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News

Recent publications and News
HOT Article Collection

An article of the group has been elected for the "HOT Article Collection" of the journal Nanoscale Advances.

The paper published in Nanoscale Adv., 2020,2, 3954-3962 describes the use of NMR spectroscopy to study the mechanism of formation of Pd and Au nanoparticles. 

New network on supramolecular chemistry (SUPRAMAT)

                             

The SUPRAMAT research team involved in this project is composed by 14 groups from 13 different public institutions in Spain:
1. Supramolecular Chemistry Group (SUPRAMOL-UIB)
2. Interdisciplinar Supramolecular Chemistry (QUIMSUPRA-ICIQ)
3. Bioinspired Supramolecular Chemistry and Materials (BIOSUPRAMAT-UJI)
4. Supramolecular Chemistry (SUPRAM-IQAC)
5. Nanostructured Molecular Systems and Materials (MSMn-UAM)
6. Supramolecular Chemistry Group (SUPRACHEM-UM)
7. Supra and Nanostructured Systems (SUNS-UB)
8. Amphiphilic Molecules and Supramolecular Polymers (SUPRAPOL-UCM)
9. Microwaves in Sustainable Organic Chemistry (MSOC-UCLM)
10. Supramolecular Chemistry Group (SUPRAMOL-UV)
11. Supramolecular Chemistry and Peptide Nanotubes (QSNTP-USC-CIQUS)
12. Molecular Material Theoretical Chemistry (MolMatTC-UV)
13. Synthesis, Spectroscopy & Simulation in Organic Chemistry (S3-UVIGO)
14. Bio-inspired Chemistry, Supramolecular and Catalysis Group (SUPRA-CAT-UG)

SUPRAMAT initiative is aimed at connecting the groups and creating high-value and quality long-term relationships. The heart of SUPRAMAT is a network with consolidated research groups sharing aspirations and challenges, experienced scientists willing to share ideas, reduce the distance between the groups and to provide young students training opportunities, development and up-skilling. All these activities will be directed towards the development of novel functional materials by using the wide knowledge of the consortium.

 

New Book Chapter on NMR Detection in Flow Reactions
NEW BOOK CHAPTER ON FLOW CHEMISTRY IN DRUG DISCOVERY

An overview of the use of flow chemistry in drug discovery is provided with focus on all stages of drug discovery, from the identification of the initial hits to the preparation of Active Pharmaceutical Ingredients and the automation and integration of new green technologies.

Effect of Microwave Irradiation in Organic Synthesis

A critical overview of the effect of microwave irradiation in Organic Synthesis is presented.

This personal account collects some new findings in this field and our work on the use of computational chemistry to develop predictive models and to determine parameters related to thermal and non‐thermal effects, with clear advantages over experimental methods where separation of these effect is almost impossible.

 

 

 

New Photoinduced Palladium-Catalyzed Negishi Cross-Coupling

In a collaboration between Janssen and UMSOC UCLM a new Photoinduced Palladium-Catalyzed Negishi Cross-Couplings Enabled by the Visible-Light Absorption of Palladium–Zinc Complexes was described.

The scope of deactivated aryl halides employed in the Negishi coupling was significantly expanded. NMR experiments confirmed that the formation of the palladium–zinc complex is key for accelerating the oxidative addition step.

                             

 

Photochemically Induced Negishi Coupling in Flow without Photocatalyst

                                                      

A New Approach to Photosensitizer-free Photocatalysis protocol in flow for the Negishi cross-coupling with an extended scope and improved yields. The scope in the photochemical reaction vs. thermal reaction, which clearly highlights the importance of light for this transformation. This is the first report describing the behavior of organozinc reagents under irradiation. Moreover, the performed mechanistic studies support that light accelerates the reduction of the light absorbing Ni(II) species into Ni(0) by a zincate. This paper adds another very synthetically useful method to the growing area of exogenous photosensitizer-free photocatalysis

Microfluidics and Photo-CIDNP

Fig. 1

We have shown that the sesibility of NMR can be enhaced untill unprecedent limits with a self-designed and buld technology.

This increase in sensibility is higher to tthe described with comercial systems and suposes an rebirth of the photo-CIDNP NMR methodology.

Thesse results have been done with NMR microcoils, designed in our group and low  Watts light sources. This results opens new possibilities in the research of biological systems and pocesses that requires low concentrations.

The results have been published in Nature Communications.http://rdcu.be/EnwU.

 

Microchips and Real-Time Photochemical Reaction Monitoring

In a paper published in analítical Chemistry (https://pubs.acs.org/doi/10.1021/acs.analchem.7b04114) we describe a small-volume nuclear-magnetic-resonance (NMR)-spectroscopy device with integrated fiber-optics for the real-time detection of UV–vis-light-assisted chemical reactions. The system with 25 nL detection volumen in an NMR chip, use LEDs or a Laser diode and permits an efficient light penetration.

A New Mathematical Model on Microwave Heating

Prof. Navarro from the Department of Applied Mathematics in collaboration with our group have developend a new numerical model to predict tjhe heating behaviour of ethanol and water subjected to microwave irradiation with a monomode reactor and in a cylindrical container.

              

NEW FLOW PROCEDURE FOR THE PREPARATION AND REACTIONS OF ORGANOMAGNESSIUM REAGENTS

JANSSEN S. A. and MSOC group have reported in Org. Let. a new procedure for the preparation of highly pure organomagnessium reagents on demand and the use in flow and/or batch.

 

Review paper on poly(1H-pyrazol-1-yl)methanes

 

    A new review paper has been published in Coord. Chem. Rev. on the organic chemistry of poly(1H-pyrazol-1-yl)methanes. The synthesis, reactivity, and nature of the coordinated metals are described along with some properties of these compounds, particularly the complete set of X-ray molecular structures.

 

 

An article of the group elected as cover in a special issue on Flow Chemistry

                        

    A paper on the Reformatsky and Blaise reaction in Flow in collaboration with JANSSEN, S.A. has been published in a special issue of Green Chemsitry on Flow chemistry and has been elected as the cover of the issue.

 

 

Network of Excellence in NMR Spectroscopy

    The MSOC by means of Dr. Mª Victoria Gómez Almagro participates in the network of excellence project "Thematic network on NMR spectroscopy". This is a project with the participation of 10 laboratories in Spain and with a multidiscilplinar and international approach.

Review on the use of NMR spectroscopy in flow chemistry

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    This review show the recent advances in the use of flow chemistry with in-line and on-line analysis by NMR. It cover from the use macro- and, microreactors, standard and custom made NMR probes involving microcoils, high resolution and benchtop NMR instruments and the use of DOE and automatic reaction monitoring and automatization. Selected applications have been collected and kinetic and thermodynamic studies are also included.

 

Book chapter on flow Chemistry

                   

    A new book chapter on the use of non-conventional techniques in sustainable chematry under flow conditions has been published by our group. The chapter it is included in the book Sustainable Flow Chemistry – Chapter 9. Methods and Applications.  Edited by L. Vaccaro and published by Wiley-VCH.

New review on computational calculations and microwave irradiation

                   graphical-abstract     

    This review, published in Chem. Soc. Rev., provides an overview of the use of Computational Chemistry in MAOS to provide a theoretical understanding of the factors that can be used to explain the improvements in MAOS and how computational calculations can be used as a predictive tool.

 

 

New book chapter on Microwaves in Green Chemistry

              Resultado de imagen

    Since the first publications on the use of microwave irradiation in synthetic chemistry, it was clear that this methodology would have a marked influence in all areas of this discipline. Reduction of reaction times, improved yields, modifications of selectivities, increased product purities and simplification of work-up procedures were described and, in most cases, these conditions and results could not be achieved by classical heating. This methodology can be included within the concept of Green Chemistry because the strong absorption of microwave irradiation by one component of the reaction would lead to shorter reaction times and improved energy efficiency. Moreover, the synergy with solvent-free conditions, solid catalysts and green solvents has expanded the green applications of this non-conventional energy source. Finally, the use of flow systems, another green methodology, has permitted the scale-up of microwave-assisted reactions under green conditions.

 

Self-assembly of T-shape 2H-benzo[d][1,2,3]-triazoles. Optical waveguide and photophysical properties

    T-shaped 2H-benzo[d][1,2,3]triazole derivatives have been synthesized by Sonogashira coupling reactions under microwave irradiation. DFT calculations were performed in order to understand the structure-property relationships – an aspect that is of vital importance for the rational design of organic self-assemblies for optoelectronic applications. Concentration-dependent 1H Pulse Field-Gradient Spin-Echo (PFGSE) NMR spectroscopy and UV/Vis spectrophotometry indicated the absence of a tendency for the aggregation of single molecules in solution. In contrast, in the solid state these compounds form organized aggregates and these were studied by scanning electron microscopy (SEM), which showed the influence that the peripheral substitution has on the morphology of the aggregates. For example, methoxy-substituted benzotriazoles self-assemble into thick and crystalline needle-like structures. However, the unsubstituted triazoles give rise to flower-like aggregates. Interestingly, the aggregates formed by benzotriazole 1c exhibit waveguide properties.

 

SMALL-VOLUME NMR spectroscopy

                   

    NMR analysis of mass-limited samples remains a major challenge, which has triggered the development of expensive superconducting ultra-high field magnets, as well as of more expensive and technologically demanding solutions as cryoprobes and hyperpolarization schemes. Mass-limited samples could also benefit from the use of miniaturized coils, since the amplitude of the NMR signal is optimal when the sizes of the coil and sample match.

    In our group, we work on the design and fabrication of NMR-chips, rf-planar microcoil integrated on top of a glass substrate, and the construction of a small-volume NMR probe in which an optimized position for the NMR-chip allows the analysis of mass- and volume limited samples for different applications.

    In parallel, we are also focused on the integration of an NMR chip  with microreactors by developing continuous-flow hyphenated systems of different activation sources with nanoliter NMR spectroscopy. Alternative modes of activation, such as microwave irradiation and light-emitting diodes (LED) are employed. In this sense, a microwave-assisted continuous-flow microreactor was hyphenated with nanoliter-volume NMR spectroscopy, providing a rapid optimization of reaction conditions with low cost and reduced amount of solvents. The main advantage of the systems deals with the fact of allowing the division of the reaction volume -usually higher than the detection volume- into several zones -each of these ones exposed to the activation source for different times when working  under flow conditions-  and the analysis of each zone separately. Therefore, choosing the appropriate flow rate, experimental variables and NMR acquisition parameters, the necessary data points for optimizing the reaction conditions can be obtained in a single constant-flow experiment. This advantage is of highly importance specially when dealing with microwave as energy source where in most cases, the time required for analysis is longer than the reaction itself.