<meta charset="utf8"></head><body>Síntesis de materiales termoeléctricos de alta ZT mediante métodos mecanoquímicos

<ol>
	<li>Zhang, X., Zhao, L. D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Thermoelectric+materials:+Energy+conversion+between+heat+and+electricity.">Thermoelectric materials: Energy conversion between heat and electricity.</a> J Mater. 1 (2), 92-105 (2015).</li><li>Beretta, D., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Thermoelectrics:+From+history,+a+window+to+the+future.">Thermoelectrics: From history, a window to the future.</a> Mater Sci Eng R Reports. 138, 210-255 (2019).</li><li>Bal&#225;&#382;, M., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Mechanochemical+synthesis+of+non-stoichiometric+copper+sulfide+Cu1.8S+applicable+as+a+photocatalyst+and+antibacterial+agent+and+synthesis+scalability+verification.">Mechanochemical synthesis of non-stoichiometric copper sulfide Cu1.8S applicable as a photocatalyst and antibacterial agent and synthesis scalability verification.</a> Faraday Discuss. 241, 367-386 (2022).</li><li>He, Y., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=High+thermoelectric+performance+in+non-toxic+earth-abundant+copper+sulfide.">High thermoelectric performance in non-toxic earth-abundant copper sulfide.</a> Adv Mater. 26 (23), 3974-3978 (2014).</li><li>Zhang, Y. X., Feng, J., Ge, Z. H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Enhanced+thermoelectric+performance+of+Cu1.8S+via+lattice+softening.">Enhanced thermoelectric performance of Cu1.8S via lattice softening.</a> Chem. Eng. J. 428, 131153 (2022).</li><li>Zhao, L. D., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Ultralow+thermal+conductivity+and+high+thermoelectric+figure+of+merit+in+SnSe+crystals.">Ultralow thermal conductivity and high thermoelectric figure of merit in SnSe crystals.</a> Nature. 508 (7496), 373-377 (2014).</li><li>Byeon, D., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Dynamical+variation+of+carrier+concentration+and+colossal+Seebeck+effect+in+Cu2S+low-temperature+phase.">Dynamical variation of carrier concentration and colossal Seebeck effect in Cu2S low-temperature phase.</a> J Alloys Compd. 826, 154155 (2020).</li><li>Cai, B., Hu, H., Zhuang, H. L., Li, J. F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Promising+materials+for+thermoelectric+applications.">Promising materials for thermoelectric applications.</a> J Alloys Compd. 806, 471-486 (2019).</li><li>Jiang, Q., Yan, H., Khaliq, J., Shen, Y., Simpson, K., Reece, M. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Enhancement+of+thermoelectric+properties+by+atomic-scale+percolation+in+digenite+CuxS.">Enhancement of thermoelectric properties by atomic-scale percolation in digenite CuxS.</a> J Mater Chem A. 2 (25), 9486-9489 (2014).</li><li>Wei, T. R., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Copper+chalcogenide+thermoelectric+materials.">Copper chalcogenide thermoelectric materials.</a> Sci China Mater. 62 (1), 8-24 (2019).</li><li>Achimovi&#269;ov&#225;, M., Re&#269;nik, A., Fabi&#225;n, M., Bal&#225;&#382;, P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Characterization+of+tin+selenides+synthesized+by+high-energy+milling.">Characterization of tin selenides synthesized by high-energy milling.</a> Acta Montan Slovaca. 16 (2), 123-127 (2011).</li><li>Aydin, M., Ahsen, A. S., Demir-Cakan, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Ball+mill-assisted+synthesis+of+carbon-free+SnSe+nanoparticles+for+sodium-ion+battery+anodes.">Ball mill-assisted synthesis of carbon-free SnSe nanoparticles for sodium-ion battery anodes.</a> J Solid State Electrochem. 27 (5), 1075-1084 (2023).</li><li>Zheng, W., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Mechanochemical+preparation+of+well-structured+copper+sulfide+for+elemental+mercury+sequestration+from+coal+combustion+flue+gas.">Mechanochemical preparation of well-structured copper sulfide for elemental mercury sequestration from coal combustion flue gas.</a> Chem Eng J. 452 (P2), 139278 (2023).</li><li>Bal&#225;&#382;, M., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Ultrafast+mechanochemical+synthesis+of+copper+sulfides.">Ultrafast mechanochemical synthesis of copper sulfides.</a> RSC Adv. 6 (91), 87836-87842 (2016).</li><li>Takacs, L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Self-sustaining+reactions+induced+by+ball+milling.">Self-sustaining reactions induced by ball milling.</a> Prog Mater Sci. 47 (4), 355-414 (2002).</li><li>Bal&#225;&#382;, M., D&#382;unda, R., Bure&#353;, R., Sop&#269;&#225;k, T., Csan&#225;di, T. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Mechanically+induced+self-propagating+reactions+(MSRs)+to+instantly+prepare+binary+metal+chalcogenides:+assessing+the+influence+of+particle+size,+bulk+modulus,+reagents+melting+temperature+difference+and+thermodynamic+constants+on+the+ignition+time.">Mechanically induced self-propagating reactions (MSRs) to instantly prepare binary metal chalcogenides: assessing the influence of particle size, bulk modulus, reagents melting temperature difference and thermodynamic constants on the ignition time.</a> RSC Mechanochem. 1 (1), 94-105 (2024).</li><li>Angerhofer, A., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Advances+in+synthesis:+general+discussion.">Advances in synthesis: general discussion.</a> Faraday Discuss. 241, 150-177 (2022).</li><li>Scholl, R., Wegerte, R., Mutter, W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Gas+pressure+and+temperature+measuring+system+(GTM)+for+in-situ+data+acquisition+during+planetary+ball+milling.">Gas pressure and temperature measuring system (GTM) for in-situ data acquisition during planetary ball milling.</a> J Metastable Nanocrystalline Mater. 8, 946-972 (2000).</li><li>Jacko, P., Bal&#225;&#382;, M., Bal&#225;&#382;, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Measuring+system+for+measuring+dynamic+temperature+changes+in+cylindrical+grinding+chambers.">Measuring system for measuring dynamic temperature changes in cylindrical grinding chambers.</a> Slovak patent. , (2023).</li><li>C&#243;rdoba, J. M., Alcal&#225;, M. D., Avil&#233;s, M. A., Sayagu&#233;s, M. J., Gotor, F. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=New+production+of+TiCxN1-x-based+cermets+by+one+step+mechanically+induced+self-sustaining+reaction:+Powder+synthesis+and+pressureless+sintering.">New production of TiCxN1-x-based cermets by one step mechanically induced self-sustaining reaction: Powder synthesis and pressureless sintering.</a> J Eur Ceram Soc. 28 (10), 2085-2098 (2008).</li><li>Takacs, L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Self-sustaining+metal-sulfur+reactions+induced+by+ball+milling.">Self-sustaining metal-sulfur reactions induced by ball milling.</a> J Maters Synth Process. 8, 181-188 (2000).</li><li>Caggiu, L., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Solvent-free+mechanochemical+approach+towards+thiospinel+MgCr2S4+as+a+potential+electrode+for+post-lithium+ion+batteries.">Solvent-free mechanochemical approach towards thiospinel MgCr2S4 as a potential electrode for post-lithium ion batteries.</a> Batteries. 6 (3), 43 (2020).</li><li>Godo&#269;&#237;kov&#225;, E., Bal&#225;&#382;, P., Criado, J. M., Real, C., Gock, E. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Thermal+behaviour+of+mechanochemically+synthesized+nanocrystalline+CuS.">Thermal behaviour of mechanochemically synthesized nanocrystalline CuS.</a> Thermochim Acta. 440 (1), 19-22 (2006).</li><li>Achimovi&#269;ov&#225;, M., Dutkov&#225;, E., T&#243;thov&#225;, E., Buj&#328;&#225;kov&#225;, Z., Brian&#269;in, J., Kitazono, S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Structural+and+optical+properties+of+nanostructured+copper+sulfide+semiconductor+synthesized+in+an+industrial+mill.">Structural and optical properties of nanostructured copper sulfide semiconductor synthesized in an industrial mill.</a> Front Chem Sci Eng. 13 (1), 164-170 (2019).</li><li>Bal&#225;&#382;, M., Zorkovsk&#225;, A., Blazquez, J. S., Daneu, N., Bal&#225;&#382;, P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Mechanochemistry+of+copper+sulphides:+phase+interchanges+during+milling.">Mechanochemistry of copper sulphides: phase interchanges during milling.</a> J Mater Sci. 52 (20), 11947-11961 (2017).</li><li>Achimovi&#269;ov&#225;, M., Bal&#225;&#382;, P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Nanocrystalline+metal+selenides:+mechanochemical+sy+thesis+and+utilizable+properties.">Nanocrystalline metal selenides: mechanochemical sy thesis and utilizable properties.</a> Nanotechnol Res J. 8 (4), 459-511 (2015).</li><li>Okereke, N. A., Ekpunobi, A. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Spectroscopic+studies+on+lead+selenide+(PbSe)+and+tin+selenide+(SnSe)+thin+films.">Spectroscopic studies on lead selenide (PbSe) and tin selenide (SnSe) thin films.</a> J Optoelectron Biomed Mater. 3 (3), 69-74 (2011).</li><li>Michalchuk, A. A. L., Emmerling, F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Time-resolved+in+situ+monitoring+of+mechanochemical+reactions.">Time-resolved in situ monitoring of mechanochemical reactions.</a> Angew Chemie - International Edition. 61 (21), e202117270 (2022).</li><li>Halasz, I., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=In+situ+and+real-time+monitoring+of+mechanochemical+milling+reactions+using+synchrotron+X-ray+diffraction.">In situ and real-time monitoring of mechanochemical milling reactions using synchrotron X-ray diffraction.</a> Nat Protoc. 8 (9), 1718-1729 (2013).</li><li>Tsuzuki, T., McCormick, P. G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Mechanochemical+synthesis+of+metal+sulphides+nanoparticles.">Mechanochemical synthesis of metal sulphides nanoparticles.</a> Nanosctructured Mater. 12 (99), 75-78 (1999).</li><li>Takeno, M. L., da Silva, G. A., Trich&#234;s, D. M., Ghosh, A., de Souza, S. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Structural+studies+of+the+layered+SnSe+produced+by+mechanical+alloying+and+melting+technique.">Structural studies of the layered SnSe produced by mechanical alloying and melting technique.</a> J Alloys Compd. 735, 489-495 (2018).</li><li>Lan, Y., Minnich, A. J., Chen, G., Ren, Z. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Enhancement+of+thermoelectric+figure-of-merit+by+a+bulk+nanostructuring+approach.">Enhancement of thermoelectric figure-of-merit by a bulk nanostructuring approach.</a> Adv Funct Mater. 20 (3), 357-376 (2010).</li><li>Munir, Z. A., Anselmi-Tamburini, U., Ohyanagi, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+effect+of+electric+field+and+pressure+on+the+synthesis+and+consolidation+of+materials:+A+review+of+the+spark+plasma+sintering+method.">The effect of electric field and pressure on the synthesis and consolidation of materials: A review of the spark plasma sintering method.</a> J Mater Sci. 41 (3), 763-777 (2006).</li></ol>

<table border="1" fo:keep-together.within-page="1" fo:keep-with-next.within-page="always">
	<tbody>
		<tr>
			<td>Copper</td>
			<td>Pometon, Germany</td>
			<td>7440-50-8</td>
			<td>Red powder</td>
		</tr>
		<tr>
			<td>D8 Advance diffractometer&#160;</td>
			<td>Bruker, Germany</td>
			<td>M88-E03036</td>
			<td>X-ray instrument</td>
		</tr>
		<tr>
			<td>DiffracPlus Evaluation package release</td>
			<td>Bruker, Germany</td>
			<td>DOC-M85-EXX002</td>
			<td>Diffraction analysis software</td>
		</tr>
		<tr>
			<td>Etaben</td>
			<td>Mikrochem, Slovakia</td>
			<td>64-17-5</td>
			<td>solution</td>
		</tr>
		<tr>
			<td>Jedit</td>
			<td>Open Source software</td>
			<td></td>
			<td>Programmer&#39;s text editor</td>
		</tr>
		<tr>
			<td>Project SAV 1.0</td>
			<td></td>
			<td></td>
			<td>Software developed to record data from in situ temeprature monitoring</td>
		</tr>
		<tr>
			<td>Pulverisette P7 planetary mill</td>
			<td>Fritsch, Germany</td>
			<td>07.5000.00</td>
			<td>The milling device, utilized in the synthesis of Cu1.8S and SnSe</td>
		</tr>
		<tr>
			<td>Selenium</td>
			<td>Acros Organic, Germany</td>
			<td>7782-49-2</td>
			<td>Gray powder</td>
		</tr>
		<tr>
			<td>Sulfur</td>
			<td>Sigma Aldrich, Germany</td>
			<td>7704-34-9</td>
			<td>Yellow powder</td>
		</tr>
		<tr>
			<td>Tin</td>
			<td>Merck, Germany</td>
			<td>7440-31-5</td>
			<td>Gray powder</td>
		</tr>
		<tr>
			<td>Topas Academic</td>
			<td>Coelho Software</td>
			<td></td>
			<td>General non-linear least squares software driven by a scripting language. Its main focus is in crystallography, solid state chemistry and optimization.</td>
		</tr>
	</tbody>
</table>

demonstrating the simplicity and in situ temperature monitoring of the mechanochemical synthesis of metal chalcogenides suitable for thermoelectrics

<meta charset="utf8"></head><body>Demostrando la simplicidad y el monitoreo de temperatura in situ de la síntesis mecanoquímica de calcogenuros metálicos adecuados para termoeléctricos

Demostrando la simplicidad y el monitoreo de temperatura in situ de la síntesis mecanoquímica de calcogenuros metálicos adecuados para termoeléctricos

Mechanochemical synthesis is an extremely useful strategy to reach thermoelectric materials due to its solvent-free one-step character, as the targeted ...

demonstrating-simplicity-situ-temperature-monitoring-mechanochemical

Research

JoVE Journal

Chemistry

Demonstrating the Simplicity and In Situ Temperature Monitoring of the Mechanochemical Synthesis of Metal Chalcogenides Suitable for Thermoelectrics

230 vistas.  Slovak Academy of Sciences. En este trabajo se presenta un protocolo para sintetizar dos calcogenuros metálicos (Cu1.8S y SnSe) adecuados para termoeléctricos mediante una síntesis mecanoquímica ultrarrápida (de segundo rango), sin disolventes y en un solo paso utilizando precursores elementales. Al mismo tiempo, demostramos el monitoreo de la temperatura en el frasco durante la molienda planetaria de bolas in situ mediante el dispositivo re...

Video: Demostrando la simplicidad y el monitoreo de temperatura in situ de la síntesis mecanoquímica de calcogenuros metálicos adecuados para termoeléctricos

Structure and Coordination Determination of Peptide-metal Complexes Using 1D and 2D 1H NMR

Copper (I) binding by metallochaperone transport proteins prevents copper oxidation and release of the toxic ions that may participate in harmful redox reactions. The Cu (I) complex of the peptide model of a Cu (I) binding metallochaperone protein, which includes the sequence MTCSGCSRPG (underlined is conserved), was determined in solution under inert conditions by NMR spectroscopy.
NMR is a widely accepted technique for the determination of solution structures of proteins and peptides. Due to difficulty in crystallization to provide single crystals suitable for X-ray crystallography, the NMR technique is extremely valuable, especially as it provides information on the solution state rather than the solid state. Herein we describe all steps that are required for full three-dimensional structure determinations by NMR. The protocol includes sample preparation in an NMR tube, 1D and 2D data collection and processing, peak assignment and integration, molecular mechanics calculations, and structure analysis. Importantly, the analysis was first conducted without any preset metal-ligand bonds, to assure a reliable structure determination in an unbiased manner.

Structure and Coordination Determination of Peptide-metal Complexes Using 1D and 2D 1H NMR

The NMR-solution structure of a metallochaperone model peptide with Cu (I) was determined, and a detailed protocol from sample preparation and 1D and 2D data collection to a three-dimensional structure is described.

Copper (I) binding by metallochaperone transport proteins prevents copper oxidation and release of the toxic ions that may participate in harmful redox ...

Investigación

Química

Anticancer Metal Complexes: Synthesis and Cytotoxicity Evaluation by the MTT Assay

Titanium (IV) and vanadium (V) complexes are highly potent anticancer agents. A challenge in their synthesis refers to their hydrolytic instability; therefore their preparation should be conducted under an inert atmosphere. Evaluation of the anticancer activity of these complexes can be achieved by the MTT assay.
The MTT assay is a colorimetric viability assay based on enzymatic reduction of the MTT molecule to formazan when it is exposed to viable cells. The outcome of the reduction is a color change of the MTT molecule. Absorbance measurements relative to a control determine the percentage of remaining viable cancer cells following their treatment with varying concentrations of a tested compound, which is translated to the compound anticancer activity and its IC50 values. The MTT assay is widely common in cytotoxicity studies due to its accuracy, rapidity, and relative simplicity.
Herein we present a detailed protocol for the synthesis of air sensitive metal based drugs and cell viability measurements, including preparation of the cell plates, incubation of the compounds with the cells, viability measurements using the MTT assay, and determination of IC50 values.

A method for synthesis of air-sensitive titanium and vanadium anticancer agents is described, along with the evaluation of their cytotoxic activity towards human cancer cell line by the MTT Assay.

Anticancerosos complejos metálicos: Síntesis y Evaluación de la citotoxicidad por el ensayo MTT

Titanium (IV) and vanadium (V) complexes are highly potent anticancer agents. A challenge in their synthesis refers to their hydrolytic instability; ...

Synthesis and Characterization of Functionalized Metal-organic Frameworks

Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and technological applications. Their signature property is their ultrahigh porosity, which however imparts a series of challenges when it comes to both constructing them and working with them. Securing desired MOF chemical and physical functionality by linker/node assembly into a highly porous framework of choice can pose difficulties, as less porous and more thermodynamically stable congeners (e.g., other crystalline polymorphs, catenated analogues) are often preferentially obtained by conventional synthesis methods. Once the desired product is obtained, its characterization often requires specialized techniques that address complications potentially arising from, for example, guest-molecule loss or preferential orientation of microcrystallites. Finally, accessing the large voids inside the MOFs for use in applications that involve gases can be problematic, as frameworks may be subject to collapse during removal of solvent molecules (remnants of solvothermal synthesis). In this paper, we describe synthesis and characterization methods routinely utilized in our lab either to solve or circumvent these issues. The methods include solvent-assisted linker exchange, powder X-ray diffraction in capillaries, and materials activation (cavity evacuation) by supercritical CO2 drying. Finally, we provide a protocol for determining a suitable pressure region for applying the Brunauer-Emmett-Teller analysis to nitrogen isotherms, so as to estimate surface area of MOFs with good accuracy.

Synthesis, activation, and characterization of intentionally designed metal-organic framework materials is challenging, especially when building blocks are incompatible or unwanted polymorphs are thermodynamically favored over desired forms. We describe how applications of solvent-assisted linker exchange, powder X-ray diffraction in capillaries and activation via supercritical CO2 drying, can address some of these challenges.

Marcos de síntesis y caracterización de funcionalizado metal-orgánico

Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and ...

Synthesis of Cd-free InP/ZnS Quantum Dots Suitable for Biomedical Applications

Fluorescent nanocrystals, specifically quantum dots, have been a useful tool for many biomedical applications. For successful use in biological systems, quantum dots should be highly fluorescent and small/monodisperse in size. While commonly used cadmium-based quantum dots possess these qualities, they are potentially toxic due to the possible release of Cd2+ ions through nanoparticle degradation. Indium-based quantum dots, specifically InP/ZnS, have recently been explored as a viable alternative to cadmium-based quantum dots due to their relatively similar fluorescence characteristics and size. The synthesis presented here uses standard hot-injection techniques for effective nanoparticle growth; however, nanoparticle properties such as size, emission wavelength, and emission intensity can drastically change due to small changes in the reaction conditions. Therefore, reaction conditions such temperature, reaction duration, and precursor concentration should be maintained precisely to yield reproducible products. Because quantum dots are not inherently soluble in aqueous solutions, they must also undergo surface modification to impart solubility in water. In this protocol, an amphiphilic polymer is used to interact with both hydrophobic ligands on the quantum dot surface and bulk solvent water molecules. Here, a detailed protocol is provided for the synthesis of highly fluorescent InP/ZnS quantum dots that are suitable for use in biomedical applications.

In this protocol, the synthesis of Cd-free InP/ZnS quantum dots (QDs) is detailed. InP-based QDs are gaining popularity due to the toxicity of Cd2+ ions that may be released through nanoparticle degradation. After synthesis, QDs are solubilized in water using an amphiphilic polymer for use in biomedical applications.

Síntesis de Cd-libre EAD / ZnS puntos cuánticos Adecuado para aplicaciones biomédicas

Fluorescent nanocrystals, specifically quantum dots, have been a useful tool for many biomedical applications. For successful use in biological systems, ...

Synthesis of Protein Bioconjugates via Cysteine-maleimide Chemistry

The chemical linking or bioconjugation of proteins to fluorescent dyes, drugs, polymers and other proteins has a broad range of applications, such as the development of antibody drug conjugates (ADCs) and nanomedicine, fluorescent microscopy and systems chemistry. For many of these applications, specificity of the bioconjugation method used is of prime concern. The Michael addition of maleimides with cysteine(s) on the target proteins is highly selective and proceeds rapidly under mild conditions, making it one of the most popular methods for protein bioconjugation.
We demonstrate here the modification of the only surface-accessible cysteine residue on yeast cytochrome c with a ruthenium(II) bisterpyridine maleimide. The protein bioconjugation is verified by gel electrophoresis and purified by aqueous-based fast protein liquid chromatography in 27% yield of isolated protein material. Structural characterization with MALDI-TOF MS and UV-Vis is then used to verify that the bioconjugation is successful. The protocol shown here is easily applicable to other cysteine - maleimide coupling of proteins to other proteins, dyes, drugs or polymers.

Synthesis of Protein Bioconjugates via Cysteine-maleimide Chemistry

This protocol details the important steps required for the bioconjugation of a cysteine containing protein to a maleimide, including reagent purification, reaction conditions, bioconjugate purification and bioconjugate characterization.

Síntesis de Proteínas bioconjugados<em&gt; vía</em&gt; Química cisteína-maleimida

The chemical linking or bioconjugation of proteins to fluorescent dyes, drugs, polymers and other proteins has a broad range of applications, such as the ...

Synthesis of a Water-soluble Metal&#8211;Organic Complex Array

We demonstrate a method for the synthesis of a water-soluble multimetallic peptidic array containing a predetermined sequence of metal centers such as Ru(II), Pt(II), and Rh(III). The compound, named as a water-soluble metal-organic complex array (WSMOCA), is obtained through 1) the conventional solution-chemistry-based preparation of the corresponding metal complex monomers having a 9-fluorenylmethyloxycarbonyl (Fmoc)-protected amino acid moiety and 2) their sequential coupling together with other water-soluble organic building units on the surface-functionalized polymeric resin by following the procedures originally developed for the solid-phase synthesis of polypeptides, with proper modifications. Traces of reactions determined by mass spectrometric analysis at the representative coupling steps in stage 2 confirm the selective construction of a predetermined sequence of metal centers along with the peptide backbone. The WSMOCA cleaved from the resin at the end of stage 2 has a certain level of solubility in aqueous media dependent on the pH value and/or salt content, which is useful for the purification of the compound.

Synthesis of a Water-soluble Metal&amp;#8211;Organic Complex Array

A potential general method for the synthesis of water-soluble multimetallic peptidic arrays containing a predetermined sequence of metal centers is presented.

Síntesis de un conjunto complejo de metal-orgánico soluble en agua

We demonstrate a method for the synthesis of a water-soluble multimetallic peptidic array containing a predetermined sequence of metal centers such as ...

Microfluidic Chips for In Situ Crystal X-ray Diffraction and In Situ Dynamic Light Scattering for Serial Crystallography

This protocol describes fabricating microfluidic devices with low X-ray background optimized for goniometer based fixed target serial crystallography. The devices are patterned from epoxy glue using soft lithography and are suitable for in situ X-ray diffraction experiments at room temperature. The sample wells are lidded on both sides with polymeric polyimide foil windows that allow diffraction data collection with low X-ray background. This fabrication method is undemanding and inexpensive. After the sourcing of a SU-8 master wafer, all fabrication can be completed outside of a cleanroom in a typical research lab environment. The chip design and fabrication protocol utilize capillary valving to microfluidically split an aqueous reaction into defined nanoliter sized droplets. This loading mechanism avoids the sample loss from channel dead-volume and can easily be performed manually without using pumps or other equipment for fluid actuation. We describe how isolated nanoliter sized drops of protein solution can be monitored in situ by dynamic light scattering to control protein crystal nucleation and growth. After suitable crystals are grown, complete X-ray diffraction datasets can be collected using goniometer based in situ fixed target serial X-ray crystallography at room temperature. The protocol provides custom scripts to process diffraction datasets using a suite of software tools to solve and refine the protein crystal structure. This approach avoids the artefacts possibly induced during cryo-preservation or manual crystal handling in conventional crystallography experiments. We present and compare three protein structures that were solved using small crystals with dimensions of approximately 10-20 &#181;m grown in chip. By crystallizing and diffracting in situ, handling and hence mechanical disturbances of fragile crystals is minimized. The protocol details how to fabricate a custom X-ray transparent microfluidic chip suitable for in situ serial crystallography. As almost every crystal can be used for diffraction data collection, these microfluidic chips are a very efficient crystal delivery method.

Microfluidic Chips for In Situ Crystal X-ray Diffraction and In Situ Dynamic Light Scattering for Serial Crystallography

This protocol describes in detail how to fabricate and operate microfluidic devices for X-ray diffraction data collection at room temperature. Additionally, it describes how to monitor protein crystallization by dynamic light scattering and how to process and analyze obtained diffraction data.

Chips de microfluídica para dispersión ligera dinámica In Situ mediante difracción de rayos x de cristal y In Situ para la cristalografía Serial

This protocol describes fabricating microfluidic devices with low X-ray background optimized for goniometer based fixed target serial crystallography. The ...

Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework

We present a method for preparing thioester molecules as the masked form of the thiol linkers and their utilization for accessing a semiconducting and porous metal-dithiolene network in the highly ordered single crystalline state. Unlike the highly reactive free-standing thiols, which tend to decompose and complicate the crystallization of metal-thiolate open frameworks, the thioester reacts in situ to provide the thiol species, serving to mitigate the reaction between the mercaptan units and the metal centers, and to improve crystallization consequently. Specifically, the thioester was synthesized in a one-pot procedure: an aromatic bromide (hexabromotriphenylene) reacted with excess sodium thiomethoxide under vigorous conditions to first form the thioether intermediate product. The thioether was then demethylated by the excess thiomethoxide to provide the thiolate anion that was acylated to form the thioester product. The thioester was conveniently purified by standard column chromatography, and then used directly in the framework synthesis, wherein NaOH and ethylenediamine serve to revert in situ the thioester to the thiol linker for assembling the single-crystalline Pb(II)-dithiolene network. Compared with other methods for thiol synthesis (e.g., by cleaving alkyl thioether using sodium metal and liquid ammonia), the thioester synthesis here uses simple conditions and economical reagents. Moreover, the thioester product is stable and can be conveniently handled and stored. More importantly, in contrast to the generic difficulty in accessing crystalline metal-thiolate open frameworks, we demonstrate that using the thioester for in situ formation of the thiol linker greatly improves the crystallinity of the solid-state product. We intend to encourage broader research efforts on the technologically important metal-sulfur frameworks by disclosing the synthetic protocol for the thioester as well as the crystalline framework solid.

Here, we present a one-pot, transition-metal-free synthesis of thiols and thioesters from aromatic halides and sodium thiomethoxide, followed by the preparation of single crystals of a metal-dithiolene network using thiol species generated in situ from the more stable and tractable thioester.

Síntesis de un componente tiol para la cristalización de un semiconductor marco Gyroidal Metal-azufre

We present a method for preparing thioester molecules as the masked form of the thiol linkers and their utilization for accessing a semiconducting and ...

Surface Functionalization of Metal-Organic Frameworks for Improved Moisture Resistance

Metal-organic frameworks (MOFs) are a class of porous inorganic materials with promising properties in gas storage and separation, catalysis and sensing. However, the main issue limiting their applicability is their poor stability in humid conditions. The common methods to overcome this problem involve the formation of strong metal-linker bonds by using highly charged metals, which is limited to a number of structures, the introduction of alkylic groups to the framework by post-synthetic modification (PSM) or chemical vapour deposition (CVD) to enhance overall hydrophobicity of the framework. These last two usually provoke a drastic reduction of the porosity of the material. These strategies do not permit to exploit the properties of the MOF already available and it is imperative to find new methods to enhance the stability of MOFs in water while keeping their properties intact. Herein, we report a novel method to enhance the water stability of MOF crystals featuring Cu2(O2C)4&#160;paddle-wheel units, such as HKUST (where HKUST stands for Hong Kong University of Science &#38; Technology), with the catechols functionalized with alkyl and fluoro-alkyl chains. By taking advantage of the unsaturated metal sites and the catalytic catecholase-like activity of CuII ions, we are able to create robust hydrophobic coatings through the oxidation and subsequent polymerization of the catechol units on the surface of the crystals under anaerobic and water-free conditions without disrupting the underlying structure of the framework. This approach not only affords the material with improved water stability but also provides control over the function of the protective coating, which enables the development of functional coatings for the adsorption and separations of volatile organic compounds. We are confident that this approach could also be extended to other unstable MOFs featuring open metal sites.

Robust functional catechol coatings were produced in one step by direct reaction of the material known as HKUST with synthetic catechols under anaerobic conditions. The formation of homogeneous coatings surrounding the entire crystal is ascribed to the biomimetic catalytic activity of Cu(II) dimers on the external surface of the crystals.

Funcionalización de superficies de Metal-Organic Frameworks para resistencia a la humedad mejorada

Metal-organic frameworks (MOFs) are a class of porous inorganic materials with promising properties in gas storage and separation, catalysis and sensing. ...

Synthesis and Bioconjugation of Thiol-Reactive Reagents for the Creation of Site-Selectively Modified Immunoconjugates

Maleimide-bearing bifunctional probes have been employed for decades for the site-selective modification of thiols in biomolecules, especially antibodies. Yet maleimide-based conjugates display limited stability in vivo because the succinimidyl thioether linkage can undergo a retro-Michael reaction. This, of course, can lead to the release of the radioactive payload or its exchange with thiol-bearing biomolecules in circulation. Both of these processes can produce elevated activity concentrations in healthy organs as well as decreased activity concentrations in target tissues, resulting in reduced imaging contrast and lower therapeutic ratios. In 2018, we reported the creation of a modular, stable, and easily accessible phenyloxadiazolyl methyl sulfone reagent &#8212; dubbed &#8216;PODS&#8217; &#8212; as a platform for thiol-based bioconjugations. We have clearly demonstrated that PODS-based site-selective bioconjugations reproducibly and robustly create homogenous, well-defined, highly immunoreactive, and highly stable radioimmunoconjugates. Furthermore, preclinical experiments in murine models of colorectal cancer have shown that these site-selectively labeled radioimmunoconjugates exhibit far superior in vivo performance compared to radiolabeled antibodies synthesized via maleimide-based conjugations. In this protocol, we will describe the four-step synthesis of PODS, the creation of a bifunctional PODS-bearing variant of the ubiquitous chelator DOTA (PODS-DOTA), and the conjugation of PODS-DOTA to the HER2-targeting antibody trastuzumab.

In this protocol, we will describe the synthesis of PODS, a phenyoxadiazolyl methyl sulfone-based reagent for the site-selective attachment of cargos to the thiols of biomolecules, particularly antibodies. In addition, we will describe the synthesis and characterization of a PODS-bearing bifunctional chelator and its conjugation to a model antibody.

Síntesis y Bioconjugation de tioles reactivos reactivos para la creación de sitio selectivamente modificados Immunoconjugates

Maleimide-bearing bifunctional probes have been employed for decades for the site-selective modification of thiols in biomolecules, especially antibodies. ...