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Superglassy membranes synthesised by polymers of intrinsic microporosity (PIMs) suffer from physical aging and show poor gas permeance over time, especially thin membranes, due to the fast rearrangement of nonequilibrium polymer chains. Herein, we constructed a novel PIM-1 thin film nanocomposite membrane (TFN) using nanosized UiO-66−NH2 (≈10 nm)/carboxylated PIM-1 (cPIM-1) as the composite filler. Unlike conventional fillers, which interact with the polymer only via the surface, the UiO-66−NH2/cPIM-1 forms a stable three-dimensional (3D) network intertwining with the polymer chains, being very effective to impede chain relaxation, and thus physical aging. Nanosizing of UiO-66−NH2 was achieved by regulating the nucleation kinetics using carbon quantum dots (CQD) during the synthesis. This led to increased surface area, and hence more functional groups to bond with cPIM-1 (via hydrogen bonding between −NH2 and −COOH groups), which also improved interfacial compatibility between the 3D network and polymer chains avoiding defect formation. As a result, the novel TFN showed significantly improved performance in gas separation along with reduced aging (i.e. ≈6 % loss in CO2 permeability over 63 days); the aged membranes had a CO2 permeance of 2504 GPU and ideal selectivity values of 37.2 and 23.8 for CO2/N2 and CO2/CH4, respectively.

Bioorthogonal catalysis employing transition metal catalysts is a promising strategy for the in situ synthesis of imaging and therapeutic agents in biological environments. The transition metal Pd has been widely used as a bioorthogonal catalyst, but bare Pd poses challenges in water solubility and catalyst stability in cellular environments. In this work, Pd(0) loaded amphiphilic polymeric nanoparticles are applied to shield Pd in the presence of living cells for the in situ generation of a fluorescent dye and anticancer drugs. Pd(0) loaded polymeric nanoparticles prepared by the reduction of the corresponding Pd(II)-polymeric nanoparticles are highly active in the deprotection of pro-rhodamine dye and anticancer prodrugs, giving significant fluorescence enhancement and toxigenic effects, respectively, in HepG2 cells. In addition, we show that the microstructure of the polymeric nanoparticles for scaffolding Pd plays a critical role in tuning the catalytic efficiency, with the use of the ligand triphenylphosphine as a key factor for improving the catalyst stability in biological environments.

This work presents a detailed analysis of the performance of X-ray magnetic circular dichroism photoemission electron microscopy (XMCD-PEEM) as a tool for vector reconstruction of magnetization. For this, 360° domain wall ring structures which form in a synthetic antiferromagnet are chosen as the model to conduct the quantitative analysis. An assessment is made of how the quality of the results is affected depending on the number of projections that are involved in the reconstruction process, as well as their angular distribution. For this a self-consistent error metric is developed which allows an estimation of the optimum azimuthal rotation angular range and number of projections. This work thus proposes XMCD-PEEM as a powerful tool for vector imaging of complex 3D magnetic structures.

Magnetic sensors are used in many technologies and industries, such as medicine, telecommunications, robotics, the Internet of Things, etc. The sensitivity of these magnetic sensors is a key aspect, as it determines their precision. In this article, we investigate how a thin windmill-like ferromagnetic system can hugely concentrate a magnetic field at its core. A magnetic sensor combined with such a device enhances its sensitivity by a large factor. We describe the different effects that provide this enhancement: the thickness of the device and its unique windmill-like geometry. An expression for the magnetic field in its core is introduced and verified using finite-element calculations. The results show that a high magnetic field concentration is achieved for a low thickness-diameter ratio of the device. Proof-of-concept experiments further demonstrate the significant concentration of the magnetic field when the thickness-diameter ratio is low, reaching levels up to 150 times stronger than the applied field.

Quantum biological tunnelling for electron transfer is involved in controlling essential functions for life such as cellular respiration and homoeostasis. Understanding and controlling the quantum effects in biology has the potential to modulate biological functions. Here we merge wireless nano-electrochemical tools with cancer cells for control over electron transfer to trigger cancer cell death. Gold bipolar nanoelectrodes functionalized with redox-active cytochrome c and a redox mediator zinc porphyrin are developed as electric-field-stimulating bio-actuators, termed bio-nanoantennae. We show that a remote electrical input regulates electron transport between these redox molecules, which results in quantum biological tunnelling for electron transfer to trigger apoptosis in patient-derived cancer cells in a selective manner. Transcriptomics data show that the electric-field-induced bio-nanoantenna targets the cancer cells in a unique manner, representing electrically induced control of molecular signalling. The work shows the potential of quantum-based medical diagnostics and treatments.

Cytochrome c (Cyt c), known for its functional redox capabilities, plays a pivotal role in biological processes such as the electron transport chain and apoptosis. However, understanding how different conjugation strategies impact its structural and redox characteristics is limited. To fill this gap, we investigated the effects of conjugating Cyt c and a zinc(II) porphyrin (Zn Porph) to gold nanoparticles (AuNPs). We used circular dichroism (CD) spectroscopy to detect structural conformational changes in Cyt c upon conjugation and time-of-flight secondary ion mass spectrometry (ToF-SIMS) to identify protein orientation. Cyt c was predicted to have different orientations depending on the size of AuNPs and methods used to conjugate the protein, it was hypothesised that the orientation of Cyt c may influence the redox properties of the protein. The electrochemical properties of Cyt c were assessed using cyclic voltammetry (CV) and differential pulse voltammetry (DPV). We used DPV-based to determine the heterogeneous rate constant (k0). The results show a lower k0for conjugated Cyt c than free Cyt c, likely due to structural changes in the protein. The spatial orientation of Cyt c had minimal influence on k0, while ligand density and AuNP size had an effect. The k0 value of Zn Porph did not decrease on conjugation. Despite these changes, Cyt c and Zn Porph maintained their electrochemical capabilities after conjugation.

Several studies have reported the successful use of bio-orthogonal catalyst nanoparticles (NPs) for cancer therapy. However, the delivery of the catalysts to the target tissues in vivo remains an unsolved challenge. The combination of catalytic NPs with extracellular vesicles (EVs) has been proposed as a promising approach to improve the delivery of therapeutic nanomaterials to the desired organs. In this study, we have developed a nanoscale bio-hybrid vector using a CO-mediated reduction at low temperature to generate ultrathin catalytic Pd nanosheets (PdNSs) as catalysts directly inside cancer-derived EVs. We have also compared their biodistribution with that of PEGylated PdNSs delivered by the EPR effect. Our results indicate that the accumulation of PdNSs in the tumour tissue was significantly higher when they were administered within the EVs compared to the PEGylated PdNSs. Conversely, the amount of Pd found in non-target organs (i.e., liver) was lowered. Once the Pd-based catalytic EVs were accumulated in the tumours, they enabled the activation of a paclitaxel prodrug demonstrating their ability to carry out bio-orthogonal uncaging chemistries in vivo for cancer therapy.

A novel approach to improve the initial performance as well as to prevent physical aging of superglassy high free volume polymer PIM-1 is reported. Bis(phenyl)fluorene-based polymer of intrinsic microporosity (Cardo-PIM-1) was used at different loadings in PIM-1 to fabricate thin film composite (TFC) membranes and freestanding membranes. The gas performances of both TFCs and thick freestanding membranes exhibited similar trends; higher CO2 permeance and higher CO2/CH4 selectivity at relatively low loadings (≤5 wt %). TFCs containing 5 wt % Cardo-PIM-1 achieved a CO2 permeance of (12600 ± 866 GPU), which corresponds to about a threefold increase as compared to the pristine TFC-PIM-1 membranes (2850 ± 254 GPU) and higher CO2/CH4 selectivity (14.6 ± 1.3) as compared to pure PIM-1 (10 ± 3). With regards to physical aging, PIM-1 TFC membranes experienced a 96 % reduction in CO2 permeance after 1 year. However, for the TFCs containing 5 wt % cardo the reduction was considerably lower (59%) and all took place at an initial stage of up to 37 days, remaining at a good and stable CO2 permeance of c.a. 5000 GPU for the remaining testing period of up to one year.

Smart materials with controlled stimuli-responsive functions are at the forefront of technological development. In this work, we present a generic strategy that combines simple components, physicochemical responses, and easy fabrication methods to achieve a dual stimuli-responsive system capable of location-specific antimicrobial cargo delivery. The encapsulated system is fabricated by combining a biocompatible inert polymeric matrix of poly(dimethylsiloxane) (PDMS) and a bioactive cargo of saturated fatty acids. We demonstrate the effectiveness of our approach to deliver antimicrobial activity for the model bacteria Escherichia coli. The system responds to two control variables, temperature and pH, delivering two levels of antimicrobial response under distinct combinations of stimuli: one response toward the planktonic media and another response directly at the surface for sessile bacteria. Spatially resolved Raman spectroscopy alongside thermal and structural material analysis reveals that the system not only exhibits ON/OFF states but can also control relocation and targeting of the active cargo toward either the surface or the liquid media, leading to different ON/OFF states for the planktonic and sessile bacteria. The approach proposed herein is technologically simple and scalable, facing low regulatory barriers within the food and healthcare sectors by using approved components and relying on fundamental chemical processes. Our results also provide a proof-of-concept platform for the design and easy fabrication of delivery systems capable of operating as Boolean logic gates, delivering different responses under different environmental conditions.

The recent claim of room temperature superconductivity in a copper-doped lead apatite compound, called LK-99, has sparked remarkable interest and controversy. Subsequent experiments have largely failed to reproduce the claimed superconductivity, while theoretical works have identified multiple key features including strong electronic correlation, structural instabilities, and dopability constraints. A puzzling claim of several recent theoretical studies is that both parent and copper-doped lead apatite structures are dynamically unstable at the harmonic level, questioning decades of experimental reports of the parent compound structures and the recently proposed copper-doped structures. In this work, we demonstrate that both parent and copper-doped lead apatite structures are dynamically stable at room temperature. Anharmonic phonon–phonon interactions play a key role in stabilizing some copper-doped phases, while most phases are largely stable even at the harmonic level. We also show that dynamical stability depends on both volume and correlation strength, suggesting controllable ways of exploring the copper-doped lead apatite structural phase diagram. Our results fully reconcile the theoretical description of the structures of both parent and copper-doped lead apatite with the experiment.

The characterization of thin films containing nanopores with diameters exceeding 50 nm poses significant challenges, especially when deploying sorption-based techniques. Conventional volumetric physisorption or mercury intrusion methods have limited applicability in thin films due to constraints in sample preparation and nondestructive testing. In this context, ellipsometric porosimetry represents a viable alternative, leveraging its optical sensitivity to thin films. With existing setups relying on the capillary condensation of volatile compounds such as water, applicability is typically restricted to pore dimensions <50 nm. In this study, we introduce two high-molar-mass hydrocarbon adsorptives, namely ethylbenzene and n-nonane. These adsorptives exhibit substantial potential in improving the accuracy of physisorption measurements beyond mesoporosity (i.e., >50 nm). Specifically, with n-nonane, applicability is extended up to 80 nm pores. Our measurement guidelines propose a nondestructive, expeditious (<60 min), low-pressure (<0.03 bar) approach to investigate nanoporous thin films with potential adaptability to diverse structural architectures.

The bacterial plant pathogen Xylella fastidiosa causes disease in several globally important crops. However, some cultivars harbour reduced bacterial loads and express few symptoms. Evidence considering plant species in isolation suggests xylem structure influences cultivar susceptibility to X. fastidiosa. We test this theory more broadly by analysing high-resolution synchrotron X-ray computed tomography of healthy and infected plant vasculature from two taxonomic groups containing susceptible and resistant varieties: two citrus cultivars (sweet orange cv. Pera, tangor cv. Murcott) and two olive cultivars (Koroneiki, Leccino). Results found the susceptible plants had more vessels than resistant ones, which could promote within-host pathogen spread. However, features associated with resistance were not shared by citrus and olive. While xylem vessels in resistant citrus stems had comparable diameters to those in susceptible plants, resistant olives had narrower vessels that could limit biofilm spread. And while differences among olive cultivars were not detected, results suggest greater vascular connectivity in resistant compared to susceptible citrus plants. We hypothesize that this provides alternate flow paths for sustaining hydraulic functionality under infection. In summary, this work elucidates different physiological resistance mechanisms between two taxonomic groups, while supporting the existence of an intertaxonomical metric that could speed up the identification of candidate-resistant plants.

Injection-induced seismicity has become one of the most critical challenges for the widespread deployment of Enhanced Geothermal Systems (EGS). In particular, some EGS development projects have led to large, damaging earthquakes that unexpectedly occurred far off the stimulated reservoir region and, in particular, after stopping fluid injection. Yet, the causative mechanisms of these seismicity patterns remain highly elusive. Here, we identify a combination of mechanisms that could explain delayed seismicity in EGS sites by conducting fully-coupled hydromechanical simulations of the hydraulic stimulation of a naturally-fractured granitic reservoir. The model comprises a sparse network of long, variably-oriented fractures interacting with a nearby, critically-oriented fault. The results show that the presence of fractures introduces notable nonlinearities in the flow field and rock deformation and significantly expands the rock volume affected by fluid injection. First, the stimulated fracture network provides highly-permeable conduits for communicating elevated pore pressure over long distances. Second, the anisotropic expansion of fractures generates shear stress that is transmitted almost instantaneously across the reservoir. The pore pressure and stress perturbations can not only cause slip along fractures, inducing (micro)seismicity during injection, but also affect the stability of nearby faults, which may not necessarily be pressurized during injection. The transferred poroelastic stresses can increase or decrease the slip tendency along different fault segments. However, the fault may reactivate only after several months following injection when a progressive pore pressure diffusion modulated by the transient fault permeability evolution brings a critically-stressed fault segment to failure conditions. We also find that the spatiotemporal evolution of seismicity depends largely on the nearby fault orientation, hydromechanical properties, and hydraulic connect

Illicit drug consumption constitutes a great concern worldwide due to its increased spread and abuse, and the negative consequences exerted on society. For instance, 3,4-methylenedioxymethamphetamine (MDMA), a synthetic amphetamine-type substance, was abused by 20 million people worldwide in 2020. This psychoactive substance exerts a myriad of effects on the human body being dangerous for the consumer’s health. Besides, MDMA has been used in the treatment of some psychiatric conditions. Therefore, the development of wearable devices for MDMA sensing in biological fluids is of great importance for forensic toxicology (e.g., monitoring of patients with suspected or known MDMA consumption) as well as for therapeutic management of patients. Herein, we report the development of a wearable electrochemical platform based on a hollow microneedle (MN) array sensor for the monitoring of MDMA in the interstitial fluid by square-wave voltammetry. First, the holes of the MN array were modified with conductive pastes to devise a MN patch with a three-electrode system. Subsequently, the functionalization of the working electrode with nanomaterials enhanced MDMA detection. Thereafter, analytical parameters were evaluated exhibiting a slope of 0.05 µA µM−1 within a linear range from 1 to 50 µM and a limit of detection of 0.75 µM in artificial interstitial fluid. Importantly, critical parameters such as selectivity, piercing capability, temperature, reversibility and stability were assessed. Overall, the obtained MN sensor exhibited excellent analytical performance, making it a promising tool for MDMA tracking in interstitial fluid for individuals on probation or under therapeutic treatment.

Implantable drug delivery systems (IDDS) are an attractive alternative to conventional drug administration routes. Oral and injectable drug administration are the most common routes for drug delivery providing peaks of drug concentrations in blood after administration followed by concentration decay after a few hours. Therefore, constant drug administration is required to keep drug levels within the therapeutic window of the drug. Moreover, oral drug delivery presents alternative challenges due to drug degradation within the gastrointestinal tract or first pass metabolism. IDDS can be used to provide sustained drug delivery for prolonged periods of time. The use of this type of systems is especially interesting for the treatment of chronic conditions where patient adherence to conventional treatments can be challenging. These systems are normally used for systemic drug delivery. However, IDDS can be used for localised administration to maximise the amount of drug delivered within the active site while reducing systemic exposure. This review will cover current applications of IDDS focusing on the materials used to prepare this type of systems and the main therapeutic areas of application.

We set up the theory for a distributed algorithm for computing persistent homology. For this purpose we develop linear algebra of persistence modules. We present bases of persistence modules, together with an operation that leads to a method for obtaining images, kernels and cokernels of tame persistence morphisms. Our focus is on developing efficient methods for the computation of homology of chains of persistence modules. Later we give a brief, self-contained presentation of the Mayer–Vietoris spectral sequence. Then we study the Persistent Mayer-Vietoris spectral sequence and present a solution to the extension problem. This solution is given by finding coefficients that indicate gluings between bars on the same dimension. Finally, we review PERMAVISS, an algorithm that computes all pages in the spectral sequence and solves the extension problem. This procedure distributes computations on subcomplexes, while focusing on merging homological information. Additionally, some computational bounds are found which confirm the distribution of the method.and present a solution to the extension problem. This solution is given by finding coefficients that indicate gluings between bars on the same dimension. Finally, we review PerMaViss, an algorithm that computes all pages in the spectral sequence and solves the extension problem. This procedure distributes computations on subcomplexes, while focusing on merging homological information. Additionally, some computational bounds are found which confirm the distribution of the method.

Investigation into the reactive oxygen species (ROS) generating abilities of photosensitizers outside of in-vitro/vivo conditions is a crucial element in the wider study of photodynamic therapy (PDT) in clinical settings. Zinc(II) phthalocyanine tetrasulfonic acid (ZnPcTS) is a water-soluble photosensitizer that can generate ROS as singlet oxygen (SO) under irradiation in the red and far-red region of the electromagnetic spectrum. The incorporation of ZnPcTS into nano-fibers of a bis-imidazolium hydrogel was demonstrated and the material was characterized with photophysical, rheological, and microscopy techniques. This supramolecular material containing ZnPcTS (named ZnPcTS_nEqBase@Gels) was found to significantly enhance the SO generation rate with respect to that of ZnPcTS in an aqueous solution. The effect is attributed mainly to reduced aggregation within the gel microenvironment compared with a solution. Furthermore, the preparation of ZnPcTS_nEqBase@Gels was carried out in the presence of varying amounts (0, 1, 2, 3, 4 eq.) of NaOH to improve the dissolution of ZnPcTSby ensuring full deprotonation of the sulfonate. The gel material containing 4 equivalents of NaOH per phthalocyanine was found to have a significantly greater SO-generating ability than the corresponding material containing no base. This phenomenon was shown to be partially a consequence of reduced aggregation as observed in the spectroscopic characterization. The enhancement in SO generation induced by this type of hybrid material makes it an attractive candidate to be used in different applications when efficient SO production is required.

Magnetic metamaterials have demonstrated promising perspectives to improve the efficiency of magnetic flux concentrators. In this work, the effects of downscaling these devices for on-chip integration is investigated. The influence of the non-linear magnetic response of the ferromagnetic components, their magnetic irreversibility, the formation of magnetic domains, as well as the effects of geometry and size of the devices are scrutinized. The results demonstrate that the implementation of metasurfaces at the microscale opens up new technological possibilities for enhancing the performance of magnetic field detectors and remotely charging small electric devices, thus paving the way toward new approaches in information and communication technologies.

General-purpose quantum computation and quantum simulation require multi-qubit architectures with precisely defined, robust interqubit interactions, coupled with local addressability. This is an unsolved challenge, primarily due to scalability issues. These issues often derive from poor control over interqubit interactions. Molecular systems are promising materials for the realization of large-scale quantum architectures, due to their high degree of positionability and the possibility to precisely tailor interqubit interactions. The simplest quantum architecture is the two-qubit system, with which quantum gate operations can be implemented. To be viable, a two-qubit system must possess long coherence times, the interqubit interaction must be well defined and the two qubits must also be addressable individually within the same quantum manipulation sequence. Here results are presented on the investigation of the spin dynamics of chlorinated triphenylmethyl organic radicals, in particular the perchlorotriphenylmethyl (PTM) radical, a mono-functionalized PTM, and a biradical PTM dimer. Extraordinarily long ensemble coherence times up to 148 µs are found at all temperatures below 100 K. Two-qubit and, importantly, individual qubit addressability in the biradical system are demonstrated. These results underline the potential of molecular materials for the development of quantum architectures.

There is a close relationship between the SARS-CoV-2 virus and lipoproteins, in particular high-density lipoprotein (HDL). The severity of the coronavirus disease 2019 (COVID-19) is inversely correlated with HDL plasma levels. It is known that the SARS-CoV-2 spike (S) protein binds the HDL particle, probably depleting it of lipids and altering HDL function. Based on neutron reflectometry (NR) and the ability of HDL to efflux cholesterol from macrophages, we confirm these observations and further identify the preference of the S protein for specific lipids and the consequent effects on HDL function on lipid exchange ability. Moreover, the effect of the S protein on HDL function differs depending on the individuals lipid serum profile. Contrasting trends were observed for individuals presenting low triglycerides/high cholesterol serum levels (LTHC) compared to high triglycerides/high cholesterol (HTHC) or low triglycerides/low cholesterol serum levels (LTLC). Collectively, these results suggest that the S protein interacts with the HDL particle and, depending on the lipid profile of the infected individual, it impairs its function during COVID-19 infection, causing an imbalance in lipid metabolism.

Cyclic di-AMP is the only known essential second messenger in bacteria and archaea, regulating different proteins indispensable for numerous physiological processes. In particular, it controls various potassium and osmolyte transporters involved in osmoregulation. In Bacillus subtilis, the K+/H+ symporter KimA of the KUP family is inactivated by c-di-AMP. KimA sustains survival at potassium limitation at low external pH by mediating potassium ion uptake. However, at elevated intracellular K+ concentrations, further K+ accumulation would be toxic. In this study, we reveal the molecular basis of how c-di-AMP binding inhibits KimA. We report cryo-EM structures of KimA with bound c-di-AMP in detergent solution and reconstituted in amphipols. By combining structural data with functional assays and molecular dynamics simulations we reveal how c-di-AMP modulates transport. We show that an intracellular loop in the transmembrane domain interacts with c-di-AMP bound to the adjacent cytosolic domain. This reduces the mobility of transmembrane helices at the cytosolic side of the K+ binding site and therefore traps KimA in an inward-occluded conformation.

Quantum tunneling rotors in a zeolitic imidazolate framework ZIF-8 can provide insights into local gas adsorption sites and local dynamics of porous structure, which are inaccessible to standard physisorption or x-ray diffraction sensitive primarily to long-range order. Using in situ high-resolution inelastic neutron scattering at 3 K, we follow the evolution of methyl tunneling with respect to the number of dosed gas molecules. While nitrogen adsorption decreases the energy of the tunneling peak, and ultimately hinders it completely (0.33 meV to zero), argon substantially increases the energy to 0.42 meV. Ab initio calculations of the rotational barrier of ZIF-8 show an exception to the reported adsorption sites hierarchy, resulting in anomalous adsorption behavior and linker dynamics at subatmospheric pressure. The findings reveal quantum tunneling rotors in metal-organic frameworks as a sensitive atomistic probe of local physicochemical phenomena.

The use of magnetic vector tomography/laminography has opened a 3D experimental window to access the magnetization at the nanoscale. These methods exploit the dependence of the magnetic contrast in transmission to recover its 3D configuration. However, hundreds of different angular projections are required leading to large measurement times. Here we present a fast method to dramatically reduce the experiment time specific for quasi two-dimensional magnetic systems. The algorithm uses the Beer-Lambert equation in the framework of X-ray transmission microscopy to obtain the 3D magnetic configuration of the sample. It has been demonstrated in permalloy microstructures, reconstructing the magnetization vector field with a reduced number of angular projections obtaining quantitative results. The throughput of the methodology is × 10–× 100 times faster than conventional magnetic vector tomography, making this characterization method of general interest for the community.

The polymer of intrinsic microporosity PIM-1 was synthesized with different topologies and negligible network content. A more rapid heating rate from room temperature yielded a predominantly di-substituted PIM-1 (D-PIM-1), whereas a marginally lower heating rate produced a more branched structure (B-PIM-1). Both polymers were acid-hydrolyzed to give carboxylic acid functionalization (cPIM-1), as indicated by FT-IR, 1H NMR, and elemental analysis. Both PIM-1 and cPIM-1 were processed into self-supported membranes and into thin film composite (TFC) membranes on a polyacrylonitrile support. For a 70% hydrolyzed polymer (D-cPIM-1-70%), the initial CO2 permeance reached 7700 GPU, with ideal selectivity of 56 for CO2/N2 and 37 for CO2/CH4. D-PIM-1 and D-cPIM-1-70% showed 85% and 52% CO2 permeance drop after 60 days’ aging, respectively. B-PIM-1, with initial CO2 permeance of 3100 GPU and ideal selectivity of 19 for CO2/N2 and 11 for CO2/CH4, showed only a 65% decrease. Polymer that was both branched and hydrolyzed (B-cPIM-1-73&81%), with CO2 permeance of 3200 GPU and selectivity of 64 for CO2/N2 and 45 for CO2/CH4, showed no decrease of CO2 permeance after 60 days. The branched structure is crucial for reducing membrane aging. Plasticization gave rise to reduced selectivity in mixed gas experiments, but nevertheless TFC membranes prepared from B-cPIM-1-81% were able to concentrate CO2 to 38% from a 10% CO2/90% N2 mixture at 4.8 bar.

Chiral diketopyrrolopyrroles appended with enantiomeric ethyl lactate functions through an ether linkage to the aryl backbone of the chromophore were synthesized via the Mitsunobu reaction. The molecules have good solubility and excellent optical properties, high molar absorption coefficients, and fluorescence quantum yields. Helical aggregates with circular dichroism arising from the supramolecular arrangement are seen in both solution and thin films, and the aggregates also display circularly polarized luminescence (glum ≈ ±0.1). The molecules assemble to give monolayers on graphite and precipitate from solution forming supramolecular twisted tapes hundreds of microns long.

We report results from an in–plane and out–of–plane impedance study on SmB6 single crystals, performed at low temperatures and over a wide frequency range. A universal equivalent circuit describes the dielectric behavior of this system across the transition, from surface to bulk dominated electrical conduction between 2 and 10 K. We identify the resistive, capacitive, and inductive contributions to the impedance. The equivalent inductance, obtained from fits to experimental data, drops drastically with increasing temperature, as the bulk starts to control electrical conduction. Self–sustained voltage oscillations, observed below 6 K across small crystals when biased with a dc current, point to a large SmB6 self–capacitance, likely brought by the surface states.

Polyvinylidene fluoride (PVDF) membranes containing hydrophobic graphene nanofillers were prepared and tested for membrane distillation applications. The nanofillers were obtained by a two-step process: 1st) chemical grafting of hydrophobic molecules, either octylamine (OA) or perfluoroctylamine (PFOA), to graphene oxide (GO) nanosheets, and 2nd) chemical reduction of functionalized GO (rGO) to remove unreacted oxygen-containing functional groups. This resulted in OA-functionalized reduced GO (OA-rGO) and PFOA-functionalized rGO (PFOA-rGO). The addition of these nanomaterials to PVDF membranes prepared by the phase inversion process led to an increase in the membrane contact angle, and therefore higher hydrophobicity, as well as an increase in the membrane porosity. When comparing both nanofillers, OA-rGO and PFOA-rGO, the latter was more efficient in achieving higher contact angles due to the presence of fluorine atoms, whereas OA-rGO led to a greater enhancement in membrane porosity as compared to PFOA-rGO. MMMs containing 0.7 wt% nanofiller loadings of OA-rGO and PFOA-rGO achieved the highest water fluxes of 9.1 and 8.8 L m−2 h−1, respectively and salt rejection above 99.9%, which was monitored for at least 162 h of operation for the former. In comparison with pure PVDF (flux of 5 L m−2 h−1), the addition of OA-rGO and PFOA-rGO nanofillers results in a flux increment of 82% and 76%, respectively.

Membrane distillation (MD) is constantly acknowledged in the research literature as a promising technology for the future of desalination, with an increasing number of studies reported year after year. However, real MD applications still lag behind with only a few pilot-plant tests worldwide. The lack of technology transfer from academia to industry is caused by important gaps between its fundamental basis and the process design. Herein, we explore critical disconnections by conducting coupled mass and heat transfer modeling and MD simulations; we use well-known MD mass and heat transfer equations to model and simulate flux over a typical MD membrane for different geometries, areas, and operational conditions in direct contact configuration. From the analysis of the results, we propose research guidelines and process development strategies, and construct an MD module performance curve. From this graph, permeate flow rate, thermal energy consumption and outlet temperatures can be determined for given feed inlet conditions (temperature and concentration). Comprehensive tools such as this MD module curve and good communication between membrane developers and process engineers are required to accelerate the process of bringing the MD technology from a still-emerging status to a maturity level.

The stochastic wave function method is proposed to study the diffusion regimes of alkali atoms on metallic surfaces. The Lindblad approach, based on the microscopic Hamiltonian information in the Caldeira-Leggett model, is presented and numerical calculations of the dynamics are carried out to characterize surface diffusion for two different systems: Na-Cu(111) and Li-Cu(111). Calculations of the intermediate scattering function for an isolated adsorbate are compared, in the Brownian limit, with results deduced from helium spin-echo (HeSE) experiments after reducing them to single adsorbate dynamics. To illustrate the method we present the dependence on momentum transfer and the temperature dependency. Results show that the experiment can be described at a quantitative level by the 1-D quantum model (reduced dimensionality).

We assume information is discrete-modulated over coherent states of the single-mode electromagnetic field and transmitted over space quantum channels. In this letter, we provide a comparison of quantum detection with classical detection for communication using on-off keying (OOK) and binary phase shift keying (BPSK) for illustrative system parameters for LEO, MEO and GEO satellites. To do so, we assume an attenuation-only (pure-loss) channel and compute the Shannon capacities for the following detection methods: classical (shot-noise limited) single-photon and coherent detectors as well as optimal quantum hypothesis-testing (Helstrom) detection. As in classical system engineering design, we also obtain theoretical references for comparison, namely, Shannon capacities and Holevo bounds for the ideal Gaussian optical channel. Our results show the ranges of transmitted power and orbital heights for which either classical or quantum detection is optimal, thus providing useful insights into design guidelines and operations of future space communication systems. We also obtain the remarkable result that the BPSK Holevo bound achieves the ultimate quantum capacity of the considered channel.

Several technologies, including photodetection, imaging, and data communication, could greatly benefit from the availability of fast and controllable conversion of terahertz (THz) light to visible light. Here, we demonstrate that the exceptional properties and dynamics of electronic heat in graphene allow for a THz-to-visible conversion, which is switchable at a sub-nanosecond time scale. We show a tunable on/off ratio of more than 30 for the emitted visible light, achieved through electrical gating using a gate voltage on the order of 1 V. We also demonstrate that a grating-graphene metamaterial leads to an increase in THz-induced emitted power in the visible range by 2 orders of magnitude. The experimental results are in agreement with a thermodynamic model that describes blackbody radiation from the electron system heated through intraband Drude absorption of THz light. These results provide a promising route toward novel functionalities of optoelectronic technologies in the THz regime.

Graphene-based 2D nanomaterials possess unique physicochemical characteristics which can be utilized in various biomedical applications, including the transport and presentation of chemotherapeutic agents. In glioblastoma multiforme (GBM), intratumorally administered thin graphene oxide (GO) nanosheets demonstrate a widespread distribution throughout the tumor volume without impact on tumor growth, nor spread into normal brain tissue. Such intratumoral localization and distribution can offer multiple opportunities for treatment and modulation of the GBM microenvironment. Here, the kinetics of GO nanosheet distribution in orthotopic GBM mouse models is described and a novel nano-chemotherapeutic approach utilizing thin GO sheets as platforms to non-covalently complex a proteasome inhibitor, bortezomib (BTZ), is rationally designed. Through the characterization of the GO:BTZ complexes, a high loading capacity of the small molecule on the GO surface with sustained BTZ biological activity in vitro is demonstrated. In vivo, a single low-volume intratumoral administration of GO:BTZ complex shows an enhanced cytotoxic effect compared to free drug in two orthotopic GBM mouse models. This study provides evidence of the potential that thin and small GO sheets hold as flat nanoscale platforms for GBM treatment by increasing the bioavailable drug concentration locally, leading to an enhanced therapeutic effect.

The acceptor crystallinity has long been associated with favourable Organic Solar Cell (OSC) properties such as high mobility and fill factor. In particular, this applies to acceptor materials such as fullerene derivatives and the most recent Non-Fullerene Acceptors (NFAs), which are now surpassing a Power Conversion Efficiency (PCE) of 19%. Although these advantages are commonly attributed to their 3-dimensional crystal packing motif in the single crystal, the bridge that links the acceptor crystal packing from single crystals to solar cells has not clearly been shown yet. In this work, we investigate the molecular organisation of seven NFAs (o-IDTBR, IDIC, ITIC, m-ITIC, 4TIC, 4TICO, and m-4TICO), following the evolution of their packing motif in single-crystals, powder, and thin films made with pure NFAs and donor:NFA blends. We observed a good correlation between the NFA single crystal packing motif and their molecular arrangement in the bulk heterojunction. The NFA packing motif affects the material's propensity to form a highly crystalline domain in the blend. We specifically found that 3D reticular packing motifs show stronger ordering than 0D herringbone ones. However, the NFA packing motif is not directly correlating with device performance parameters. Although higher NFA crystallinity yields higher mobility, we found the domain purity to be more important for obtaining high efficiency organic solar cells by governing bimolecular recombination.

Addition of an excess of ZnMe2 to a mixture of [Ru(PPh3)3HCl] and IMes (IMes=1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene) yields the bis-cyclometallated complex, [Ru(IMes)“(PPh3)2] 2, together with the mono-cyclometallated, Ru−Zn heterobimetallic complex [Ru(IMes)′(PPh3)2(ZnMe)] 3. Treatment of 2 with H2, PhSiH3 or pinacolborane yields the previously reported complex, [Ru(IMes)′(PPh3)2H] 1, the synthesis of which has been reinvestigated. Further studies of small molecule reactivity show that 1 adds H2 to give [Ru(IMes)(PPh3)2H4] 4, whilst 2 reacts with catecholborane to give [Ru(IMes-Bcat)′(PPh3)2H] 5, in which (IMes-Bcat)′ signifies a borylated NHC ligand that is singly-metallated onto Ru. Treatment of 2 with CO gives the 18-electron dicarbonyl product [Ru(IMes)”(PPh3)(CO)2] 6. Compounds 1–3, 5 and 6 have been structurally characterised.

There is a need to develop rapidly responsive chemical sensors for the detection of low concentrations of volatile organic solvents (VOCs). Platinum pincer complexes have shown promise as sensors because of their colours and vapochromic and solvatochromic properties, that may be related to the non-covalent interactions between the pincer complexes and the guest VOCs. Here we report an investigation into a series of Pt(II) complexes based on the 1,3-di(pyridine)benzene tridentate (N⁁C⁁N) skeleton with the formula [Pt(N⁁C(R)⁁N)(CN)] (R = C(O)Me 2, C(O)OEt 3, C(O)OPh 4) with the fourth coordination site occupied by a cyanide ligand. Solid-state samples of the complexes have been tested with a range of volatiles including methanol, ethanol, acetone, dichloromethane and water, and while 2 displays thermochromism, 3 and 4 display rapidly reversible vapochromism and solvatochromism. These results are correlated with X-ray powder and single crystal X-ray structural data including an assessment of the crystal packing and the void space in the crystalline space. The cyanide ligand and the R substituents are involved in hydrogen bonding that creates the voids within the structures and interact with the solvent molecules that influence the Pt⋯Pt separation in the crystalline state.

The synthesis, spectroelectrochemical and structural characteristics of highly electron-accepting diketopyrrrolopyrrole (DPP) molecules with adjoining pyridinium rings is reported, along with an assessment of their toxicity, which is apparently low. The compounds show reversible electrochemistry and in one subfamily a massive increase in molar extinction coefficient upon electrochemical reduction.

Magneto-optical techniques are key tools for the characterization of magnetic effects at the nanoscale. Here, we present the dark-field magneto-optical Kerr effect (DFMOKE), a technique we have recently developed for the characterization of three-dimensional magnetic nanostructures. We introduce the principles of DFMOKE, based on the separation of an incident beam into multiple reflected beams when focusing on a 3D nano-geometry. We show the key modifications needed in a standard focused MOKE magnetometer to perform these measurements. Finally, we showcase the power of this method by detecting the magnetic switching of a single tilted 3D nanowire, independently from the switching of a magnetic thin film that surrounds it. We obtain independent and simultaneous switching detection of the nanowire and the film for all nanowire dimensions investigated, allowing us to estimate a magnetic sensitivity of 7 × 10-15 A m2 for DFMOKE in the setup used. We conclude the article by providing perspectives of future avenues where DFMOKE can be a very powerful characterization tool in future investigations of 3D magnetic nanostructures.

2D materials offer the ability to expose their electronic structure to manipulations by a proximity effect. This could be harnessed to craft properties of 2D interfaces and van der Waals heterostructures in devices and quantum materials. We explore the possibility to create an artificial spin polarized electrode from graphene through proximity interaction with a ferromagnetic insulator to be used in a magnetic tunnel junction (MTJ). Ferromagnetic insulator/graphene artificial electrodes were fabricated and integrated in MTJs based on spin analyzers. Evidence of the emergence of spin polarization in proximitized graphene layers was observed through the occurrence of tunnel magnetoresistance. We deduced a spin dependent splitting of graphene's Dirac band structure (∼15 meV) induced by the proximity effect, potentially leading to full spin polarization and opening the way to gating. The extracted spin signals illustrate the potential of 2D quantum materials based on proximity effects to craft spintronics functionalities, from vertical MTJs memory cells to logic circuits.

Cylindrical magnetic nanowires are promising systems for the development of three-dimensional spintronic devices. Here, we simulate the evolution of magnetic states during fabrication of strongly-coupled cylindrical nanowires with varying degrees of overlap. By varying the separation between wires, the relative strength of exchange and magnetostatic coupling can be tuned. Hence, we observe the formation of six fundamental states as a function of both inter-wire separation and wire height. In particular, two complex three-dimensional magnetic states, a 3D Landau Pattern and a Helical domain wall, are observed to emerge for intermediate overlap. These two emergent states show complex spin configurations, including a modulated domain wall with both Néel and Bloch character. The competition of magnetic interactions and the parallel growth scheme we follow (growing both wires at the same time) favours the formation of these anti-parallel metastable states. This works shows how the engineering of strongly coupled 3D nanostructures with competing interactions can be used to create complex spin textures.

Periodic arrays of sub-wavelength-scale holes in plasmonic metal films are known to provide resonant transmission peaks via the extraordinary optical transmission (EOT) effect. Active control of the spectral position of such transmission peaks can be obtained by adding a layer of phase-change material (PCM) to the EOT device. Switching the PCM layer between its amorphous and crystalline states can shift the spectral position of the resonance, enabling potential applications in the fields of active filtering and sensing (e.g., multispectral sensing), and for signal modulation. Here, the design, fabrication, and characterization of active EOT devices are targeted at various important regions of the optical spectrum.

Raw data for this publication, including Fourier-resolved magneto-optical Kerr effect maps and selected analysis of them, as shown in the paper.

An optimized design for a broadband Raman optical amplifier in standard single-mode fiber covering the C and L bands is presented, to be used in combination with wideband optical phase conjugation (OPC) nonlinearity compensation. The use of two Raman pumps and fiber Bragg grating reflectors at different wavelengths for the transmitted (C band) and conjugated (L band) WDM channels is proposed to extend bandwidth beyond the limits imposed by single-wavelength pumping, for a total 10 THz. Optimization of pump and reflector wavelength, as well as pump powers, allows us to achieve low asymmetry across the whole transmission band for optimal nonlinearity compensation. System performance is simulated to estimate OSNR, gain flatness and nonlinear Kerr distortion.