Social cognition in two brothers with Becker muscular dystrophy: an exploratory study revealing divergent behavioral phenotypes.

BACKGROUND AND OBJECTIVE: Only few studies investigated social cognition in Becker muscular dystrophy (BMD). However, brain dystrophin deficiency could be a neural substrate for cognitive, emotional, and neuropsychological features in BMD. METHODS: We compared interoceptive accuracy and interpersonal comfort distance in two brothers with BMD presenting with the same genetic deletion and a healthy control. When possible, we collected neuropsychological and psychopathological assessments. RESULTS: Our BMD patients were significantly different in interoceptive accuracy, with patient 1 being extremely accurate and patient 2 being significantly less accurate than his brother but more accurate than the control. Interestingly, they presented opposite patterns of interpersonal distance. Patient 1 was comfortable with very short interpersonal distance (≤50 cm from the confederate/object) vs the control and patient 2. By contrast, patient 2 preferred larger distance vs the control and patient 1. Patient 1 also presented difficulties in social and emotional skills on the psychopathological assessment. CONCLUSIONS: We are aware this is a small sample; nonetheless, this is also the first description of such aspects in BMD and the first report ever of such divergent behavioral pattern. As impaired social cognition affects the quality of life and social relationship, further studies are needed for a closer understanding of involved mechanisms.

Formation of Catalytic Hotspots in ATP-Templated Assemblies.

The self-assembly of surfactant-based structures that rely for their formation on the combination of a thermodynamically controlled and a dissipative pathway is described. Adenosine triphosphate (ATP) acts as a high-affinity template and triggers assembly formation at low surfactant concentrations. The presence of these assemblies creates the conditions for the activation of a dissipative self-assembly process by a weak-affinity substrate. The substrate-induced recruitment of additional surfactants leads to the spontaneous formation of catalytic hotspots in the ATP-stabilized assemblies that cleave the substrate. As a result of the two self-assembly processes, catalysis can be observed at a surfactant concentration at which low catalytic activity is observed in the absence of ATP.

Deficits in naming pictures of objects are associated with glioma infiltration of the inferior longitudinal fasciculus: A study with diffusion MRI tractography, volumetric MRI, and neuropsychology.

It has been suggested that the inferior longitudinal fasciculus (ILF) may play an important role in several aspects of language processing such as visual object recognition, visual memory, lexical retrieval, reading, and specifically, in naming visual stimuli. In particular, the ILF appears to convey visual information from the occipital lobe to the anterior temporal lobe (ATL). However, direct evidence proving the essential role of the ILF in language and semantics remains limited and controversial. The first aim of this study was to prove that patients with a brain glioma damaging the left ILF would be selectively impaired in picture naming of objects; the second aim was to prove that patients with glioma infiltrating the ATL would not be impaired due to functional reorganization of the lexical retrieval network elicited by the tumor. We evaluated 48 right-handed patients with neuropsychological testing and magnetic resonance imaging (MRI) before and after surgery for resection of a glioma infiltrating aspects of the left temporal, occipital, and/or parietal lobes; diffusion tensor imaging (DTI) was acquired preoperatively in all patients. Damage to the ILF, inferior frontal occipital fasciculus (IFOF), uncinate fasciculus (UF), arcuate fasciculus (AF), and associated cortical regions was assessed by means of preoperative tractography and pre-/pos-toperative MRI volumetry. The association of fascicles damage with patients' performance in picture naming and three additional cognitive tasks, namely, verbal fluency (two verbal non-visual tasks) and the Trail Making Test (a visual attentional task), was evaluated. Nine patients were impaired in the naming test before surgery. ILF damage was demonstrated with tractography in six (67%) of these patients. The odds of having an ILF damage was 6.35 (95% CI: 1.27-34.92) times higher among patients with naming deficit than among those without it. The ILF was the only fascicle to be significantly associated with naming deficit when all the fascicles were considered together, achieving an adjusted odds ratio of 15.73 (95% CI: 2.30-178.16, p = .010). Tumor infiltration of temporal and occipital cortices did not contribute to increase the odd of having a naming deficit. ILF damage was found to be selectively associated with picture naming deficit and not with lexical retrieval assessed by means of verbal fluency. Early after surgery, 29 patients were impaired in naming objects. The association of naming deficit with percentage of ILF resection (assessed by 3D-MRI) was confirmed (beta = -56.78 ± 20.34, p = .008) through a robust multiple linear regression model; no significant association was found with damage of IFOF, UF or AF. Crucially, postoperative neuropsychological evaluation showed that naming scores of patients with tumor infiltration of the anterior temporal cortex were not significantly associated with the percentage of ILF damage (rho = .180, p > .999), while such association was significant in patients without ATL infiltration (rho = -.556, p = .004). The ILF is selectively involved in picture naming of objects; however, the naming deficits are less severe in patients with glioma infiltration of the ATL probably due to release of an alternative route that may involve the posterior segment of the AF. The left ILF, connecting the extrastriatal visual cortex to the anterior region of the temporal lobe, is crucial for lexical retrieval on visual stimulus, such as in picture naming. However, when the ATL is also damaged, an alternative route is released and the performance improves.

Maternal input to children with sex chromosome trisomies.

BACKGROUND: Although language difficulties are one of the most distinctive characteristics of the neuropsychological profile of children with sex chromosome trisomies (SCT), the analysis of the maternal input addressed to them is a neglected topic. AIMS: The present study aims to analyse the lexical, morphosyntactic, and functional features of the input addressed to children with SCT comparing them with those of the input directed to typically developing children (TD). METHODS & PROCEDURES: Participants were 38 mothers and their 8-month-old children, 19 with SCT and 19 TD children. Maternal utterances, collected during video-recorded play sessions, have been transcribed and coded. OUTCOMES & RESULTS: No significant differences between groups have been found in the lexical and syntactic characteristics of maternal input. However, considering the input functional features, the proportion of directives and questions was significantly higher in the maternal input addressed to children with SCT than in the input addressed to TD children whereas the opposite pattern was found in the proportion of affect-salient speech. CONCLUSIONS & IMPLICATIONS: The awareness of a possible delay in their children's language development could influence the way the mothers speak to them. In particular, the functional features of maternal input could be affected. Support groups for parents of children with SCT at the preverbal stage could be useful to reassure the mothers about their role in their children's language development. What this paper adds What is already known on the subject Studies in the literature identified a high percentage of language delays or impairments in children with SCT. To date, according to our knowledge, there are no studies that analyse the linguistic input addressed to these children. What this study adds The lexical and syntactic features of maternal input addressed to 8-month-old children with SCT are adequate to the children's communicative skills. However, the mothers of children with SCT seem to provide additional scaffolding in their verbal input, using a lower proportion of affect-salient speech and a higher proportion of questions. In addition, a higher proportion of directives suggests the use of a more demanding style. Clinical implications of this study The awareness of possible language delays could influence the functional features of input leading mothers to use a more supportive and demanding input. Support groups for parents of children with SCT at the preverbal stage could be useful to reassure the mothers about their role in their children's language development.

Nucleotide-Selective Templated Self-Assembly of Nanoreactors under Dissipative Conditions.

Nature adopts complex chemical networks to finely tune biochemical processes. Indeed, small biomolecules play a key role in regulating the flux of metabolic pathways. Chemistry, which was traditionally focused on reactions in simple mixtures, is dedicating increasing attention to the network reactivity of highly complex synthetic systems, able to display new kinetic phenomena. Herein, we show that the addition of monophosphate nucleosides to a mixture of amphiphiles and reagents leads to the selective templated formation of self-assembled structures, which can accelerate a reaction between two hydrophobic reactants. The correct matching between nucleotide and the amphiphile head group is fundamental for the selective formation of the assemblies and for the consequent up-regulation of the chemical reaction. Transient stability of the nanoreactors is obtained under dissipative conditions, driven by enzymatic dephosphorylation of the templating nucleotides. These results show that small molecules can play a key role in modulating network reactivity, by selectively templating self-assembled structures that are able to up-regulate chemical reaction pathways.

Highly Charged Ruthenium(II) Polypyridyl Complexes as Effective Photosensitizer in Photodynamic Therapy.

A comparative study between two novel, highly water soluble, ruthenium(II) polypyridyl complexes, [Ru(phen)2 L'] and [Ru(phen)2 Cu(II)L'] (L and L-CuII ), containing the polyaazamacrocyclic unit 4,4'-(2,5,8,11,14-pentaaza[15])-2,2'-bipyridilophane (L'), is herein reported. L and L-CuII interact with calf-thymus DNA and efficiently cleave DNA plasmid when light-activated. They also possess great penetration abilities and photo-induced biological activities, evaluated on an A375 human melanoma cell line, with L-CuII being the most effective. Our study highlights the key role of the Fenton active CuII center within the macrocycle framework, that would play a synergistic role with light activation in the formation of cytotoxic ROS species. Based on these results, an optimal design of RuII polypyridyl systems featuring specific CuII -chelating polyamine units could represent a suitable strategy for the development of novel and effective photosensitizers in photodynamic therapy.

The predictive power of transcranial sonography in movement disorders: a longitudinal cohort study.

Transcranial sonography (TCS) is a noninvasive, easily performed, and commonly available neuroimaging technique useful for the study of brain parenchyma in movement disorders. This tool has been increasingly used in the diagnosis of Parkinson's disease and atypical parkinsonism. The aim of the study was to evaluate the applicability of this technique as supportive tool in the early diagnosis of movement disorders. We performed TCS on 315 individuals which were diagnosed as healthy controls or affected by idiopathic Parkinson's disease, monogenetic subtypes of Parkinson's disease, atypical parkinsonism, and Dementia with Lewy bodies. Five TCS diagnostic patterns were defined on the basis of substantia nigra's and lenticular nuclei's echogenicity. TCS evaluations were performed by two blinded neuro-sonographers. Clinical diagnosis on all individuals was performed at baseline and at 4-year follow-up. The concordance rate between TCS patterns and clinical diagnosis and the specificity of TCS pattern to discriminate each group of individuals were compared at baseline and at follow-up. The concordance rate between TCS patterns and clinical diagnosis of all individuals was 84% at baseline and increased at follow-up (91%) significantly (p = 0.01). The specificity of TCS pattern in the comparison between patients diagnosed as affected by idiopathic Parkinson's disease and atypical parkinsonism showed a significant increase at follow-up (p = 0.03). Our study strongly confirms the role of TCS as a noninvasive and cost-effective tool in early diagnosis of movement disorders.

Temporal Control over Transient Chemical Systems using Structurally Diverse Chemical Fuels.

The next generation of adaptive, intelligent chemical systems will rely on a continuous supply of energy to maintain the functional state. Such systems will require chemical methodology that provides precise control over the energy dissipation process, and thus, the lifetime of the transiently activated function. This manuscript reports on the use of structurally diverse chemical fuels to control the lifetime of two different systems under dissipative conditions: transient signal generation and the transient formation of self-assembled aggregates. The energy stored in the fuels is dissipated at different rates by an enzyme, which installs a dependence of the lifetime of the active system on the chemical structure of the fuel. In the case of transient signal generation, it is shown that different chemical fuels can be used to generate a vast range of signal profiles, allowing temporal control over two orders of magnitude. Regarding self-assembly under dissipative conditions, the ability to control the lifetime using different fuels turns out to be particularly important as stable aggregates are formed only at well-defined surfactant/fuel ratios, meaning that temporal control cannot be achieved by simply changing the fuel concentration.

Boosting carbon quantum dots/fullerene electron transfer via surface group engineering.

The design of novel nanostructures with tailored opto-electronic properties is a crucial step for third-generation photovoltaics, and the development of cheap and environmentally compatible materials is still a challenge. Carbon quantum dots (CQDs) emerged as promising candidates but usually a low processability and poor electron-donor properties hampered their photovoltaic applications. We tackle these issues through the synthesis and photophysical characterization of N-doped CQDs functionalized with different thiophene-containing groups. Functionalization was aimed at enhancing the electron donating properties of the carbon dots and improving the solubility in nonpolar solvents. The increased solubility in organic solvents allowed us to investigate the photoinduced interactions of the functionalized carbon dots with the fullerene derivative PCBM in solution and in solid blends. The investigation was carried out by cyclic voltammetry, photoluminescence spectroscopy and electron paramagnetic resonance (EPR). The remarkable oxidation potential shift of the functionalized carbon dots with respect to the pristine materials and the HOMO-LUMO energies strongly suggest them as good electron donors towards PCBM. The electron transfer process between CQDs and PCBM resulted in efficient fluorescence quenching in solution and in total quenching in solid blends. By using EPR spectroscopy in the solid blends, we demonstrated the efficient electron transfer by observing the photoinduced formation of a PCBM radical anion in the presence of functionalized CQDs. Time-resolved EPR allowed us to identify differences in the charge transport efficiency for different CQD:PCBM blends. The enhanced processability of CQDs with PCBM and the promising charge-generation and separation properties pave the way to the development of "all-carbon" photovoltaic devices.

Evaluation of gold nanoparticles toxicity towards human endothelial cells under static and flow conditions.

A new in vitro model system, adding advection and shear stress associated with a flowing medium, is proposed for the investigation of nanoparticles uptake and toxicity towards endothelial cells, since these processes are normally present when nanoparticles formulations are intravenously administered. In this model system, mechanical forces normally present in vivo, such as advection and shear stress were applied and carefully controlled by growing human umbilical vein endothelial cells inside a microfluidic device and continuously infusing gold nanoparticle (Au NPs) solution in the device. The tests performed in the microfluidic device were also run in multiwells, where no flow is present, so as to compare the two model systems and evaluate if gold nanoparticles toxicity differs under static and flow culture conditions. Full characterization of Au NPs in water and in culture medium was accomplished by standard methods. Two-photon fluorescence correlation spectroscopy was also employed to map the flow speed of Au NPs in the microfluidic device and characterize Au NPs before and after interactions with the cells. Au NPs uptake in both in vitro systems was investigated through electron and fluorescence microscopy and ICP-AES, and NPs toxicity measured through standard bio-analytical tests. Comparison between experiments run in multiwells and in microfluidic device plays a pivotal role for the investigation of nanoparticle-cell interaction and toxicity assessment: our work showed that administration of equal concentrations of Au NPs under flow conditions resulted in a reduced sedimentation of nanoparticle aggregates onto the cells and lower cytotoxicity with respect to experiments run in ordinary static conditions (multiwells).

Lifetime shortening and fast energy-tansfer processes upon dimerization of a A-π-D-π-A molecule.

Time-resolved fluorescence and transient absorption experiments uncover a distinct change in the relaxation dynamics of the homo-dimer formed by two 2,5-bis[1-(4-N-methylpyridinium)ethen-2-yl)]-N-methylpyrrole ditriflate (M) units linked by a short alkyl chain when compared to that of the monomer M. Fluorescence decay traces reveal characteristic decay times of 1.1 ns and 210 ps for M and the dimer, respectively. Transient absorption spectra in the spectral range of 425-1050 nm display similar spectral features for both systems, but strongly differ in the characteristic relaxation times gathered from a global fit of the experimental data. To rationalize the data we propose that after excitation of the dimer the energy localizes on one M branch and then decays to a dark state, peculiar only of the dimer. This dark state relaxes to the ground state within 210 ps through non-radiative relaxation. The nature of the dark state is discussed in relation to different possible photophysical processes such as excimer formation and charge transfer between the two M units. Anisotropy decay traces of the probe-beam differential transmittance of M and the dimer fall on complete different time scales as well. The anisotropy decay for M is satisfactorily ascribed to rotational diffusion in DMSO, whereas for the dimer it occurs on a faster time scale and is likely caused by energy-transfer processes between the two monomer M units.

Response of Coccomyxa cimbrica sp.nov. to Increasing Doses of Cu(II) as a Function of Time: Comparison between Exposure in a Microfluidic Device or with Standard Protocols.

In this study, we explore how the in vitro conditions chosen to cultivate and observe the long-term (up to 72 h) toxic effect of Cu(II) on the freshwater microalga Coccomyxa cimbrica sp.nov. can affect the dose response in time. We test three different cultivation protocols: (i) under static conditions in sealed glass cells, (ii) in a microfluidic device, where the sample is constantly circulated with a peristaltic pump, and (iii) under continuous agitation in plastic falcons on an orbital shaker. The advantage and novelty of this study resides in the fact that each condition can mimic different environmental conditions that alga cells can find in nature. The effect of increasing dose of Cu(II) as a function of time (24, 48, and 72 h) is monitored following chlorophyll a fluorescence intensity from single cells. Fluorescence lifetime imaging experiments are also explored to gain information on the changes induced by Cu(II) in the photosynthetic cycle of this microalga.

Photophysics and dynamics of surface plasmon polaritons-mediated energy transfer in the presence of an applied electric field.

The possibility to transfer energy between molecular excitons across a metal film up to 150 nm thick represents a very attractive solution to control and improve the performances of thin optoeletronic devices. This process involves the presence of coupled surface plasmon polaritons (SPPs) at the two dielectric-metal interfaces, capable of mediating the interactions between donor and acceptor, located on opposite sides of the metal film. In this Article, the photophysics and the dynamics of an efficient SPP-mediated energy transfer between a suitable dye and a conjugated polymer is characterized by means of steady-state and time-resolved photoluminescence techniques. The process is studied in model multilayer structures (donor/metal/acceptor) as well as in electrically pumped heterostructures (donor/metal cathode/acceptor/anode), to verify the effects of applied electric fields on the efficiency and the dynamics of SPP-mediated energy transfer. A striking enhancement of the overall luminescence was recorded in a particular range of applied bias, suggesting the presence of cooperative effects between optical and electrical stimulations.

Neuromuscular disorders and transition from pediatric to adult care in a multidisciplinary perspective: a narrative review of the scientific evidence and current debate.

Objective: Standards of care and new genetic and molecular therapies have contributed to increasing life expectancy of patients with neuromuscular diseases (NMDs). This review presents the clinical evidence for an adequate transition from pediatric to adult care in patients with NMDs considering both physical and psychosocial aspects and attempts at identifying a general pattern of transition in the literature that can be used for all patients with NMDs. Method: A search was performed on PubMed, Embase and Scopus using generic terms that could be referred to the transition construct specifically related to NMDs. A narrative approach was used to summarise the available literature. Results: Our review shows that few or no studies explored the transition process from pediatric to adult care in neuromuscular diseases and tried to identify a general pattern of transition applicable to all NMDs. Conclusions: A transition process taking into consideration physical, psychological, social needs of patient and caregiver could produce positive outcomes. However, there is still no unanimous agreement in the literature on what it consists of and how to achieve an optimal and effective transition.

Acceptability and feasibility of the World Health Organization's Caregiver Skills Training implemented in the Italian National Health System.

LAY ABSTRACT: Across the globe, children with neurodevelopmental disorders, including autism, have limited access to care through public services. To improve access to care the World Health Organization developed a novel, open-access programme: the Caregiver Skills Training programme. The Caregiver Skills Training consists of nine group sessions and three individual home visits, focused on training the caregiver on how to use everyday play and home routines as opportunities for learning and development. We implemented Caregiver Skills Training in public child neuropsychiatry services in Italy and examined with questionnaires and focus groups how feasible it was to deliver the programme in public health settings and how acceptable and relevant it was for caregiver users. We found that the Caregiver Skills Training was largely considered acceptable and relevant for families and feasible to deliver. We discuss potential solutions to address the specific implementation challenges that were identified, such as strategies to improve training of interventionists and overcome barriers to caregiver participation.

Supporting Caregivers Remotely During a Pandemic: Comparison of WHO Caregiver Skills Training Delivered Online Versus in Person in Public Health Settings in Italy.

Feasibility, acceptability and effectiveness data of a virtual adaptation of the WHO Caregiver Skills Training (CST; n = 25) were compared with those of a pilot RCT of CST delivered in person (n = 43) against treatment as usual (TAU; n = 43). Virtual CST was delivered with high levels of integrity, but received lower ratings in some caregiver- and facilitator-rated acceptability and feasibility dimensions. Qualitative analysis identified both benefits (flexibility, convenience, clinical usefulness) and challenges, (technological issues, distraction from family members, emotional distance). Virtual and in-person CST improved significantly more on caregiver competence than TAU; there were no other significant effects. Potential for use of virtual CST as a clinical response in contexts where in-person delivery is not possible is discussed.

Systematic Review and Meta-analysis: The Science of Early-Life Precursors and Interventions for Attention-Deficit/Hyperactivity Disorder.

OBJECTIVE: To evaluate which early neurocognitive and behavioral precursors are associated with the development of attention-deficit/hyperactivity disorder (ADHD) and whether these are currently targeted in early interventions. METHOD: We conducted 2 systematic reviews and meta-analyses of empirical studies to examine the following: (1) early-life (0-5 years) neurocognitive and behavioral precursors associated with familial likelihood for ADHD, an early ADHD diagnosis/elevated ADHD symptoms, and/or the presence of later-childhood ADHD; and (2) interventions delivered to children aged 0 to 5 years targeting the identified precursors or measuring these as outcomes. Standardized mean differences (Hedges' g) and pre-post-treatment change scores (SMD) were computed. RESULTS: A total of 149 studies (165,095 participants) investigating 8 neurocognitive and behavioral domains met inclusion criteria for part 1. Multi-level random-effects meta-analyses on 136 studies revealed significant associations between ADHD and poorer cognitive (g = -0.46 [95% CIs: -0.59, -0.33]), motor (g = -0.35 [CIs: -0.48, -0.21]) and language (g = -0.43 [CIs: -0.66, -0.19]) development, social (g = 0.23 [CIs: 0.03, 0.43]) and emotional (g = 0.46 [CIs: 0.33, 0.58]) difficulties, early regulatory (g = 0.30 [CIs: 0.18, 0.43]) and sleep (g = 0.29 [CIs: 0.14, 0.44]) problems, sensory atypicalities (g = 0.52 [CIs: 0.16, 0.88]), elevated activity levels (g = 0.54 [CIs: 0.37, 0.72]), and executive function difficulties (g = 0.34 [CIs: 0.05, 0.64] to -0.87 [CIs: -1.35, -0.40]). A total of 32 trials (28 randomized, 4 nonrandomized, 3,848 participants) testing early interventions that targeted the identified precursors met inclusion criteria for part 2. Multi-level random-effects meta-analyses on 22 studies revealed significant intervention-related improvements in ADHD symptoms (SMD = 0.43 [CIs: 0.22, 0.64]) and working memory (SMD = 0.37 [CIs: 0.06, 0.69]). CONCLUSION: Children aged 0 to 5 years with current or later-emerging ADHD are likely to experience difficulties in multiple neurocognitive/behavioral functions. Early interventions show some effectiveness in reducing ADHD symptoms, but their effects on neurocognitive/behavioral difficulties require further study.

A multimethod approach to assessing motor skills in boys and girls with autism spectrum disorder.

LAY ABSTRACT: Motor peculiarities are often reported in children with autism spectrum disorder and may predict subsequent adaptive functioning and quality of life. Although the sex bias in the prevalence of the disorder is well documented, little is known about differences in motor profile in males and females with autism spectrum disorder. Our goal was to study differences in motor functioning of boys and girls with autism spectrum disorder aged 3-11 years compared with typically developing children. Their motor performances were evaluated using a multimethod approach, including standardized motor tests, caregiver reports, and a detailed motion capture analysis of a simple reach-to-drop movement. We found that, irrespective of sex, children with autism spectrum disorder had worse scores than typically developing children on standardized tests and on caregiver reports. Interestingly, girls with autism spectrum disorder, but not boys, presented altered motor anticipation in reach-to-drop. Our findings emphasize the need for more sex-specific assessment of motor function in autism spectrum disorder.

A fullerene-distyrylbenzene photosensitizer for two-photon promoted singlet oxygen production.

Novel compounds endowed with a high two-photon absorption (TPA) cross-section and a high singlet oxygen quantum yield, are sought after for their possible application in anti-cancer therapies. In this paper we present a prototype macromolecule bearing a distyrylbenzene dimer as TPA unit and a [60]fullerene moiety for singlet oxygen generation. Linear absorption and emission spectra are measured, to help understanding the interactions between the single molecular units. The TPA absorption properties of the distyrylbenzene alone as well as bound to the methanofullerene unit are recorded with the TPA-induced fluorescence technique. An appreciable enhancement of the TPA cross-section was observed in the molecular conjugate.Singlet oxygen generation has been detected exciting the sample both in the Vis and NIR through one- and two-photon absorption processes, respectively. Although functionalization decreases the overall singlet oxygen quantum yield of fullerene, the presence of the distyrylbenzene antenna allows two-photon generation of singlet oxygen through an energy transfer process.

Time-gated fluorescence signalling under dissipative conditions.

Precise control over specific functions in the time domain is ubiquitous in biological systems. Here, we demonstrate time-gated fluorescence signalling under dissipative conditions exploiting an ATP-fueled self-assembly process. A temporal ATP-concentration gradient allows the system to pass through three states, among which only the intermediate state generates a fluorescent signal from a hydrophobic dye entrapped in the assemblies. The system can be reactivated by adding a new batch of ATP. The results indicate a strategy to rationally programme the temporal emergence of functions in complex chemical systems.