Impact of the dicyanomethylene substitution position on the cyclophane macrocycle formation in carbazole-based biradicals

π-Conjugated biradical compounds, featuring unique unsaturated valences and radical centers in the ground state, are fundamentally important for understanding the nature of chemical bonds and have potential applications in material science. [1] Recently, it has been demonstrated that several -conjugated mono- and biradicals systems form long strain -bonds between two unpaired electrons resulting in macrocyclic or staircase oligomers or polymers by self-assembly processes. [2] Therefore, these materials are potential building blocks for dynamic covalent chemistry (DCC) since the aggregates can be formed or broken upon soft external stimuli. For instance, 2,7-dicyanomethylene-9-(2-ethylhexyl)carbazole biradical (p-Cz-alkyl in Figure 1) reversibly converts upon soft stimuli (temperature, pressure, light) to a cyclophane tetramer as a result from the formation (or bond cleavage) of long C-C single bonds.[3] Here, we present an experimental and theoretical study in order to investigate how the N-substitution and the change from para- to meta-dicyanomethylene substitution on carbazole-based biradicals affects their biradical character and thus, their tendency to act as useful motifs for DCC (see Figure 1).Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tec

Novel antimicrobial zein film for controlled release of lauroyl arginate (LAE)

Novel antimicrobial biopolymer films based on the incorporation of ethyl-Nα-dodecanoyl-l-arginate hydrochloride (LAE) in zein matrices were manufactured and characterized as materials for LAE controlled released applications such as active food packaging. Characterization of the films’ functional properties revealed that incorporation of LAE (5 and 10%) in the biopolymer matrix did not cause substantial changes in morphological, optical, thermal, mechanical and barrier properties. As the mechanism of action of these films is mainly based on release of the antimicrobial, this process was characterized when the active biofilms were exposed to three food simulants (water, 3% acetic acid, and 10% alcohol) at three temperatures (4, 23, and 37 °C). The data obtained revealed that, with the exception of exposure to water at 4 °C which achieved a release of more than 80% of the LAE incorporated, the agent was almost completely extracted in all conditions. Release of LAE was faster at higher temperatures, and the diffusion coefficient values varied according to the Arrhenius law, and increased with temperature. Antibacterial activity of films was assayed against Listeria monocytogenes and Escherichia coli. Zein films with 5% LAE produced 2.02 and 3.07 log reduction against L. monocytogenes and E. coli, respectively, after 5 days of storage at 4 °C. Greater antibacterial activity was observed with films containing 10% LAE (5 log reduction) at 37 °C. This work highlighted that LAE incorporation in a packaging film constructed with renewable polymer materials offers an interesting and efficient hurdle for control of bacterial contamination in foods.The authors acknowledge the financial support of the Spanish Ministry of Economy and Competitiveness, projects AGL2012-39920-C03-01. M.K. thanks the Ministry of Sciences, Research and Technology of Iran for her grant. I.D. thanks the CSIC for her postdoctoral contract (JAE-DOC).Peer reviewe

Formation of stimuli-responsive cyclophanes by self-assembly: the case of carbazole-based biradicals

Dynamic covalent bonds has recently received lot of attention because of their unique feature to become reversible under mild conditions.[1] In this context, π-conjugated biradical compounds has emerged as essential building blocks.[2] For instance, we have demonstrated that 2,7-dicyanomethylene-9-(2-ethylhexyl)carbazole biradical reversibly converts to a macrocycle cyclophane upon soft stimuli (temperature, pressure, light), showing strong chromic effects.[3] We now extent this study towards longer conjugated carbazole backbone (i.e., indolocarbazole shown in Figure 1), aiming at investigating how the elongation of the conjugated backbone impacts on the formation of stimuli-responsive cyclophanes. The self-assembly process is investigated both in solution and solid state by linking theory and experiments.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Carbazole-based Diradicals for Dynamic Covalent Chemistry

Dynamic covalent chemistry (DCC) is focused on the creation of structural scaffolds based on chemical components that interact through strong but reversible bonds. In fact, dynamic covalent bonds receive lot of attention because of their unique feature to become reversible under mild conditions.1 conjugated diradical compounds has emerged as essential building blocks in DCC.2 In this work, we will review our most recent works on the formation of stimuli-responsive cyclophanes by self-assembly of carbazole-based diradicals. To this end, we use a combined experimental and theoretical approach that links vibrational spectroscopy with DFT calculations. In this sense, it is interesting to note that we have recently demonstrated the potential of a para-substituted carbazole with terminal dicyanomethylene (DCM) groups to act as building blocks in DCC.3 This quinoid carbazole monomer transforms to a macrocycle cyclophane upon soft external stimuli (temperature, pressure, light), showing strong chromic features. In addition, we have also recently explored how the different DCM substitution position affects the interesting chromoactive properties of carbazole compounds.4 Finally, we are currently exploring the effect of the elongation of the carbazole backbone on the formation of stimuli-responsive cyclophanes.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

On-design and off-design thermodynamic analysis of a hybrid multi-stage solar thermal tower power plant

[ENConcentrated solar power (CSP) is one challenging renewable technology for the future production of electricity. Within this concept central receiver solar plants combined with gas turbines are being investigated because of their promising efficiencies and reduced water consumption. Hybrid plants incorporate a combustion chamber in such a way that in periods of low solar irradiance power output can be kept approximately constant and so, electricity production is predictable. An integrated, non-complex solar thermodynamic model of a hybrid multi-stage gas turbine solar plant is developed employing a reduced number of parameters with a clear physical meaning. The solar subsystem is modelled in detail, taking into account the main heliostats field losses factors as cosine effect, blocking, or attenuation. The model is implemented in our own software, developed in Mathematica® language, considering as reference Gemasolar solar field (Seville, Spain). First, an on-design analysis is performed for four different working fluids (dry air, nitrogen, carbon dioxide, and helium), for different number of expansion and compression stages, and for recuperative and non-recuperative modes. Moreover, heliostats field configuration is determined for the design point and its associated efficiency is computed. A pre-optimization process is carried out regarding the pressure ratio of the gas turbine for different configurations. Some significant efficiency and power rises can be obtained when pressure ratio is adapted for each specific configuration and working fluid. Three particular plant configurations are chosen for the off-design analysis due to their interesting behaviours. For these configurations, a dynamic study is performed for four representative of each season. Then, efficiencies and solar share are plotted against time. In addition, fuel consumption and greenhouse emissions are computed for all seasons. Heliostats efficiency varying with the season and the solar time is also forecasted. Keywords: Dynamic analysis, On-design pre-optimization, Multi-stage gasJunta de Castilla y León of Spain (project SA017P17

Multiresponsive chromic soft materials: formation of strongly coupled σ-dimers from IndoloCarbazole-based biradicaloids

Dynamic covalent chemistry is focused on the creation of structural scaffolds based on chemical components that interact through strong but reversible bonds. In fact, dynamic covalent bonds receive lot of attention because of their unique feature to become reversible under mild conditions.1 π-conjugated biradical compounds has emerged as essential building blocks in DCC (dynamic covalent chemistry).2 We have recently demonstrated the potential of a para-substituted carbazole with terminal dicyanomethylene groups to act as building blocks in DCC.3 In fact, this quinoid carbazole monomer transform to a macrocycle cyclophane upon soft external stimuli (temperature, pressure, light), showing strong chromic features. Here, we explore the effect of the elongation of the carbazole backbone on the formation of stimuli-responsive cyclophanes by self-assembly. To this end, we use a join experimental and theoretical approach that links vibrational spectroscopy (Raman and IR) with DFT calculationsUniversidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Thermo-economic study of hybrid parabolic dish solar power plants in different regions of Spain

[EN]Small-scale hybrid parabolic dish Concentrated Solar Power (CSP) systems coupled to a micro-gas turbine are a promising option to obtain electrical energy in a distributed manner. During the day, solar energy is used to produce electricity and the absence of sunlight can be overcome with the combustion of a fossil or renewable fuel. This study presents the technical feasibility and thermo-economic model of a hybridized power plant in different regions of Spain, considering the local climatic conditions. The implemented model aims to provide a realistic view of the behaviour of the system, using a reduced number of selected parameters with a clear physical meaning. The irreversibilities taking place in all subsystems (solar part, combustion chamber, micro-gas turbine, and the corresponding heat exchangers) have been considered in the model, developed in Mathematica® language. The model considers the instant solar irradiance and ambient temperature dynamically, providing an estimation of the power output, the associated fuel consumption, and the most relevant pollutant emissions (CO2, CH4 and NO2) linked to combustion, for hybrid and combustion only operating modes at selected geographical locations in Spain. The considered power output ranges between 7 to 30 kWe which is achieved by varying the design specifications. The levelized cost of electricity (LCoE) indicator is estimated as a function of investment, interest rate, maintenance and fuel consumption actual costs in Spain. The electricity costs from hybrid parabolic dish are between 22% and 27% lower compared to pure combustion power plant, while specific fuel consumption and therefore CO2 emissions can be reduced up to 33%. This model shows the potential of hybrid solar dishes to become cost-competitive against non-renewable ones from the point of view of electricity costs and significant reduction in gas emission levels in regions with high solar radiation and low water resources.Junta de Castilla y Leó

On-design pre-optimization and off-design analysis of hybrid Brayton thermosolar tower power plants for different fluids and plant configurations

[EN]A working fluid performs a Brayton cycle that is fed by a heat input from a solar power tower and from a combustion chamber, which burns natural gas. This hybrid system is described by a complete model that includes all the main losses and irreversibility sources (optical and thermodynamic). Numerical implementation and validation is performed based on a Spanish commercial plant. On-design computations are carried out varying the pressure ratio for four working fluids (dry air, nitrogen, carbon dioxide, and helium), for different number of stages and for recuperative and non-recuperative configurations. When adjusting the pressure ratio, an improvement of about 7% in overall thermal efficiency is predicted for a dry air single-stage recuperative configuration with respect to a standard commercial gas turbine. A study about the main energy losses in each plant subsystem for some particular plant layouts is accomplished. A two-compression and expansion stages recuperative Brayton cycle working with air is expected to give overall thermal efficiencies about 0.29 at design conditions, which is about a 47% increase with respect to the simplest single-stage configuration. It is stressing that fuel consumption from the reheaters maybe higher than that of the main combustion chamber for multi-stage layouts. Off-design hourly curves of output records for the four seasons throughout a day are analyzed. Greenhouse emissions are also analyzed. Specific carbon dioxide emissions are smaller for helium than for dry air, when they both work in a single-stage non-recuperative configurationJunta de Castilla y León SA017P1

Cyclophane self-assembly from carbazole-based diradicals

The investigation of π-conjugated diradical compounds, featuring radical centers in the ground state, is key to understanding the nature of chemical bonds.[1] Occasionally, these systems can form long σ C-C bonds between two unpaired electrons resulting in macrocyclic or staircase oligomers or polymers by self-assembly processes. Furthermore, these new C-C bonds are longer than an ordinary bond between two sp3 carbon resulting in reversible dissociation/formation behavior between isolated radical species and cyclophane structures. Therefore, these materials are potential building blocks for dynamic covalent chemistry (DCC).[2] Hereinto, we present an experimental and theoretical study of carbazole and indolocarbazole-based diradicals (Figure 1) with dicyanomethylene (DCM) groups in different positions (para-DCM or meta-DCM) to identify new building blocks to obtain multi-responsive materials.[3-5] To this end, we investigated the dynamic interconversion between the isolated diradical and the cyclophane structures under external stimuli such as temperature, pressure and so on. Specifically, our main aim is to study how the DCM substitution and the elongation of the conjugated core affect the diradical character and to understand the connection between this parameter and the cyclophanes stability. In addition, we want to investigate if this transformation is reversible or not.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech