tip. The near-field nature of the collected Raman signals is evaluated through measuring the decay of the Raman signal with respect to the tip-sample separation. Key words: tip-enhanced Raman spectroscopy, localized surface plasmon resonance, near-field spectroscopy, radial polarization, atomic force microscopy, spatial resolution, enhancement factor, single-walled carbon nanotubes. Des fagots de nanofils de carbone simple-paroi, prepares par torche plasma puis purifies sont deposes sur des lamelles de microscope dans la perspective de mesurer la resolution spatiale de mesures Raman locales exaltees par effet de pointe. A cette fin, des cartographies ainsi que des spectres Raman sont collectes dans des conditions experimentales optimisees basees sur l'utilisation d'un objectif de microscope a forte ouverture numerique (O.N. 1.4) et d'une excitation avec une polarisation radiale a 632, 8 nm afin d'exciter selectivement le plasmon de surface localise et de confiner ce dernier a l'extremite de la pointe en or. Le champ proche Raman est evalue en analysant la decroissance du signal collecte en fonction de la distance entre la pointe et l'echantillon. Mots-cles: spectroscopie Raman exaltee par effet de pointe, plasmon de surface localise, microscopie en champ proche, polarisation radiale, microscopie a force atomique, resolution spatiale, facteur d'exaltation, nanofils de carbone a simple paroi., Introduction The discovery of surface-enhanced Raman spectroscopy (SERS) in the early 1970's was a milestone in improving the inherent low efficiency of inelastic Raman scattering. (1, 2) The improved sensitivity [...]

A gold nanoparticle platform is described in which post-synthesis surface modifications can be conducted using kinetically-tunable strain-promoted cycloaddition chemistry, which is dependent on the electronic properties of the complementary dipolar species. This permits chemoselective reactivity with one reactive dipole over another less reactive dipole, providing exciting opportinities for kinetically-directed self-sorting strategies. [ABSTRACT FROM AUTHOR]

The bottom‐up synthesis of self‐assembled micro‐compartmentalised systems that mimic basic characteristics of living cells is rapidly evolving. These types of systems are termed "protocells" and can be chemically programmed to grow and divide, to send and receive chemical signals, to transcript and translate chemical information, to adhere to surfaces or to other protocells, and to perform rudimental enzyme‐mediated metabolic processes. An emerging protocell model that is attracting great attention is the colloidosome. Colloidosomes are microcapsules with a chemically crosslinked, semipermeable membrane composed of amphiphilic nanoparticles. Colloidosomes display important advantages over other protocell models (e. g. vesicles and coacervate micro‐droplets) due to their physical‐chemical properties that can be easily tuned through the careful engineering of their synthetic building blocks. In this review, we deliver an overview of the different types of colloidosomes that have been developed thus far and discuss how organic chemistry contributes to the design and bottom‐up synthesis of novel types of colloidosomes endowed with advanced chemically programmed bio‐inspired functions. [ABSTRACT FROM AUTHOR]

The present work reports on the structural study of a film made of a hybrid blend of biopolymers used as an enzyme carrier. A cellulose derivative (HPMC) and chitosan (CS) were combined in order to formulate a film on which Mucor miehei lipase was immobilized. The film was successfully used as a biocatalyst; however, little is known about the structure of the system. Therefore, small-angle X-ray scattering, Fourier transform infrared spectroscopy (FTIR), optical microscopy, and scanning electron microscopy (SEM), as well as microindentation measurements, were used to shed light on the structure of the promising biocatalyst. Among the results, intermolecular hydrogen bonds were observed between the amide groups of the two polymers and the lipase. The presence of the enzyme does not seem to affect the mechanical properties of the matrix. The used film after 35 cycles of reaction seemed to be fatigued and had lost part of its humidity, explaining the reduction of the enzyme activity. [ABSTRACT FROM AUTHOR]

The precise assembly of protocell building blocks into prototissues that are stable in water, capable of sensing the external environment and which display collective behaviours remains a considerable challenge in prototissue engineering. We have designed a microfluidic platform that enables us to build bespoke prototissues from predetermined compositions of two types of protein–polymer protocells. We can accurately control their size, composition and create unique Janus configurations in a way that is not possible with traditional methods. Because we can control the number and type of the protocells that compose the prototissue, we can hence modulate the collective behaviours of this biomaterial. We show control over both the amplitude of thermally induced contractions in the biomaterial and its collective endogenous biochemical reactivity. Our results show that microfluidic technologies enable a new route to the precise and high-throughput fabrication of tissue-like materials with programmable collective properties that can be tuned through careful assembly of protocell building blocks of different types. We anticipate that our bespoke prototissues will be a starting point for the development of more sophisticated artificial tissues for use in medicine, soft robotics, and environmentally beneficial bioreactor technologies. [ABSTRACT FROM AUTHOR]

The design and synthesis of a novel acid‐degradable polyethylene glycol‐based N‐hydroxysuccinimide (NHS) ester‐activated crosslinker is reported. The crosslinker is reactive towards nucleophiles and features a central ketal functional group that is stable at pH > 7.5 and rapidly hydrolyses at pH > 6.0. The crosslinker is used to (i) fabricate acid‐degradable polysaccharide hydrogels that exhibit controlled degradation upon exposure to an acidic environment or via endogenous enzyme activity; and (ii) construct hydrogel‐filled protein‐polymer microcompartments (termed proteinosomes) capable of pH‐dependent membrane disassembly. Taken together the results provide new opportunities for the fabrication of pH‐responsive soft materials with potential applications in drug delivery, tissue engineering, and soft‐matter bioengineering. [ABSTRACT FROM AUTHOR]

Prototissues comprise free-standing 3D networks of interconnected protocell consortia that communicate and display synergistic functions. Significantly, they can be constructed from functional molecules and materials, providing unprecedented opportunities to design tissue-like architectures that can do more than simply mimic living tissues. They could function under extreme conditions and exhibit a wide range of mechanical properties and bio-inspired metabolic functions. In this perspective, I will start by describing recent advancements in the design and synthetic construction of prototissues. I will then discuss the next challenges and the future impact of this emerging research field, which is destined to find applications in the most diverse areas of science and technology, from biomedical science to environmental science, and soft robotics. [ABSTRACT FROM AUTHOR]

Polyelectrolyte/nucleotide multiphase complex coacervate droplets are produced by internalized aqueous two-phase separation and used for the spatially dependent chemical transfer of sugar molecules, providing a step towards the development of membrane-free "organelles" within coacervate-based protocells. [ABSTRACT FROM AUTHOR]

Cancer targeting can be used for both tumor diagnosis and therapy. Recently, gold nanoparticles (AuNPs) have found utility in this field as they are very small in size, and thus display an enhanced permeability and retention effect, allowing them to be taken up by tumor cells through 'passive targeting.' However, this accumulation is non-specific. Conversely, AuNPs functionalized with targeting entities such as peptides, antibodies, or small molecules can specifically target tumors through interaction with cancer-specific protein receptors. In this study, targeted AuNPs were developed using an azide-modified peptide that was able to react with alkyne-functionalized AuNPs through an interfacial strain-promoted azide-alkyne cycloaddition. Small (3 nm) AuNPs were made water-soluble through PEGylation and functionalized with dibenzocyclooctyne to add the alkyne functionality. For the targeting entity, a pan-bombesin peptide ([D-Phe6,β-Ala11,Phe13,Nle14]bombesin(6-14)) was chosen as it binds to all four receptor subtypes of the gastrin releasing peptide receptor, which is highly expressed in prostate cancer. Prostate cancer (PC-3) cells were incubated with the targeted AuNPs and studied via transmission electron microscopy. AuNPs conjugated with bombesin showed higher accumulation in PC-3 cells than either the blocking or control studies. These results suggest that these small, water-soluble, bombesin-functionalized AuNPs have potential applications in targeting prostate cancer as diagnostic or therapeutic entities. [ABSTRACT FROM AUTHOR]

The ability to regulate small-molecule release from metallic nanoparticle substrates offers unprecedented opportunities for nanocarrier-based imaging, sensing, and drug-delivery applications. Herein we report a novel and highly specific release methodology off gold nanoparticle (AuNP) surfaces based on the bioorthogonal Staudinger-Bertozzi ligation. A thiol ligand bearing the molecular cargo, a Rhodamine B dye derivative, was synthesized and used to modify small water-soluble 5 nm AuNPs. Upon incorporation into the AuNP monolayer, we observed efficient quenching of the dye emission, resulting in a very low level of fluorescence emission that provided the baseline from which cargo release was monitored. We examined the ability of these AuNPs to react with azide molecules via Staudinger-Bertozzi ligation on the nanoparticle surface by monitoring the fluorescence emission after the introduction of an organic azide. We observed an immediate increase in emission intensity upon azide addition, which corresponded to the release of the dye into the bulk solution. The 31P NMR spectrum of the AuNP product also agrees with the formation of the ligation product. Thus this system represents a novel and highly specific release methodology off AuNP surfaces that can have potential applications in drug delivery, sensing, and materials science. [ABSTRACT FROM AUTHOR]

In this study, we report the design, synthesis, and characterization of small 3 nm water soluble gold nanoparticles (AuNPs) that feature cyclopropenone-masked strained alkyne moieties capable of undergoing interfacial strain-promoted cycloaddition (i-SPAAC) with azides after exposure to UV-A light. A strained alkyne precursor was incorporated onto AuNPs by direct ligand exchange of a thiol-modified cyclopropenone-masked dibenzocyclooctyne (photoDIBO) ligand. These photoDIBO-AuNPs were characterized by 1H NMR, IR, and UV/Vis spectroscopy, as well as transmission electron microscopy (TEM) and thermogravimetric analysis (TGA), and the extent of modification was quantified. Upon irradiation with UV-A light, photoDIBO-AuNPs underwent efficient and quantitative regeneration of the parent strained alkyne by photochemical decarbonylation to afford DIBO-derivatized AuNPs. DIBO-AuNPs were found to react cleanly and rapidly ( k=5.3×10−2 m−1 s−1) by an interfacial strain-promoted alkyne-azide cycloadditon (i-SPAAC) with benzyl azide, which served as a simple model system. Furthermore, DIBO-AuNPs were reacted with various azides and a nitrone (interfacial strain-promoted alkyne-nitrone cycloaddition, i -SPANC) to showcase the generality of this approach for the facile modification of AuNP surfaces and their properties. The cyclopropenone-based photo-triggered click chemistry at the interface of water-soluble AuNPs offers exciting opportunities for the atom-by-atom control and assembly of functional materials for applications in materials and biomaterials science as well as in chemical biology. [ABSTRACT FROM AUTHOR]

Front Cover: Colloidosomes as a Protocell Model: Engineering Life-Like Behaviour through Organic Chemistry (Eur. J. Org. B The Front Cover b illustrates an adapted brightfield microscopy image of colloidosome protocells produced from gold nanoparticles using the Pickering emulsions technique. The artwork highlights the role of organic chemistry in the engineering of colloidosomes with life-like behaviors, which is the subject of this review article. [Extracted from the article]

A series of 12 thiolated oligopeptides of α-aminoisobutyric acid (Aib) were used to make self-assembled monolayers (SAMs) on carefully annealed gold plates. These peptides, which form 310-helices and have a strong dipole moment along the main peptide axis, were devised to give rise from zero to seven C=O⋅⋅⋅H−N intramolecular hydrogen bonds. The orientation of the natural dipole moment of the peptide was controlled by linking the thiolated moiety to either the nitrogen or carbon terminus. To assess the interactions between the chains forming the monolayer and determine the effect of the peptide orientation, the SAMs were characterized by polarization-modulation infrared-reflection absorption spectroscopy, in comparison with the FTIR behavior of the free peptides in solution. The stability of the peptide SAMs toward electroreduction was studied by cyclic voltammetry in 0.1 m NaOH. We show that electrodesorption is significantly affected by both peptide length and orientation in a way consistent with a strong effect exerted by the dipole moment of the peptide. [ABSTRACT FROM AUTHOR]

The maleimide moiety can undergo a wide variety of organic reactions, including Diels-Alder reactions, dipolar cycloadditions, and Michael-type additions, making it a suitable moiety for further elaboration of the functionality at the interface of gold nanoparticles (AuNPs) through key reactions that are useful in a host of applications. This account will cover: (1) our approach to prepare maleimide-AuNPs, (2) our survey of the scope of the reactivity of organic-solvent-soluble maleimide-AuNPs, which are very slow, impractical, and required the development of high-pressure techniques in AuNP chemistry yielding dramatic results, and (3) the extension of these ideas to prepare water-soluble small AuNPs to expand the scope of the organic transformation to aqueous environments. Within each of these sections there were challenges that had to be overcome, and we will describe the evolution of the ideas so that readers can get a glimpse of our thinking and problem solving as we proceeded. 1 Introduction 2 Maleimide-AuNPs: The Synthetic Strategy 3 Reactivity of the Organic-Solvent-Soluble Maleimide-AuNP Template 4 Synthesis of the Water-Soluble Maleimide-AuNP Template 5 Reactivity of the Water-Soluble Maleimide-AuNP Template 6 Concluding Remarks. [ABSTRACT FROM AUTHOR]

An azide-functionalized nitronyl nitroxide was synthesized and its reactivity towards the Staudinger-Bertozzi ligation was explored. Whereas a model reaction in solution showed the conversion of nitronyl nitroxide to an imino nitroxide radical, the same reaction at the interface of gold nanoparticles allowed for successful covalent incorporation of the nitronyl nitroxide radical onto the nanoparticles. [ABSTRACT FROM AUTHOR]

Prepared by simple pour and mix chemistry, gold nanosponges (AuNS) are versatile structures for surface-enhanced Raman spectroscopy (SERS). An investigation into the enhancement is performed by relating the nanostructure's morphology to the SERS signal. The potential of the AuNS in SERS-based molecular and biomolecular detection is introduced. [ABSTRACT FROM AUTHOR]

Maleimide-terminated triethylene glycol thiolate monolayer-protected gold nanoparticles (Mal -EG4-AuNPs) with a core size of 2.5 ± 0.7 nm were prepared. Mal-EG4-AuNPs were modified in high yields via interfacial 1,3-dipolar cycloaddition and Diels-Alder reactions with a variety of nitrones and dienes, respectively. The resulting cycloadduct-modified AuNPs were characterized using 1H NMR spectroscopy and were verified by comparison of the spectra to those of the products of the model reactions with the same nitrones and dienes. TEM analysis showed that the reaction conditions did not affect the shape or size of the gold core, suggesting that this is an efficient methodology to modify small water soluble AuNPs under ambient pressure and biological temperature with high yields and a reasonable reaction time. [ABSTRACT FROM AUTHOR]

An efficient method for the large-scale preparation of rhodamine B clickable derivatives has been developed. Starting from inexpensive rhodamine B as the starting material it was possible to functionalize the carboxylic functionality of rhodamine B with an azide, a strained-alkyne, a substituted triphenylphosphine, a thiol, and a maleimide. Through the synthetic strategy it was possible to obtain stable and pure clickable rhodamine compounds that can be readily used not only for chemoselectively probing biomolecules, but also for materials science. [ABSTRACT FROM AUTHOR]

A protection–deprotection strategy for strained alkynes used for bioorthogonal chemistry is reported. A strained alkyne can be protected with dicobalt–octacarbonyl and we demonstrate for the first time that a strained alkyne can be re-formed and isolated under mild reaction conditions for further bioorthogonal reactivity. The protection–deprotection strategy herein reported will expand the versatility of strained alkynes for the preparation of substrates in chemical biology and materials applications. [ABSTRACT FROM AUTHOR]

Versatile water- and organic solvent-soluble AuNPs that incorporate an interfacial strained alkyne capable of efficient pour and mix strain promoted interfacial cycloadditions with azide partners have been synthesized and carefully characterized for the first time. The use of XPS to quantitate the loading of the strained alkyne on the AuNPs is noteworthy. The reactivity towards the interfacial strain promoted azide-alkyne cycloaddition reaction was demonstrated by using azide-decorated polymersomes as bioorthogonal reaction partners. [ABSTRACT FROM AUTHOR]

A contrast agent suitable for magnetic resonance imaging based on small, water soluble gold nanoparticles (AuNP) conjugated to over 50 Gd3+ chelators has been prepared by using an interfacial Michael addition in aqueous media. The resultant chelator–AuNP conjugates have been successfully characterised by 1H NMR spectroscopy, IR spectroscopy, ICP-OES, ζ-potential analysis, TEM and MRI. T1-weighted in vivo images of mouse kidney were obtained using the agent at 9.4 T. A preliminary in vivo experiment produced no ill effects and the clearance profile of the agent suggests it is suitable for animal testing at clinically relevant concentrations. [ABSTRACT FROM AUTHOR]

The synthesis of a diiminopyridine (DIMPY) ligand containing pendant mixed sandwich cobaltocene functionalities on the imine nitrogens was prepared and characterized (18). Its reactivity with 2 equiv of GeCl2 dioxane and SnCl2 in THF yields the respective Lewis base mediated autoionization products (l8Ge and 18Sn). Analogous low-valent complexes utilizing an N,N'- difFerocenyl diiminopyridine support were also prepared (lSGe and 15Sn). All compounds were characterized by spectroscopic and X-ray crystallographic methods. Electrochemical studies were conducted for both ISSn and the precursor of 18. [ABSTRACT FROM AUTHOR]

The time-dependent progression from gold nanosponges (AuNS) to discrete small gold nanoparticles (AuNPs) mediated by H2O2 in MES buffer is blocked by the addition of a thiol, glutathione. This represents an important improvement for the plasmonic ELISA, and also leads to a time-dependent approach for the synthesis of AuNS and AuNPs in water with precise control over nanostructure size. [ABSTRACT FROM AUTHOR]

Improved methodology to prepare maleimide-functionalized,water-soluble,small (<3 nm) gold nanoparticles using a retro-Diels–Alderstrategy that we developed for similar organic-soluble AuNP's is described.Importantly, our results suggest that a recent paper by Zhu, Waengler,Lennox, and Schirrmacher describing a similar strategy gave resultsinconsistent with the formation of the titled maleimide-modified AuNP(Zhu, J.; Waengler, C.; Lennox, R. B.; Schirrmacher, R. Langmuir2012, 28, 5508) as the major product,but consistent with the major product being an adduct derived fromthe hydrolysis of maleimide formed under the conditions used for therequired deprotection of the maleimide. Our methodology provides anefficient and accessible route to pure maleimide-modified small AuNP'sthat circumvents the formation of the hydrolysis product. The maleimide-modifiedsmall AuNP's are versatile because they are soluble in water and ina wide range of organic solvents and their reactivity can now be properlyexploited as a reactive moiety in Michael addition for bioconjugationstudies in aqueous solution. [ABSTRACT FROM AUTHOR]

A new reversible, redox active diiminopyridine ligand (1Fc) containing pendant ferrocene functionalities was isolated and fully characterized. The reaction of 1Fc with chalcogen pseudohalides of sulfur, selenium, and tellurium yielded the respective N,N',N"-chelated chalcogen dications. Phosphorus chemistry proceeded in a related manner but, in this case, by the direct addition of 1Fc with PI3 to yield the N,N',N"-chelated P(I) cation. These species represent the first synthesized main group complexes involving a redox active diiminopyridine ligand containing pendant ferrocenes. Electrochemical studies of the free ligand shows a reversible two-electron process. The chelated phosphorus cation, however, displayed three events, the first being a quasi-reversible two-electron process, involving the oxidation at the P(I) center, resulting in a P(III) cation. The subsequent reversible one- and two-electron processes arise from the ligand framework and pendant ferrocenes, respectively. [ABSTRACT FROM AUTHOR]

Although different chemistries for the spatio‐temporal localization of molecules and gradients of chemical signals within soft materials are now available, the achievement of spatio‐temporal patterns of mechanical properties in such materials and their characterization remain considerable challenges. This study presents the syntheses of two novel photo‐sensitive and thermoresponsive hydrogel systems, a photo‐stiffening and a photo‐softening hydrogel. Their potential for fabricating soft materials with patterned mechanical properties is then demonstrated by fabricating an actuator whose higher‐order bending properties can be switched on with light, and by encoding mechanical properties for digital information encryption and storage. Microindentation and a custom‐made data analysis software are essential for the characterization of all the materials. From a general perspective, this work opens a route to the fabrication of soft materials with patterned mechanical properties, addressing an important emerging challenge in soft materials science with applications in soft robotics and information encryption and storage. [ABSTRACT FROM AUTHOR]

An interfacial strain promoted azide–alkyne cycloaddition (I-SPACC) is introduced as a method to prepare robust nanomaterial hybrids. This is demonstrated with a reaction between a novel dibenzocyclooctyne-modified single walled carbon nanotubes (DBCO-SWCNT) and a versatile water-soluble azide modified gold nanoparticle (N3-EG4-AuNP). [ABSTRACT FROM AUTHOR]

A CNT–AuNP hybrid has been synthesized through the Michael addition reaction between thiol-functionalized single-wall CNT and small water-soluble Maleimide–AuNP. The resilience and stability of this hybrid nanosystem is ensured by a covalent bond linking the nanoparticle to the CNT and by the fact that the functionalization reaction involves the organic shell of the AuNP and not its metallic core. [ABSTRACT FROM AUTHOR]

Gold Nanoparticles The functionalization of gold nanoparticle (AuNP) surfaces to manipulate their chemical interactions at the interface is crucial for applications in chemical biology and materials science. A cyclopropenone‐based photochemistry was developed on AuNPs to provide access to interfacial strained alkynes that undergo fast and clean interfacial strain‐promoted alkyne‐azide and alkyne‐nitrone cycloaddition (i‐SPAAC and i‐SPANC, respectively) with azides and nitrones, which serves as a simple and versatile way to tailor AuNP surface properties and functionality. For more information, see the Full Paper by V. V. Popik, M. S. Workentin et al. on page 1052 ff. [ABSTRACT FROM AUTHOR]

Review: [30 refs. [ABSTRACT FROM AUTHOR]

The achievement of light-responsive behaviours is an important target for protocell engineering to allow control of fundamental protocellular processes such as communication via diffusible chemical signals, shape changes or even motility at the flick of a switch. As a step towards this ambitious goal, here we describe the synthesis of a novel poly(ethylene glycol)-based crosslinker, reactive towards nucleophiles, that effectively degrades with UV light (405 nm). We demonstrate its utility for the fabrication of the first protocell membranes capable of light-induced disassembly, for the photo-generation of patterns of protocells, and for the modulation of protocell membrane permeability. Overall, our results not only open up new avenues towards the engineering of spatially organised, communicating networks of protocells, and of micro-compartmentalised systems for information storage and release, but also have important implications for other research fields such as drug delivery and soft materials chemistry., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)