Juan Pérez-Mercader

Emergent Properties of Giant Vesicles Formed by a Polymerization-Induced Self-Assembly (PISA) Reaction

Giant micrometer sized vesicles are of obvious interest to the natural sciences as well as engineering, having potential application in fields ranging from drug delivery to synthetic biology. Their formation often requires elaborate experimental techniques and attempts to obtain giant vesicles from chemical media in a one-pot fashion have so far led to much smaller nanoscale structures. Here we show that a tailored medium undergoing controlled radical polymerization is capable of forming giant polymer vesicles. Using a protocol which allows for an aqueous reaction under mild conditions, we observe the macroscale consequences of amphiphilic polymer synthesis and the resulting molecular self-assembly using fluorescence microscopy. The polymerization process is photoinitiated by blue light granting complete control of the reaction, including on the microscope stage. The self-assembly process leads to giant vesicles with radii larger than 10 microns, exhibiting several emergent properties, including periodic growth and collapse as well as phototaxis.

Noise induced oscillations and coherence resonance in a generic model of the nonisothermal chemical oscillator

Oscillating chemical reactions are common in biological systems and they also occur in artificial non-biological systems. Generally, these reactions are subject to random fluctuations in environmental conditions which translate into fluctuations in the values of physical variables, for example, temperature. We formulate a mathematical model for a nonisothermal minimal chemical oscillator containing a single negative feedback loop and study numerically the effects of stochastic fluctuations in temperature in the absence of any deterministic limit cycle or periodic forcing. We show that noise in temperature can induce sustained limit cycle oscillations with a relatively narrow frequency distribution and some characteristic frequency. These properties differ significantly depending on the noise correlation. Here, we have explored white and colored (correlated) noise. A plot of the characteristic frequency of the noise induced oscillations as a function of the correlation exponent shows a maximum, therefore indicating the existence of autonomous stochastic resonance, i.e. coherence resonance.

Direct optical observations of vesicular self-assembly in large-scale polymeric structures during photocontrolled biphasic polymerization

In this report, we employ a photo-controlled polymerization protocol featuring a fluorescent initiator to follow the evolution of the generated self-assembled microscopic structures in a phase-separating dispersion polymerization medium. We observe the growth of polymer vesicles with final diameters of tens of microns. The formed structures respond to illumination with visible light at the absorbance maximum of the photoinitiator, demonstrating that the reaction mixture remains active even after transferring to an optical microscope slide and that the “blebbing” of vesicles and their growth continue until a mature size is reached.

Long-Range Correlations in the Fossil Record and the Fractal Nature of Macroevolution

Recent studies on the fossil record time series has shown that there is consistent evidence for self-similarity i.e., long-range correlations with power-law behavior. The existence of such fractal structures means that, when looking at a given time frame, some basic properties remain the same if a change of scale is performed. To sum up: there is no characteristic time scale, as we could expect if some type of periodic or other low-dimensional dynamics were present. A possible explanation for such long-range order is a dynamical process operating at all scales, as it is the case for systems in the neighborhood of critical points. In this paper these results are further explored by extending previous data analysis and examining the relevance of recent theoretical approaches to the statistical features of the fossil record. Submitted to Proc. Roy. Soc. London B.

The thermodynamic efficiency of computations made in cells across the range of life

Biological organisms must perform computation as they grow, reproduce and evolve. Moreover, ever since Landauer’s bound was proposed, it has been known that all computation has some thermodynamic cost—and that the same computation can be achieved with greater or smaller thermodynamic cost depending on how it is implemented. Accordingly an important issue concerning the evolution of life is assessing the thermodynamic efficiency of the computations performed by organisms. This issue is interesting both from the perspective of how close life has come to maximally efficient computation (presumably under the pressure of natural selection), and from the practical perspective of what efficiencies we might hope that engineered biological computers might achieve, especially in comparison with current computational systems. Here we show that the computational efficiency of translation, defined as free energy expended per amino acid operation, outperforms the best supercomputers by several orders of magnitude, and is only about an order of magnitude worse than the Landauer bound. However, this efficiency depends strongly on the size and architecture of the cell in question. In particular, we show that the useful efficiency of an amino acid operation, defined as the bulk energy per amino acid polymerization, decreases for increasing bacterial size and converges to the polymerization cost of the ribosome. This cost of the largest bacteria does not change in cells as we progress through the major evolutionary shifts to both single- and multicellular eukaryotes. However, the rates of total computation per unit mass are non-monotonic in bacteria with increasing cell size, and also change across different biological architectures, including the shift from unicellular to multicellular eukaryotes. This article is part of the themed issue ‘Reconceptualizing the origins of life’.

Periodic Perturbation of Chemical Oscillators: Entrainment and Induced Synchronization

It is well known that a large number of catalyst-carrying beads immersed in an oscillatory chemical medium (Belousov-Zhabotinsky reaction) display collective oscillatory behavior. Using a light sensitive version of BZ, we show that this collective behavior can be entrained to an external light source with an oscillatory intensity. Thus, the emerging collective behavior can be controlled by an external perturbation.

Effect of noise correlation on noise-induced oscillation frequency in the photosensitive Belousov-Zhabotinsky reaction in a continuous stirred tank reactor.

We report on the experimental study of noise-induced oscillations in the photosensitive Ru(bpy)3(2+)-catalyzed Belousov-Zhabotinsky reaction in a continuous stirred tank reactor (CSTR). In the absence of deterministic oscillations and any external periodic forcing, oscillations appear when the system is perturbed by stochastic fluctuations in light irradiation with sufficiently high amplitude in the vicinity of the bifurcation point. The frequency distribution of the noise-induced oscillations is strongly affected by noise correlation. There is a shift of the noise-induced oscillation frequency toward higher frequencies for an intermediate range of the noise correlation exponent, indicating the occurrence of coherence resonance. Our findings indicate that, in principle, noise correlation can be used to direct chemical reactions toward certain behavior.

Correction: Thermoresponsive gels directly obtained via visible light-mediated polymerization-induced self-assembly with oxygen tolerance

Correction for ‘Thermoresponsive gels directly obtained via visible light-mediated polymerization-induced self-assembly with oxygen tolerance’ by Kaixuan Ren et al., Polym. Chem., 2017, DOI: 10.1039/c7py00558j.

Controlled Synthesis of Uniform, Micrometer-Sized Ruthenium-Functionalized Poly(N-Isopropylacrylamide) Gel Particles and their Application to the Catalysis of the Belousov-Zhabotinsky Reaction

Ruthenium-functionalized poly(N-isopropyl acrylamide)-based chemically oscillating microgels with diameters between 1 and 6 µm are synthesized by a modified precipitation polymerization approach. It is found that the initial amount of N-isopropyl acrylamide (NIPAAm) can significantly affect the final sizes of the microgels. 2.5 g of initial NIPAAm results in microgels with maximum average diameter of ≈6 ± 0.5 µm. Making use of their fluorescence due to their ruthenium contents and their larger sizes compared to microgels prepared using other traditional methods, the impact of changes in the NaBrO3 concentrations on their microscopic behavior is studied using a combination of fluorescence microscopy and dynamic light scattering techniques. When increasing the concentration of NaBrO3 in a solution, the microgels first experience a decrease in size followed by aggregation that leads to the loss of colloidal stability. Finally, the redox potential behavior and optical performance of the Belousov-Zhabotinsky reaction catalyzed by these microgels are studied by electrochemical and spectroscopic means.

Noise-Induced and Control of Collective Behavior in a Population of Coupled Chemical Oscillators

Synchronization of intercommunicating individual oscillators is an important form of collective behavior used in nature as a mechanism to face dangers, act collectively, and communicate. The involvement of the medium where oscillators exist is an important ingredient. Because of their nature and their multiple different components, the medium and the environment are often perceived as stochastic relative to the deterministic nature of the individuals on some scale. This injects energy/matter into the system in ways that can enhance or de-enhance communication in a stochastic manner. Here we experimentally consider a large number of coupled nonlinear-chemical oscillators under the effect of a controlled normally distributed noise. Experiments show that the collective behavior of the oscillator is triggered by this stochastic perturbation, and we observe the dependence on the noise parameters. Our results point to the potential use of environmental fluctuations in determining the emergence and properties of collective behaviors in complex systems.