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Stone cultural heritage buildings are frequently affected by different alteration phenomena and in particular, on heritage marbles the presence of chromatic discolouration, as the red stains, is one of the most widespread. In this paper, small fragments of red stains originated on marble exposed to different environmental contexts were analysed to reveal the presence and distribution of lead compounds at the micro-scale level. The samples come from slabs of historical religious buildings in Florence (Santa Maria del Fiore Cathedral and the San Giovanni Baptistery) and from the monumental fountains conserved in the Medicean Villa La Petraia (Florence). The presence and distribution of lead compounds: minium (Pb 3 O 4 ), carbonates such as cerussite (PbCO 3 ) and hydrocerussite (Pb 3 (CO 3 ) 2 (OH) 2 ) and plattnerite (PbO 2 ), was revealed using 2D high lateral resolution micro-X-Ray Powder Diffraction (μ-XRPD) and μ-Raman spectroscopy. Additional information were provided by Scanning Electron Microscopy, the elemental distribution performed with micro-X-Ray Fluorescence mapping enable to verify the possible presence of light elements and the use of FTIR chemical imaging confirmed the absence of organic compounds.

The charge-trapping mechanism in conjugated polymers is a performance obstacle in many optoelectronic devices harnessed for non-volatile memory applications. Herein, a carbonyl-decorated organic 2D-polymer (TpDb)-based charge-trapping memory device has been developed with a wide memory window (3.2 V) with low programming and erasing voltages of +3/-2 and -3/+2. The TpDb was synthesized by a potentially scalable solid-state aldol condensation reaction. The inherent structural defects and the semi-conjugated nature of the enone network in TpDb offer effective charge-trapping through the localization of charges in specific functional groups (CO). The interlayer hydrogen bonding enhances the packing density of the 2D-polymer layers thereby improving the memory storage properties of the material. Furthermore, the TpDb exhibits excellent features for non-volatile memory applications including over 10 000 cycles of write/read endurance and a prolonged retention performance of 10 4 seconds at high temperatures (100 °C).

Ouzo is a well-known drink in Mediterranean countries, with ingredients water, alcohol and trans -anethole oil. The oil is insoluble in water, but completely soluble in alcohol, so when water is added to the spirit, the available alcohol is depleted and the mixture exhibits spontaneous emulsification. This process is commonly known as the louche or ouzo effect. Although the phase boundaries of this archetypal ternary mixture are well known, the properties of coexisting phases have not previously been studied. Here, we present a detailed experimental investigation into the phase behaviour, including tie-lines connecting coexisting phases, determination of the critical point (also called the plait point in ternary systems) and measurements of the surface tension and density for varying alcohol concentrations. Additionally, we present a theory for the thermodynamics and phase diagram of the system. With suitable selection of the interaction parameters, the theory captures nearly all features of the experimental work. This simple model can be used to determine both bulk and non-uniform ( e.g. interfacial) properties, paving the way for a wide range of future applications of the model to ternary mixtures in general. We show how our accurate equilibrium phase diagram can be used to provide improved understanding of non-equilibrium phenomena.

The soft part of the Earth's surface - the ground beneath our feet - constitutes the basis for life and natural resources, yet a general physical understanding of the ground is still lacking. In this critical time of climate change, cross-pollination of scientific approaches is urgently needed to better understand the behavior of our planet's surface. The major topics in current research in this area cross different disciplines, spanning geosciences, and various aspects of engineering, material sciences, physics, chemistry, and biology. Among these, soft matter physics has emerged as a fundamental nexus connecting and underpinning many research questions. This perspective article is a multi-voice effort to bring together different views and approaches, questions and insights, from researchers that work in this emerging area, the soft matter physics of the ground beneath our feet. In particular, we identify four major challenges concerned with the dynamics in and of the ground: (I) modeling from the grain scale, (II) near-criticality, (III) bridging scales, and (IV) life. For each challenge, we present a selection of topics by individual authors, providing specific context, recent advances, and open questions. Through this, we seek to provide an overview of the opportunities for the broad Soft Matter community to contribute to the fundamental understanding of the physics of the ground, strive towards a common language, and encourage new collaborations across the broad spectrum of scientists interested in the matter of the Earth's surface.

The family of radical-cation salts β''-(BEDT-TTF) 4 [(A)M 3+ (C 2 O 4 ) 3 ]·guest (M = Fe, Cr, Ga, Al, Co, Mn, Rh, Ru; A = K + , H 3 O + , NH 4 + ) has produced superconductors, metals, semiconductors, and metal-insulators through introduction of different guest molecules into the structure. We present three new additions to the family β''-(BEDT-TTF) 4 [(A)Cr(C 2 O 4 ) 3 ]·guest with the guest molecules toluene, phenol, or salicylaldehyde. These new guests are liquid or solid additives within the electrocrystallisation medium. All three salts show metallic behaviour from room temperature down to <10 K and do not show a superconducting transition., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Curcumin is a medicinal agent that exhibits anti-cancer and anti-Alzheimer's disease properties. It has a keto-enol moiety that gives rise to many of its chemical properties including metal complexation and acid-base equilibria. A previous study has shown that keto-enol tautomerization at this moiety is implicated in the anti-Alzheimer's disease effect of curcumin, highlighting the importance of this process. In this study, tautomerization of curcumin in methanol, acetone and acetonitrile was investigated using time-resolved 1 H nuclear magnetic resonance spectroscopy. Curcumin undergoes hydrogen-deuterium exchange with the solvents and the proton resonance peak corresponding to the hydrogen at the α-carbon position (C α ) decays as a function of time, signifying deuteration at this position. Because tautomerization is the rate limiting step in the deuteration of curcumin at the C α position, the rate of tautomerization is inferred from the rate of deuteration. The rate constant of tautomerization of curcumin shows a temperature dependence and analysis using the Arrhenius equation revealed activation energies ( E a ) of tautomerization of (80.1 ± 5.9), (64.1 ± 1.0) and (68.3 ± 5.5) kJ mol -1 in methanol, D 2 O/acetone and D 2 O/acetonitrile, respectively. Insight into the role of water in tautomerization of curcumin was further offered by density functional theory studies. The transition state of tautomerization was optimized in the presence of water molecules. The results show a hydrogen-bonded solvent bridge between the diketo moiety and C α of curcumin. The E a of tautomerization of curcumin shows a strong dependence on the number of water molecules in the solvent bridge, indicating the critical role played by the solvent bridge in catalyzing tautomerization of curcumin.

The search for low-diffusion barriers and high-capacity anode materials is considered a key step in boosting the efficiency of metal-ion batteries. Herein, we investigate the impact of a series of conducting polymers (CPs), namely, polyacetylene (PA), polypyrrole (PP), poly- p -phenylene (PPPh), and polythiophene (PT), on enhancing the material design and anodic performance of boron nitride nanosheet (BNNS)-based Li-ion and Na-ion batteries. For this purpose, first principle DFT simulations, utilizing both clustered and periodic models, are systematically performed to assess the stability of such nanostructures and their electronic behavior as potential anodic materials. It is revealed that frontier molecular orbitals calculated for BNNSs are stabilized upon association with the series of CPs, resulting in a reduction in the energy gaps of CP-BNNSs by nearly 50%, which in turn improves the charge transfer properties and cell reaction kinetics. A remarkable improvement in the cell voltage is predicted for PP and PT functionalized BNNSs, reaching approximately 3.5 V for Li + and 3.0 V for Na + ions. The outcome of the study emphasizes the influence of the size of metal ions, whether mono- or di-valent, and the nature of adsorbed conducting polymers. Manipulating the electronic features of boron nitride nanostructured surfaces through non-covalent functionalization with conducting polymers could pave the way for the design of highly efficient energy storage anodic CP-BNNS-based systems.

The scission and homologation of CO is a fundamental process in the Fischer-Tropsch reaction. However, given the heterogeneous nature of the catalyst and forcing reaction conditions, it is difficult to determine the intermediates of this reaction. Here we report detailed mechanistic insight into the scission/homologation of CO by two-coordinate iron terphenyl complexes. Mechanistic investigations, conducted using in situ monitoring and reaction sampling techniques (IR, NMR, EPR and Mössbauer spectroscopy) and structural characterisation of isolable species, identify a number of proposed intermediates. Crystallographic and IR spectroscopic data reveal a series of migratory insertion reactions from 1 Mes to 4 Mes . Further studies past the formation of 4 Mes suggest that ketene complexes are formed en route to squaraine 2 Mes and iron carboxylate 3 Mes , with a number of ketene containing structures being isolated, in addition to the formation of unbound, protonated ketene (8). The synthetic and mechanistic studies are supported by DFT calculations., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The increased adoption of non-invasive laser-based techniques for analysis of cultural assets has recently called into question the non-invasiveness of the techniques in practical operation. The methods to assess the occurrence of radiation-induced alteration on paintings are very limited and none of them can predict damage. Here we present a novel multimodal imaging approach to understand the time and spatial evolution and types of laser-induced surface alterations, through simultaneous monitoring using visible and near infrared (VIS-NIR) reflectance hyperspectral imaging (HSI) and thermal imaging during Raman spectroscopy. The resultant physical and chemical changes were examined in detail by optical coherence tomography and synchrotron based micro-X-ray powder diffraction. HSI was found to be the most sensitive in detecting laser induced alternations compared with conventional methods. It is orders of magnitude more sensitive than Raman spectroscopy and even synchrotron-based micro-X-ray powder diffraction. In cases of thermally driven alterations, transient and reversible reflectance changes were found to be the first indications of laser-induced modifications and can therefore be used as precursors to prevent damage. VIS-NIR reflectance spectroscopy should be used to monitor laser-based analysis and potentially other radiation-based techniques in situ to mitigate laser induced alteration.

Two-dimensional covalent organic frameworks (2D-COFs) are a class of crystalline porous organic polymers, consisting of 2D-planar sheets stacked together perpendicularly via noncovalent forces. Since their discovery, 2D-COFs have attracted extensive attention for optoelectronic and adsorption applications. Owing to the layer stacking nature of 2D COFs, various new slipped structures that are energetically favourable can be designed. These interlayer slipped structures are actively responsible for tuning (mostly enhancing) the optoelectronic properties, thermal properties, and mechanical strength of 2D COFs. This review summarizes the effect of interlayer slipping on the energetic stability, electronic behaviour and gas adsorption properties of 2D layered COFs, which is explained through computational modelling simulations. Since computational modelling offers a deep insight into electronic behaviour at the atomic scale, which is potentially impossible through experimental techniques, the introduction and role of computational techniques in such studies have also been described.

Colloidal suspensions are the basis of a wide variety of coatings, prepared as liquids and then dried into solid films. The processes at play during film formation, however, are difficult to observe directly. Here, we demonstrate that optical coherence tomography (OCT) can provide fast, non-contact, precise profiling of the dynamics within a drying suspension. Using a scanning Michelson interferometer with a broadband laser source, OCT creates cross-sectional images of the optical stratigraphy of a sample. With this method, we observed the drying of colloidal silica in Hele-Shaw cells with 10 μm transverse and 1.8 μm depth resolution, over a 1 cm scan line and a 15 s sampling period. The resulting images were calibrated to show how the concentration of colloidal particles varied with position and drying time. This gives access to important transport properties, for example, of how collective diffusion depends on particle concentration. Looking at early-time behaviours, we also show how a drying front initially develops, and how the induction time before the appearance of a solid film depends on the balance of diffusion and evaporation-driven motion. Pairing these results with optical microscopy and particle tracking techniques, we find that film formation can be significantly delayed by any density-driven circulation occurring near the drying front.

Motivated by recent experimental results that reveal rich collective dynamics of thousands-to-millions of active liquid crystal skyrmions, we have developed a coarse-grained, particle-based model of the dynamics of skyrmions in a dilute regime. The basic physical mechanism of skyrmion motion is related to squirming undulations of domains with high director twist within the skyrmion cores when the electric field is turned on and off. The motion is not related to mass flow and is caused only by the reorientation dynamics of the director field. Based on the results of the "fine-grained" Frank-Oseen continuum model, we have mapped these squirming director distortions onto an effective force that acts asymmetrically upon switching the electrical field on or off. The resulting model correctly reproduces the skyrmion dynamics, including velocity reversal as a function of the frequency of a pulse width modulated driving voltage. We have also obtained approximate analytical expressions for the phenomenological model parameters encoding their dependence upon the cholesteric pitch and the strength of the electric field. This has been achieved by fitting coarse-grained skyrmion trajectories to those determined in the framework of the Frank-Oseen model.

Density functional theory calculations were performed to identify product, reactant and intermediate dissociative/associative structures for the oxygen abstraction and addition reactions: Rh 10 O n + CO → Rh 10 O n -1 + CO 2 , n = 1-5 and Rh 10 O n + N 2 O → Rh 10 O n +1 + N 2 , n = 0-4 reactions. In the case of the oxygen abstraction reactions, the energetics of the reaction path were very similar in energy regardless of the number of oxygen atoms on the Rh 10 O n cluster, whereas for the addition of oxygen to the Rh 10 O n cluster, the reaction was found to become significantly less exothermic with each successive addition of oxygen.

Semi-solid extrusion (SSE) 3D printing has recently attracted increased attention for its pharmaceutical application as a potential method for small-batch manufacturing of personalised solid dosage forms. It has the advantage of allowing ambient temperature printing, which is especially beneficial for the 3D printing of thermosensitive drugs. In this study, the effects of polymeric compositions (single hydroxypropyl methylcellulose (HPMC) system and binary HPMC + polyvinylpyrrolidone (PVP) system), disintegrant (silicon oxide (SiO 2 )), and active pharmaceutical ingredients (tranexamic acid (TXA) and paracetamol (PAC)) on the printability of semisolid inks and the qualities of SSE printed drug-loaded tablets were investigated. Printability is defined by the suitability of the material for the process in terms of its physical properties during extrusions and post-extrusion, including rheology, solidification time, avoiding slumping, etc. The rheological properties of the inks were investigated as a function of polymeric compositions and drug concentrations and further correlated with the printability of the inks. The SSE 3D printed tablets were subjected to a series of physicochemical properties characterisations and in vitro drug release performance evaluations. The results indicated that an addition of SiO 2 would improve 3D printing shape fidelity ( e.g. , pore area and porosity) by altering the ink rheology. The pores of HPMC + PVP + 5PAC prints completely disappeared after 12 hours of drying (pore area = 0 mm 2 ). An addition of SiO 2 significantly improved the pore area of the prints which are 3.5 ± 0.1 mm 2 . It was noted that the drug release profile of PAC significantly increased ( p < 0.05) when additive SiO 2 was incorporated in the formulation. This could be due to a significantly higher porosity of HPMC + PVP + SiO 2 + PAC (70.3 ± 0.2%) compared to HPMC + PVP + PAC (47.6 ± 2.1%). It was also likely that SiO 2 acted as a disintegrant speeding up the drug release process. Besides, the incorporation of APIs with different aqueous solubilities, as well as levels of interaction with the polymeric system showed significant impacts on the structural fidelity and subsequently the drug release performance of 3D printed tablets.

Try and encapsulate microparticles inside the cores of microcapsules and you will often find that particles adhere to the liquid-liquid interface in a phenomenon known as Pickering stabilization. Particles will remain irreversibly trapped and embedded within the subsequently formed microcapsule membrane. In cases where the encapsulant particles must remain suspended inside the microcapsule core to retain their desired properties or behaviours, Pickering stabilization is detrimental. Here we demonstrate a general procedure using yield stress materials as the core material, where the yield stress of the gel is strong enough to suspend particles against sedimentation, but weak enough to allow spatial manipulation of encapsulant particles using an external field. This external field imparts enough force on particles to disrupt the supporting network and allow particle mobility after encapsulation.

In the current era, alternative but environment-friendly sources of energy have gained attention to meet the growing energy demands. In particular, the focus of research has been solar energy and using it to fulfill energy demands. Solar energy is either directly converted into electrical energy or stored for later use. Solar cells are a practical way to turn solar energy into electrical energy. Various materials are being investigated to manufacture solar cell devices that can absorb a maximum number of photons present in sunlight. The present study reports thermally evaporated in situ Cu-doped SnS photon absorber thin films with tunable physical properties. This study mainly explored the effects of changing Cu concentrations on the physical features of light absorption of SnS thin films. The thin films were formed by simultaneous resistive heating of Cu and SnS powders on glass substrates at 150 °C. The X-ray diffraction patterns revealed pure SnS thin films having orthorhombic polycrystalline crystal structures oriented preferentially along the (111) plane. Raman spectroscopy confirmed this phase purity. Photoconductivity studies showed phase dependence on Cu content that improved with increasing concentrations of Cu. The optical bandgap energy was also found to be dependent on Cu content and was observed at 1.10-1.47 eV for SnS thin films with variation in the Cu content, i.e. , 0-18%. According to the hot probe method, all films displayed p-type conductivity for the substitution of Cu metal atoms. These findings demonstrated that the prepared thin films are substantial candidates as low-cost, suitably efficient, thin-film solar cells featuring environmentally-friendly active layers that absorb sunlight.

The intricate process of biomineralization, e.g. in sea urchins, involves the precise interplay of highly regulated mineralization proteins and the spatiotemporal coordination achieved through compartmentalization. However, the investigation of biomineralization effector molecules, e.g. proteins, is challenging, due to their very low abundance. Therefore, we investigate the functional mimicry in the bioinspired precipitation of calcium carbonate (CaCO 3 ) with artificial peptides selected from a peptide library by phage display based on peptide-binding to calcite and aragonite, respectively. The structure-directing effects of the identified peptides were compared to those of natural protein mixes isolated from skeletal (test) structures of two sea urchin species ( Arbacia lixula and Paracentrotus lividus ). The calcium carbonate samples deposited in the absence or presence of peptides were analyzed with a set of complementary techniques with regard to morphology, polymorph, and nanostructural motifs. Remarkably, some of the CaCO 3 -binding peptides induced morphological features in calcite that appeared similar to those obtained in the presence of the natural protein mixes. Many of the peptides identified as most effective in exerting a structure-directing effect on calcium carbonate crystallization were rich in basic amino acid residues. Hence, our in vitro mineralization study further highlights the important, but often neglected, role of positively charged soluble organic matrices associated with biological and bioinspired CaCO 3 deposition.

The most advanced structure prediction methods are powerless in exploring the conformational ensemble of disordered peptides and proteins and for this reason the "protein folding problem" remains unsolved. We present a novel methodology that enables the accurate prediction of spectroscopic fingerprints (circular dichroism, infrared, Raman, and Raman optical activity), and by this allows for "tidying up" the conformational ensembles of disordered peptides and disordered regions in proteins. This concept is elaborated for and applied to a dodecapeptide, whose spectroscopic fingerprint is measured and theoretically predicted by means of enhanced-sampling molecular dynamics coupled with quantum mechanical calculations. Following this approach, we demonstrate that peptides lacking a clear propensity for ordered secondary-structure motifs are not randomly, but only conditionally disordered. This means that their conformational landscape, or phase-space, can be well represented by a basis-set of conformers including about 10 to 100 structures. The implications of this finding have profound consequences both for the interpretation of experimental electronic and vibrational spectral features of peptides in solution and for the theoretical prediction of these features using accurate and computationally expensive techniques. The here-derived methods and conclusions are expected to fundamentally impact the rationalization of so-far elusive structure-spectra relationships for disordered peptides and proteins, towards improved and versatile structure prediction methods., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Macroscopic scale hollow microcrystals are a promising group of materials for gas and liquid uptake as well as sensing. In this contribution we describe the structure of hollow hexagonal cross-section crystals formulated as salts of a silicon catecholate anion and a tetramethylenediamine (TEMED) cation. Using a combination of X-ray single crystal diffraction, Raman spectroscopy and quantum chemistry we explore the structural properties of the hollow microcrystals. With the X-ray structural data as a starting point and assisted with quantum chemistry we compute Raman tensors to fit polarisation sensitive spectral responses and predict the orientation and packing of unit cells in respect to the long and short axis of the synthesised microcrystals. Using these newly developed methods for predicting molecular Raman responses in space with dependence on local orientation, we present the quantitative analysis of experimental Raman images of both hexagonal and tetragonal cross section hollow microcrystals formed from silicon catecholate anions using different amines as counterions. We describe the distributions of chemical components at the surfaces and edges of microcrystals, address the effect of catcholate hydrophobicity on water uptake and discuss possible strategies in chemical and post-assembly modifications to widen the functional properties of this group of environmentally friendly silicon organic framework (SOF) materials.

Covalent organic frameworks (COFs) are ideal host matrices for biomolecule immobilization and biocatalysis due to their high porosity, various functionalities, and structural robustness. However, the porosity of COFs is limited to the micropore dimension, which restricts the immobilization of enzymes with large volumes and obstructs substrate flow during enzyme catalysis. A hierarchical 3D nanostructure possessing micro-, meso-, and macroporosity could be a beneficial host matrix for such enzyme catalysis. In this study, we employed an in situ CO 2 gas effervescence technique to induce disordered macropores in the ordered 2D COF nanostructure, synthesizing hierarchical TpAzo COF-foam. The resulting TpAzo foam matrix facilitates the immobilization of multiple enzymes with higher immobilization efficiency (approximately 1.5 to 4-fold) than the COF. The immobilized cellulolytic enzymes, namely β-glucosidase (BGL), cellobiohydrolase (CBH), and endoglucanase (EG), remain active inside the TpAzo foam. The immobilized BGL exhibited activity in organic solvents and stability at room temperature (25 °C). The enzyme-immobilized TpAzo foam exhibited significant activity towards the hydrolysis of p -nitrophenyl-β-d-glucopyranoside (BGL@TpAzo-foam: K m and V max = 23.5 ± 3.5 mM and 497.7 ± 28.0 μM min -1 ) and carboxymethylcellulose (CBH@TpAzo-foam: K m and V max = 18.3 ± 4.0 mg mL -1 and 85.2 ± 9.6 μM min -1 and EG@TpAzo-foam: K m and V max = 13.2 ± 2.0 mg mL -1 and 102.2 ± 7.1 μM min -1 ). Subsequently, the multi-enzyme immobilized TpAzo foams were utilized to perform a one-pot tandem conversion from carboxymethylcellulose (CMC) to glucose with high recyclability (10 cycles). This work opens up the possibility of synthesizing enzymes immobilized in TpAzo foam for tandem catalysis., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Many biological systems are made to operate more quickly, efficiently, and with more power by storing elastic energy. This work introduces a straightforward bioinspired design for the quick manufacture of pre-stressed soft magnetic actuators. The actuator requires a lower magnetic field strength to be activated and can regain its original shape without the need for external stimuli. These characteristics are demonstrated in this work through the creation of actuators with round and helical shape structures inspired by the tendril plant and chameleon's tongue. Both the final form of the actuator and its actuation sequence may be programmed by controlling the direction and strength of the force utilised to pre-stress the elastomeric layer. Analytical models are presented to trace the actuators' energy storage, radius, and pitch. High-speed shape recovery after releasing the magnetic force and a strong grasping force are achieved due to the stored mechanical elastic energy. Experiments are conducted to analyse the shape changes, grasping action, and determine the actuation force. The manufacture of the grippers with zero-magnetic field strength holding capacities of up to 20 times their weight is made possible by the elastic energy that actuators store in their pre-stressed elastomeric layer. The outcomes of our research show that a unique magnetic field-controlled soft actuator can be created in different shapes and designs based on requirements.

Silver nanoparticles (AgNPs) represent one of the most commercialised metal nanomaterials, with an extensive number of applications that span from antimicrobial products to electronics. Bare AgNPs are very susceptible to aggregation, and capping agents are required for their protection and stabilisation. The capping agents can endow new characteristics which can either improve or deteriorate AgNPs (bio)activity. In the present work, five different capping agents were studied as stabilizing agents for AgNPs: trisodium citrate (citrate), polyvinylpyrrolidone (PVP), dextran (Dex), diethylaminoethyl-dextran (Dex DEAE ) and carboxymethyl-dextran (Dex CM ). The properties of the AgNPs were studied using a set of methods, including transmission electron microscopy, X-ray diffraction, thermogravimetric analysis and ultraviolet-visible and infrared spectroscopy. Coated and bare AgNPs were also tested against Escherichia coli , methicillin-resistance Staphylococcus aureus and Pseudomonas aeruginosa to analyse their capacity to suppress bacterial growth and eradicate biofilms of clinically relevant bacteria. The results showed that all the capping agents endow long-term stability for the AgNPs in water; however, when the AgNPs are in bacterial culture media, their stability is highly dependent on the capping agent properties due to the presence of electrolytes and charged macromolecules such as proteins. The results also showed that the capping agents have a substantial impact on the antibacterial activity of the AgNPs. The AgNPs coated with the Dex and Dex CM were the most effective against the three strains, due to their better stability which resulted in the release of more silver ions, better interactions with the bacteria and diffusion into the biofilms. It is hypothesized that the antibacterial activity of capped AgNPs is governed by a balance between the AgNPs stability and their ability to release silver ions. Strong adsorption of capping agents like PVP on the AgNPs endows higher colloidal stability in culture media; however, it can decrease the rate of Ag + release from the AgNPs and reduce the antibacterial performance. Overall, this work presents a comparative study between different capping agents on the properties and antibacterial activity of AgNPs, highlighting the importance of the capping agent in their stability and bioactivity., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Mercury is considered to be one of the most toxic elements to humans. Due to pollution from industry and artisanal gold mining, mercury species are present globally in waters used for agriculture, aquaculture, and drinking water. This review summarises methods reported for preserving mercury species in water samples and highlights the associated hazards and issues with each. This includes the handling of acids in an uncontrolled environment, breakage of sample containers, and the collection and transport of sample volumes in excess of 1 L, all of which pose difficulties for both in situ collection and transportation. Literature related to aqueous mercury preservation from 2000-2021 was reviewed, as well as any commonly cited and relevant references. Amongst others, solid-phase extraction techniques were explored for preservation and preconcentration of total and speciated mercury in water samples. Additionally, the potential as a safe, in situ preservation and storage method for mercury species were summarised. The review highlighted that the stability of mercury is increased when adsorbed on a solid-phase and therefore the metal and its species can be preserved without the need for hazardous reagents or materials in the field. The mercury species can then be eluted upon return to a laboratory, where sensitive analytical detection and speciation methods can be better applied. Developments in solid phase extraction as a preservation method for unstable metals such as mercury will improve the quality of representative environmental data, and further improve toxicology and environmental monitoring studies.

Laminar jamming (LJ) technology is a hot topic because it allows for the transition from conventionally quick, precise, and high-force rigid robots to flexible, agile, and secure soft robots. This article introduces a novel conceptual design of meta-laminar jamming (MLJ) actuators with a polyurethane shape memory polymer (SMP)-based meta-structure fabricated by 4D printing (4DP). The sustainable MLJ actuators behave as soft/hard robots via hot and cold programming accompanied by negative air pressure. The advantage of MLJ actuators over conventional LJ actuators is that a continuous negative air pressure is not required to stimulate the actuator. SMP meta-structures with circle, rectangle, diamond, and auxetic shapes are 4D printed. Mechanical properties of the structures are evaluated through three-point bending and compression tests. Shape memory effects (SMEs) and shape recovery of meta-structures and MLJ actuators are investigated via hot air programming. MLJ actuators with auxetic meta-structure cores show a better performance in terms of contraction and bending with 100% shape recovery after stimulation. The sustainable MLJ actuators have the capabilities of shape recovery and shape locking with zero input power while holding 200 g weight. The actuator can easily lift and hold objects of varying weights and shapes without requiring any power input. This actuator has demonstrated its versatility in potential applications, such as functioning as an end-effector and a gripper device.

In many applications, the main limitation of X-ray absorption methods is that the signals measured are a function of the attenuation coefficient, which tells us almost nothing about the chemical or crystallographic nature of objects under inspection. To calculate fundamental crystallographic parameters requires the measurement of diffracted photons from a sample. Standard laboratory diffraction methods have been refined for well over a century and provide 'gold standard' structural models for well-prepared samples and single crystals but have little applicability for thick heterogeneous samples as demanded by many screening applications. We present a new high-energy X-ray diffraction probe, which in comparison with previous depth-resolving hollow beam techniques, requires a single beam, point detector and a simple swept aperture to resolve sample signatures at unknown locations within an inspection space. We perform Monte Carlo simulations to support experiments on both single- and multiple-material localisation and identification. The new probe is configured and tested using low-cost commercial components to provide a rapid and cost-effective solution for applications including explosives detection, process control and diagnostics.

We use Raman microscopy to describe the structure and chemical composition of both conidiophore and hyphae of Botrytis cinerea , a common plant pathogen. To interpret experimental data, we use density functional theory (DFT) to compute Raman tensors specific to an important fungal glycopeptide, a segment of α-chitin, and several naphthalene-based precursors of increasing complexity, which we propose play a role in the melanin synthesis pathway. Using spectral interpretations based on quantum chemical validation, we review microscopy images reconstructed for specific Raman activities and describe differences in distributions of structural components, photo-protective secondary naphthalene-based pigments, and proteins in both spores and hyphal filaments. Comparison of our results with literature data on other fungi suggests an example of convergent evolution expressed at the level of secondary metabolites specific to plant pathogenic fungi. Our results indicate that pre-resonant Raman monitoring of melanin precursors may help assessment of local Botrytis population biology to aid agricultural production., Competing Interests: The authors declare no conflicts., (This journal is © The Royal Society of Chemistry.)

Polymer chemistry, composition and molar mass are factors that are known to affect cytotoxicity, however the influence of polymer architecture has not been investigated systematically. In this study the influence of the position of the cationic charges along the polymer chain on cytotoxicity was investigated while keeping constant the other polymer characteristics. Specifically, copolymers of various architectures, based on a cationic pH responsive monomer, 2-(dimethylamino)ethyl methacrylate (DMAEMA) and a non-ionic hydrophilic monomer, oligo(ethylene glycol)methyl ether methacrylate (OEGMA) were engineered and their toxicity towards a panel of cell lines investigated. Of the seven different polymer architectures examined, the block-like structures were less cytotoxic than statistical or gradient/tapered architectures. These findings will assist in developing future vectors for nucleic acid delivery., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

We describe a surface charge imaging method for heterogeneous biosilicas based on relationships between zeta ( ζ ) potential, feature size of nanoparticles, and PDMPO fluorescence and apply it to silicified structures from plants and diatoms. The methodology provides the first opportunity to map the surface charge of large heterogeneous biosilica materials and indicates that local surface charge is related to morphology below the diffraction limit ( ca. 20-130 nm) with sharper features showing less negative zeta potential equivalent surface charge suggesting that the zeta potential of silica structures can be adjusted by engineering surface morphology. We show that the approach can be used to study living silicified biological tissues without recourse to sectioning and fixation. Further, the approach could be used for the study of other metal oxides possessing hydroxylated moieties. The method has potential to open up opportunities for the engineering of materials with defined charge characteristics for the solution of biomedical engineering problems including materials for tissue replacement.

Elucidating the precise stacking configuration of a covalent organic framework, COF, is critical to fully understand their various applications. Unfortunately, most COFs form powder crystals whose atomic characterisations are possible only through powder X-ray diffraction (PXRD) analysis. However, this analysis has to be coupled with computational simulations, wherein computed PXRD patterns for different stacking configurations are compared with experimental patterns to predict the precise stacking configuration. This task is often computationally challenging firstly because, computation of these systems mostly rely on the use of semi-empirical methods that need to be adequately parametrised for the system being studied and secondly because some of these compounds possess guest molecules, which are not often taken into account during computation. COF-1 is an extreme case in which the presence of the guest molecule plays a critical role in predicting the precise stacking configuration. Using this as a case study, we mapped out a full PES for the stacking configuration in the guest free and guest containing system using the GFN-xTB semi-empirical method followed by a periodic energy decomposition analysis using first-principles Density Functional Theory (DFT). Our results showed that the presence of the guest molecule leads to multiple low energy stacking configurations with significantly different lateral offsets. Also, the semi-empirical method does not precisely predict DFT low energy configurations, however, it accurately accounts for dispersion. Finally, our quantum-mechanical analysis demonstrates that electrostatic-dispersion model suggested Hunter and Sanders accurately describes the stacking in 2D COFs as opposed to the newly suggested Pauli-dispersion model.

Solid porous and crystalline covalent organic frameworks (COFs) are characterized by their higher specific BET surface areas and functional pore walls, which allow the adsorption of various bioactive molecules inside the porous lattices. We have introduced a perylene-based COF, PER@PDA-COF-1, which acts as an effective porous volumetric reservoir for an anticancer drug, mitoxantrone (MXT). The drug-loaded COF (MXT-PER@PDA-COF-1) exhibited zero cellular release of MXT towards cancer cells, which can be attributed to the strong intercalation between the anthracene-dione motif of the drug and the perylene-based COF backbone. Here, we have introduced a strategy involving the serum-albumin-triggered intracellular release of mitoxantrone from MXT-PER@PDA-COF-1. The serum albumin acts as an exfoliating agent and as a colloidal stabilizer in PBS medium (pH = 7.4), rapidly forming a protein corona around the exfoliated COF crystallites and inducing the sustained release of MXT from the COF into tumorigenic cells., Competing Interests: The authors declare no competing financial interests., (This journal is © The Royal Society of Chemistry.)

Oral delivery remains one of the most convenient routes for drug administration compared to intravenous, intramuscular, and via suppositories. However, due to the risk of degradation, and proteolysis of molecules in the acidic gastric medium, as well as the difficulty of transporting large molecules through the intestinal membrane, more than half of the therapeutic molecules are prohibited for oral administration. Moreover, most of the large molecules and biological therapeutics are not available in oral dosage form due to their instability in the stomach and inability of intestinal absorption. To achieve expected bioavailability, an orally administered therapeutic molecule must be protected within the stomach, and transportation facilitated via the small intestine. In this project, we have introduced a hybrid carrier, composed of Taurocholic Acid (TA) and β-Glucan (TAG), that is shown to be effective for the simultaneous protection of the biologics in acidic buffer and simulated gastric juice as well as facilitate enhanced absorption and transportation via the small intestine. In this project, we have used an eGFP encoded plasmid as a model biologic to prepare particles mediated with TAG. TAG show the potential of enhancing transfection and expression of eGFP as we have observed two fold higher expression in the cell upon coincubation for 4 h. In vivo studies on orally dosed mice showed that eGFP expression in the liver was significantly higher in TAG containing particles compared to particles without TAG. The findings suggest that the TAG carrier is capable of not only preserving biologics but also transporting them more efficiently to the liver. As a result, this strategy can be employed for a variety of liver-targeted therapeutic delivery to treat a variety of liver diseases.

Tight-binding approaches bridge the gap between force field methods and Density Functional Theory (DFT). Density Functional Tight Binding (DFTB) has been employed for a wide range of systems including proteins, clays and 2D and 3D materials. DFTB is 2-3 orders of magnitude faster than DFT, allowing calculations containing up to ca. 5000 atoms. The efficiency of DFTB comes via pre-computed integrals, which are parameterized for each pair of atoms, and the requirement for this parameterization has previously prevented widespread use of DFTB for Metal-Organic Frameworks. The GFN-xTB (Geometries, Frequencies, and Non-covalent interactions Tight Binding) method provides parameters for elements up to Z ≤ 86. We have therefore employed GFN-xTB to periodic optimizations of the Computation Ready Experimental (CoRE) database of MOF structures. We find that 75% of all cell parameters remain within 5% of the reference (experimental) value and that bonds containing metal atoms are typically well conserved with a mean average deviation of 0.187 Å. Therefore GFN-xTB provides the ability to calculate MOF structures more accurately than force fields, and ca. 2 orders of magnitude faster than DFT. We therefore propose that GFN-xTB is a suitable method for screening of hypothetical MOFs ( Z ≤ 86), with the advantage of accurate binding energies for adsorption applications.

Nanometer scale rods of superparamagnetic iron oxide have been encapsulated, along with the anti-cancer therapeutic carnosine, inside porous poly(lactic- co -glycolic acid) microbeads with a uniform morphology, synthesised using microfluidic arrays. The sustained and externally triggered controlled release from these vehicles was demonstrated using a rotating Halbach magnet array, quantified via liquid chromatography, and imaged in situ using magnetic resonance imaging (MRI) and scanning electron microscopy (SEM). In the absence of the external magnetic trigger, the carnosine was found to be released from the polymer in a linear profile; however, over 50% of the drug could be released within 30 minutes of exposure to the rotating magnetic field. In addition, the release of carnosine embedded on the surface of the nano-rods was delayed if it was mixed with the iron oxide nano rods before the encapsulation. These new drug delivery vesicles have the potential to pave the way towards the safe and triggered release of onsite drug delivery, as part of a theragnostic treatment for glioblastoma., Competing Interests: The authors declare no conflict of interest., (This journal is © The Royal Society of Chemistry.)

The physics of self-propelled objects at the nanoscale is a rapidly developing research field where recent experiments have focused on the motion of individual catalytic enzymes. Contrary to the experimental advancements, theoretical understanding of the possible self-propulsion mechanisms at these scales is limited. A particularly puzzling question concerns the origins of the reportedly high diffusivities of the individual enzymes. Here we start with the fundamental principle of microscopic reversibility (MR) of chemical reactions powering self-propulsion and demonstrate that MR can lead to an increase of the particle mobility and of the short- and long-time diffusion coefficients as compared to dynamics where MR is neglected. Furthermore, the derived diffusion coefficients are enhanced due to the action of an external force. These results can shed new light on interpretations of the measured diffusivities and help to test the relevance of MR for the active motion of individual nanoswimmers.

Derivatives of the widely used 1,6-diphenyl-1,3,5-hexatriene molecular probe have been considered using a multiscale approach involving spin-flip time-dependent density functional theory, classical molecular dynamics and hybrid quantum mechanics/molecular mechanics. We identify a potential probe of membrane phase ( i.e. to preferentially detect liquid-ordered regions of lipid bilayers), which exhibits restricted access to a conical intersection in the liquid-ordered phase but is freely accessible in less ordered molecular environments. The characteristics of this probe also mark it as a candidate for an aggregation induced emission fluorophore.

We report the first examples of radical-cation salts of BEDT-TTF with spiroborate anions [B(mandelate) 2 ] - and [B(2-chloromandelate) 2 ] - , synthesized from either enantiopure or racemic bidentate mandelate or chloromandelate ligands. In the salts prepared using enantiopure ligands only one of two diastereoisomers of the spiroborate anion is incorporated, with the boron centre having the same stereochemistry as the enantiopure ligand. For the racemic salts one racemic pair of spiroborate anions containing an R and an S mandelate ligand is incorporated. In certain solvents helical crystals were obtained when using spiroborate anions with enantiopure ligands. Electrical and magnetic properties, and band structure calculations are reported.

We report how Raman difference imaging provides insight on cellular biochemistry in vivo as a function of sub-cellular dimensions and the cellular environment. We show that this approach offers a sensitive diagnostic to address blood biochemistry at the cellular level. We examine Raman microscopic images of the distribution of the different hemoglobins in both healthy (discocyte) and unhealthy (echinocyte) blood cells and interpret these images using pre-calculated, accurate pre-resonant Raman tensors for scattering intensities specific to hemoglobins. These tensors are developed from theoretical calculations of models of the oxy, deoxy and met forms of heme benchmarked against the experimental visible spectra of the corresponding hemoglobins. The calculations also enable assignments of the electronic transitions responsible for the colour of blood: these are mainly ligand to metal charge transfer transitions., Competing Interests: The authors declare no competing interests., (This journal is © The Royal Society of Chemistry.)

A hydrophobic heptapeptide, with sequence AFILPTG, as part of a phage capsid protein binds effectively to silica particles carrying negative charge. Here, we explore the silica binding activity of the sequence as a short polypeptide with polar N and C terminals. To describe the structural changes that occur on binding, we fit experimental infrared, Raman and circular dichroism data for a number of structures simulated in the full configuration space of the hepta-peptide using replica exchange molecular dynamics. Quantum chemistry was used to compute normal modes of infrared and Raman spectra and establish a relationship to structures from MD data. To interpret the circular dichroism data, instead of empirical factoring of optical activity into helical/sheet/random components, we exploit natural transition orbital theory and specify the contributions of backbone amide units, side chain functional groups, water, sodium ions and silica to the observed transitions. Computed optical responses suggest a less folded backbone and importance of the N-terminal when close to silica. We further discuss the thermodynamics of the interplay of charged and hydrophobic moieties of the polypeptide on association with the silica surface. The outcomes of this study may assist in the engineering of novel artificial bio-silica heterostructures.

The mechanical properties of a disordered heterogeneous medium depend, in general, on a complex interplay between multiple length scales. Connecting local interactions to macroscopic observables, such as stiffness or fracture, is thus challenging in this type of material. Here, we study the properties of a cohesive granular material composed of glass beads held together by soft polymer bridges. We characterise the mechanical response of single bridges under traction and shear, using a setup based on the deflection of flexible micropipettes. These measurements, along with information from X-ray microtomograms of the granular packings, then inform large-scale discrete element model (DEM) simulations. Although simple, these simulations are constrained in every way by empirical measurement and accurately predict mechanical responses of the aggregates, including details on their compressive failure, and how the material's stiffness depends on the stiffness and geometry of its parts. By demonstrating how to accurately relate microscopic information to macroscopic properties, these results provide new perspectives for predicting the behaviour of complex disordered materials, such as porous rock, snow, or foam.

We report the first example of a chiral BDH-TTP radical-cation salt. Chirality is induced in the structure via the use of a chiral spiroboronate anion where three stereocentres are present, one on each chiral ligand and one on the boron centre. Despite starting from a labile racemic mixture of BS and BR enantiomers, only one enantiomer is present in the crystal lattice. The anions pack in a novel double anion layer which is the thickest anion layer found in a BDH-TTP salt. This material is chiral and shows metallic behaviour down to at least 4.2 K.

Although street artists have the know-how to blow bubbles over one meter in length, the bubble width is typically determined by the size of the hoop, or wand they use. In this article we explore a regime in which, by blowing gently downwards, we generate bubbles with radii up to ten times larger than the wand. We observe the big bubbles at lowest air speeds, analogous to the dripping mode observed in droplet formation. We also explore the impact of the surfactant chosen to stabilize the bubbles. We are able to create bubbles of comparable size using either Fairy liquid, a commercially available detergent often used by street artists, or sodium dodecyl sulfate (SDS) solutions. The bubbles obtained from Fairy liquid detach from the wand and are stable for several seconds, however those from SDS tend to burst just before detachment.

Over the last decade, 3D bioprinting has received immense attention from research communities for developing functional tissues. Thanks to the complexity of tissues, various bioprinting methods have been exploited to figure out the challenges of tissue fabrication, in which hydrogels are widely adopted as a bioink in cell printing technologies based on the extrusion principle. Thus far, there is a wealth of literature proposing the crucial parameters of extrusion-based bioprinting of hydrogel biomaterials (e.g., hydrogel properties, printing conditions, and tissue scaffold design) toward enhancing performance. Despite the growing research in this field, numerous challenges that hinder advanced applications still exist. Herein, the most recently reported hydrogel-based bioprinted scaffolds, i.e., skin, bone, cartilage, vascular, neural, and muscular (including skeletal, cardiac, and smooth) scaffolds, are systematically discussed with an emphasis on the advanced fabrication techniques from the tissue engineering perspective. The methods covered include multiple-dispenser, coaxial, and hybrid 3D bioprinting. The present work is a unique study to figure out the opportunities of the novel techniques to fabricate complicated constructs with structural and functional heterogeneity. Finally, the principal challenges of current studies and a vision of future research are presented.

The G-protein coupled receptors (GPCRs) superfamily comprise similar proteins arranged into families or classes thus making it one of the largest in the mammalian genome. GPCRs take part in many vital physiological functions making them targets for numerous novel drugs. GPCRs share some distinctive features, such as the seven transmembrane domains, they also differ in the number of conserved residues in their transmembrane domain. Here we provide an introductory and accessible review detailing the computational advances in GPCR pharmacology and drug discovery. An overview is provided on family A-C GPCRs; their structural differences, GPCR signalling, allosteric binding and cooperativity. The dielectric constant (relative permittivity) of proteins is also discussed in the context of site-specific environmental effects., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

In this work, we investigated the effect of the suspension properties on the drying dynamics and the resulting film peeling instability. To do so, a comprehensive series of experiments were conducted using drops of aqueous mixtures of colloidal silica dispersions and polyethylene oxide (PEO) additives. Time-lapse digital microscope images of the evaporating droplets show that film peeling can be discouraged and eventually eliminated with an increase in PEO concentration and molecular weight. This is due to the additives modifying the suspension properties which in turn modify the drying front length across the evaporating surface. Our result extends the understanding of the physics of film failure which is relevant information for various industrial processes such as in inkjet printing and coating applications.

Materials exhibiting both chirality and conductivity do not exist in nature and very few examples have been synthesised. We report here the synthesis of a chiral molecular metal which remains metallic down to at least 4.2 K. This material also exhibits room-temperature switching capabilities with a transition upon cooling below 10 °C.

We report the fabrication of a solution-processed n-type Thin Film Transistor (TFT) with current on/off ratios of 10 4 , a turn-on voltage ( V ON ) of 1.2 V and a threshold voltage ( V T ) of 6.2 V. The TFT incorporates an insoluble and intractable dielectric layer ( k = 7-9) prepared in situ from solution-processed and then photopolymerised ligand-stabilised, inorganic/organic TiO 2 nanorods. A solution processed zinc oxide (ZnO) layer acts as the semiconductor. The new surface-modified TiO 2 nanorods were synthesised using a ligand replacement process with a monolayer coating of photopolymerisable 10-undecynylphosphonic acid (10UCYPA) to render them both soluble in common organic solvents and be photopolymerisable using UV-illumination after having been deposited on substrate surfaces from solution and drying., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

This work shows the enhancement of the visible photocatalytic activity of TiO 2 NPs film using the localized surface plasmonic resonance of Au nanostructures. We adopted a simple yet effective surface treatment to tune the size distribution, and plasmonic resonance spectrum of Au nanostructured films on glass substrates, by hot plate annealing in air at low temperatures. A hybrid photocatalytic film of TiO 2 :Au is utilized to catalyse a selective photodegradation reaction of Methylene Blue in solution. Irradiation at the plasmonic resonance wavelength of the Au nanostructures provides more effective photodegradation compared to broadband artificial sunlight of significantly higher intensity. This improvement is attributed to the active contribution of the plasmonic hot electrons injected into the TiO 2 . The broadband source initiates competing photoreactions in the photocatalyst, so that carrier transfer from the catalyst surface to the solution is less efficient. The proposed hybrid photocatalyst can be integrated with a variety of device architectures and designs, which makes it highly attractive for low-cost photocatalysis applications., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The advantages of two dimensional covalent organic framework membranes to achieve high flux have been demonstrated, but the capability of easy structural modification to manipulate the pore size has not been fully explored yet. Here we report the use of the Langmuir-Blodgett method to synthesize two ultrathin covalent organic framework membranes ( TFP-DPF and TFP-DNF ) that have a similar framework structure to our previously reported covalent organic framework membrane ( TFP-DHF ) but different lengths of carbon chains aiming to rationally control the pore size. The membrane permeation results in the applications of organic solvent nanofiltration and molecular sieving of organic dyes showed a systematic shift of the membrane flux and molecular weight cut-off correlated to the pore size change. These results enhanced our fundamental understanding of transport through uniform channels at nanometer scales. Pore engineering of the covalent organic framework membranes was demonstrated for the first time., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

We demonstrate electrically controlled linear translation and precision positioning of a colloidal particle in a soft matter device. The basis of transportation is the time dependent electric field reconfiguration and manipulation of a topological line defect between two distinct hybrid aligned nematic liquid crystal domains having opposing tilt orientations. Deliberately tuning an applied voltage relative to a low threshold value (5.7 V at 1 kHz) permits defect trapping of the colloidal particle and allows subsequent control over the particle's velocity and bidirectional linear movement over millimeter distances, without the need for externally imposed flow nor for lateral confining walls.