The authors thank the Laboratory Directed Research and Development program at the Savannah River National Laboratory (SRNL) for funding. We thank Dr. Fernando Fondeur for collection and interpretation of the FT-IR spectra and Dr. John Seaman of the Savannah River Ecology Laboratory for the use of the DLS instrument for particle size measurements. We also thank the Dr. Daniel Chan of the University of Washington and the National Institute of Health (Grant #1R01DE021373-01), for funding experiments investigating the ion exchange reactions with Au(III). The Savannah River National Laboratory is operated by Savannah River Nuclear Solutions, LLC for the Department of Energy under contract DE-AC09-08SR22470.

1. Synthesis of Nano-monosodium Titanate (nMST)
<ol>
	<li>Prepare 10 ml of solution #1 by adding 0.58 ml of 25 wt % sodium methoxide solution to 7.62 ml of isopropanol followed by 1.8 ml of titanium isopropoxide.</li>
	<li>Prepare 10 ml of solution #2 by adding 0.24 ml of ultrapure water to 9.76 ml of isopropanol.</li>
	<li>Add 280 ml of isopropanol to a 3-neck 500-ml round bottom flask, followed by 0.44 ml of Triton X-100 (average MW: 625 g/mol). Stir the solution well with a magnetic stir bar.</li>
	<li>Prepare a dual channel syringe pump to deliver solutions #1 and #2 at a rate of 0.333&#160;ml/min.</li>
	<li>Load solutions #1 and #2 into two separate 10-ml syringes fitted with a length of tubing that will allow delivery of the solution from the syringe pump to below the solution level in the 500-ml round bottom flask.</li>
	<li>While stirring, add all of solutions #1 and #2 (10 ml each) to the reaction using the syringe pump programmed in step 1.4.</li>
	<li>After the addition is complete, cap the flask and continue to stir for 24 hr at RT.</li>
	<li>Uncap the flask and heat the reaction mixture to ~82 &#176;C (refluxing isopropanol) for 45-90 min, followed by purging with nitrogen while maintaining heating. As isopropanol is evaporated, add ultrapure water intermittently to replace the evaporated isopropanol.</li>
	<li>After most of the isopropanol has evaporated and the volume of water added is approximately 50 ml, remove the heat and allow the reaction mixture to cool.</li>
	<li>Collect the product by filtering through a 0.1-&#181;m nylon filter paper, and wash several times with water to remove the surfactant and any residual isopropanol. Do not filter to dryness. After washing is complete, transfer the slurry from the filter into a pre-weighed bottle or vial, and store as an aqueous slurry.</li>
	<li>Determine the yield by determining the weight percent solids of the slurry. This can be done by measuring the weight of an aliquot of the slurry before and after drying.</li>
</ol>
2. Au(III) Ion Exchange
<ol>
	<li>Transfer 6.50 g of 4.23 wt % nMST slurry to a 50-ml centrifuge tube. This amount may vary based on the actual weight percent of the nMST slurry produced in step 1.10 above, and determined in step 1.11.</li>
	<li>Weigh out 0.0659 g of HAuCl4&#183;3H2O into a 1-dram glass vial. The target Ti:Au mass ratio is 4:1.</li>
	<li>Dissolve the HAuCl4&#183;3H2O in ~ 1 ml of water, then transfer to the centrifuge tube containing the nMST. Rinse the vial several times with additional water to ensure all of the HAuCl4&#183;3H2O is transferred to the centrifuge tube containing the nMST.</li>
	<li>Dilute the suspension with additional water, as necessary, to bring the total volume to 11 ml. Target a final Au(III) concentration of approximately 15 mM.</li>
	<li>Wrap the centrifuge tube in foil to keep the suspension in the dark, and then tumble the suspension on a shaker rotisserie for a minimum of 4 days.</li>
	<li>Collect the product by centrifuging at 3,000 x g for 15 min to isolate the solids. Wash the solids three times with distilled water by redispersing in water, and reisolate by centrifuging at 3,000 x g for 15 min to remove any unexchanged Au(III).</li>
	<li>Store the final product either as an aqueous suspension by redispersing in water, or as a moist solid by decanting off the final wash water and capping the tube. Store the product in the dark.</li>
</ol>
3. Preparation of the Peroxotitanate
<ol>
	<li>Transfer 5 g of a 9.8 wt % slurry of nMST to a small flask.</li>
	<li>Weigh out 0.154 g of 30 wt % H2O2 solution. The target H2O2:Ti molar ratio is 0.25:1.</li>
	<li>While stirring the nMST suspension well add the 0.154 g of H2O2 solution drop-wise. Upon H2O2 addition, the suspension of white solids immediately turns yellow.</li>
	<li>After the addition is complete stir the reaction at ambient temperature for 24 hr.</li>
	<li>Collect the product by filtering through a 0.1-&#181;m nylon filter, and wash several times with water to remove any unreacted H2O2. Do not filter to dryness. After washing is complete, transfer the slurry from the filter into a pre-weighed bottle or vial, and store as an aqueous slurry.</li>
</ol>

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The authors have nothing to disclose.

The presence of extraneous water, for example from impure reagents, can alter the outcome of the reaction, leading to larger or more polydisperse particles. Therefore, care should be taken to ensure dry reactants are used. The titanium isopropoxide and sodium methoxide should be stored in a desiccator when not in use. High purity isopropanol should also be used for the synthesis.
Temperature was found to play a key role in the conversion of the product from a gel to particulate form. TEM images before and after heating to 82 &#176;C show the product appears as a semi-particulate/semi-gel-like state prior to heating, but after heating the product appears solid and particulate in nature. Thus, the low temperature heating for 45-90 min&#160;is needed to complete particulate formation of the nMST.
As noted in this paper, the addition of a surfactant is critical to control the final size of the monosodium titanate. However, for the MST to serve as an effective ion exchanger, the surfactant must be removed so that all sites are accessible for the ion-exchange reaction. Thus, the choice of a suitable surfactant must consider not only the particle growth properties, but also chemical properties that allow the surfactant to be easily and effectively removed by economical means. In the case of the Triton X series of surfactants, these surfactants are very soluble in water and can be effectively removed by rinsing with water. For other surfactants, effective removal may require rinsing with a non-aqueous liquid.
The technique described in this work has expanded the range of particle sizes of MST that can be prepared, down into the nano regime. This has opened up the possibility for new applications for these materials, including their use as therapeutic metal delivery platforms. The decrease in particle size also increases the sorption kinetics, making the materials more efficient ion-exchangers. Modifications of the conditions used in this technique could further expand the range of particle sizes available, not only to smaller nanomaterials, but also to produce particles of larger size if that is desirable for a particular application.
While this technique is limited to the synthesis of materials that can be prepared using a sol-gel synthesis, it could be applied to other materials beyond MST. Not only could this technique be applied to RT sol-gel syntheses, like the one described, but application to a hydrothermal synthesis could also be envisioned. In the hydrothermal synthesis, the addition of the surfactant to the precursor solution could serve to limit the size of the precursor material formed, leading to faster reaction during the hydrothermal step, and also the possible formation of smaller particles of the final product.

Titanium dioxide and alkali metal titanates are widely used in a variety of applications such as pigments in paint and skin care products and as photocatalysts in energy conversion and utilization.1-3 Sodium titanates have been shown to be effective materials to remove a range of cations over a wide range of pH conditions through cation exchange reactions.4-7
In addition to the applications just described, micron-sized sodium titanates and sodium peroxotitanates have recently been shown to also serve as a therapeutic metal delivery platform. In this application, therapeutic metal ions such as Au(III), Au(I), and Pt(II) are exchanged for the sodium ions of monosodium titanate (MST). In vitro tests with the noble metal-exchanged titanates indicate suppression of the growth of cancer and bacterial cells by an unknown mechanism.8,9
Historically, sodium titanates have been produced using both sol-gel and hydrothermal synthetic techniques resulting in fine powders with particle sizes ranging from a few to several hundred microns.4,5,10,11 More recently, synthetic methods have been reported that produced nanosize titanium dioxide, metal-doped titanium oxides, and a variety of other metal titanates. Examples include sodium titanium oxide nanotubes (NaTONT) or nanowires by reaction of titanium dioxide in excess sodium hydroxide at elevated temperature and pressure,12-14 sodium titanate nanofibers by reaction of peroxotitanic acid with excess sodium hydroxide at elevated temperature and pressure,15 and sodium and cesium titanate nanofibers by delamination of acid-exchanged micron-sized titanates.16
The synthesis of nanosize sodium titanates and sodium peroxotitanates is of interest to enhance ion exchange kinetics, which are typically controlled by film diffusion or intraparticle diffusion. These mechanisms are largely controlled by the particle size of the ion exchanger. In addition, as a therapeutic metal delivery platform, the particle size of the titanate material would be expected to significantly affect the nature of the interaction between the metal-exchanged titanate and the cancer and bacterial cells. For example, bacterial cells, which are typically on the order of 0.5 &#8211; 2 &#181;m, would likely have different interactions with micron size particles versus nanosized particles. In addition, non-phagocytic eukaryotic cells have been shown to only internalize particles with a size of less than 1 micron.17 Thus, the synthesis of nanosize sodium titanates is also of interest to facilitate metal delivery and cellular uptake from the titanate delivery platform. Reducing the size of sodium titanates and peroxotitanates will also increase the effective capacity in metal ion separations and enhance photochemical properties of the material.16,18 This paper describes a protocol developed to synthesize nanosize monosodium titanate (nMST) under mild sol-gel conditions.19 The preparation of the corresponding peroxide modified nMST; along with an ion-exchange reaction to load the nMST with Au(III) are also described.

<table border="0" cellpadding="0" cellspacing="0" width="923">
	<tbody>
		<tr>
			<td>Titanium(IV) isopropoxide</td>
			<td>Sigma Aldrich</td>
			<td>377996</td>
			<td>99.999% trace metals basis</td>
		</tr>
		<tr>
			<td>Isopropyl alcholol, 99.9%</td>
			<td>Sigma Aldrich</td>
			<td>650447</td>
			<td>HPLC grade (Chomasolv)</td>
		</tr>
		<tr>
			<td>Sodium methoxide in methanol</td>
			<td>Sigma Aldrich</td>
			<td>156256</td>
			<td>25 wt%</td>
		</tr>
		<tr>
			<td>Triton X-100</td>
			<td>Sigma Aldrich</td>
			<td>T9284</td>
			<td>BioXtra</td>
		</tr>
		<tr>
			<td>hydrogen tetrachloroaurate(III) trihydrate</td>
			<td>Sigma Aldrich</td>
			<td>G4022</td>
			<td>ACS reagent grade</td>
		</tr>
		<tr>
			<td>hydrogen peroxide (30 wt%)</td>
			<td>Fisher</td>
			<td>H325</td>
			<td>Certified ACS</td>
		</tr>
		<tr>
			<td>10-mL syringes</td>
			<td>Fisher</td>
			<td>14-823-16E</td>
			<td></td>
		</tr>
		<tr>
			<td>Dual channel syringe pump</td>
			<td>Cole Parmer</td>
			<td>EW-74900-10</td>
			<td>Or equivalent programmable dual channel syringe pump</td>
		</tr>
		<tr>
			<td>Tygon tubing 1/8 inch ID, 1/4 inch OD</td>
			<td>Cole Parmer</td>
			<td>EW-0640776</td>
			<td></td>
		</tr>
		<tr>
			<td>Tygon tubing 1/16 inch ID, 1/8 inch OD</td>
			<td>Cole Parmer</td>
			<td>EW-0740771</td>
			<td></td>
		</tr>
		<tr>
			<td>0.1-&#181;m Nylon filter</td>
			<td>Fisher</td>
			<td>R01SP04700</td>
			<td></td>
		</tr>
		<tr>
			<td>Labquake shaker rotisserie</td>
			<td>Thermo Scientific</td>
			<td>4002110Q</td>
			<td></td>
		</tr>
	</tbody>
</table>

synthesis and reaction chemistry of nanosize monosodium titanate

This paper describes the synthesis and peroxide-modification of nanosize monosodium titanate (nMST), along with an ion-exchange reaction to load the material with Au(III) ions. The synthesis method was derived from a sol-gel process used to produce micron-sized monosodium titanate (MST), with several key modifications, including altering reagent concentrations, omitting a particle seed step, and introducing a non-ionic surfactant to facilitate control of particle formation and growth. The resultant nMST material exhibits spherical-shaped particle morphology with a monodisperse distribution of particle diameters in the range from 100 to 150&#160;nm. The nMST material was found to have a Brunauer-Emmett-Teller (BET) surface area of 285 m2g-1, which is more than an order of magnitude higher than the micron-sized MST. The isoelectric point of the nMST measured 3.34 pH units, which is a pH unit lower than that measured for the micron-size MST. The nMST material was found to serve as an effective ion exchanger under weakly acidic conditions for the preparation of an Au(III)-exchange nanotitanate. In addition, the formation of the corresponding peroxotitanate was demonstrated by reaction of the nMST with hydrogen peroxide.

MST is synthesized using a sol-gel method in which tetraisopropoxytitanium(IV) (TIPT), sodium methoxide, and water are combined and reacted in isopropanol to form seed particles of MST.4 Micron-sized particles are then grown by controlled addition of additional quantities of the reagents. The resultant particles feature an amorphous core and an outer fibrous region having dimensions of about 10 nm wide by 50 nm in length.20
Figure 1A shows a typical particle size distribution, as measured by dynamic light scattering (DLS), for micron-sized MST prepared using the established sol-gel method. This synthesis produces a multimodal distribution of particles, with the majority around 1 &#181;m. Initial attempts to reduce the particle size of the MST investigated eliminating the seed step and using much more dilute reagent concentrations. In the diluted reaction the final solvent:TIPT volume ratio was 165 compared to 5.14 in the micron-sized MST synthesis, representing a reagent dilution of ~32 during the synthesis. As seen in Figure 1B, this resulted in a bimodal distribution with particle sizes centered at 50-100 nm and at 500 nm after 24 hr of reaction. After 48 hr, a trimodal distribution is observed with the appearance of particles measuring 1,000 nm (1 &#181;m) in size (Figure 1C). DLS measurements at shorter reaction times show a bimodal distribution of particle sizes similar to that shown in Figure 1B except the distribution is centered at smaller particle sizes. Thus, we conclude that the reduced reagent concentration and absence of the seed step leads to smaller particles produced initially, but particle growth continues resulting in a mixture of both nano and micron-sized MST.
Over the last decade there have been a number of papers reporting the addition of surfactants in sol&#8211;gel syntheses to control particle size resulting in the production of nanosize titanium dioxide, metal-doped titanium dioxides and multi-metal titanium oxides.21-26 Based on these findings, we initiated a series of tests to determine if the addition of surfactant to the MST synthesis would control particle growth allowing the sole production of nanosize particles. A number of non-ionic surfactants (Brig 52; Merpol A; Triton X series (X-15, X-45, X-100, X-165, X-405); TWEEN 20; 2,4,7,9-tetramethyl-5-decyne-4,7-diol ethoxylate; and Zonyl FS300) as well as one anionic surfactant (sodium docusate) and one cationic surfactant (CTAB) were screened.
Initial experiments screened surfactants at a concentration of 0.12 moles of surfactant per mole of TIPT. Products from these reactions were screened using DLS for polydispersity and average particle size. Triton X-100, Triton X-165, Brij 52, and Zonyl FS300 showed a good combination of small particle size (Zave &#60; 150 nm) and monodispersity, with Triton X-100 and Triton X-165 showing the most narrow range of particle sizes. Additional experiments were then performed to examine a range of surfactant concentrations from 0.012 to 1.2 moles of surfactant per mole of TIPT. Higher surfactant concentrations resulted in broader distributions of particle sizes, while lower concentrations resulted in bimodal distributions suggesting that there was insufficient surfactant to limit the growth of particles. Triton X-100 at 0.12 moles per mole of TIPT appeared close to optimal for the synthesis of uniform nMST particles (Figures 2 and 3).
Temperature plays a key role in the conversion of the product from a gel to particulate form. Transmission electron microscopy (TEM) images before and after heating to 82 &#176;C show the product appears as a semi-particulate/semi-gel-like state prior to heating, but after heating the product appears solid and particulate in nature. Thus, the low temperature heating for 45-90 min&#160;is needed to complete particulate formation of the nMST.
Additional characterization of the nMST included determination of surface area and isoelectric point (IEP). Surface area measurements were obtained by Brunauer-Emmett-Teller (BET) analysis of nitrogen absorption isotherms. The BET surface area measured 285 m2g-1 for the nMST compared to only 20 m2g-1 for the micron-sized MST. The higher surface area for the nMST is consistent with the much smaller particle size of the nMST. Zeta potential measurements were performed over a range of pH conditions to determine the IEP for the nano and microtitanates. The IEPs determined are as follows: nMST = 3.34; peroxide-modified nMST = 2.05; MST = 4.46; peroxide-modified MST = 3.43. The nMST exhibited a lower IEP than MST indicating a higher fraction of surface sites available for protonation. This would be expected given the order of magnitude higher surface area of the nMST. Conversion of the nMST to the peroxide-modified nMST form lowered the IEP by more than a pH unit. A similar trend was observed upon conversion of MST to the peroxo form. The lower IEP for the peroxide-modified nMST and peroxide-modified MST materials likely results from the presence of non-bridging peroxo species that can be easily protonated and deprotonated.
The success of the surface modification of the nMST by H2O2 can be immediately observed from the color change from white to yellow. This color change is due to the &#951;2-bound protonated hydroperoxo-titanium ligand-to-metal-charge-transfer absorption band at 385 nm.27,28 Fourier transform infrared spectroscopy (FT-IR) also confirmed the formation of the peroxotitanate species as evidenced by the appearance of an absorption band at 883 cm-1 for the peroxide modified nMST (Figure 4) which is absent in the untreated nMST material. This band is very near the region of 845-875 cm-1 that is reported for the O-O stretching vibration in peroxides.29 TEM and scanning electron microscopy (SEM) analyses indicated that the particle size and morphology were retained after the peroxide reaction.
To determine the extent of the Au(III) ion-exchange, samples of the Au(III)-loaded solids were digested in hot nitric acid, followed by analysis of the diluted solution by inductively coupled plasma &#8211; emission spectroscopy (ICP-ES). The Au(III) loadings range from 71.4 mg Au/g nMST to 128.7 mg Au/g, with an average value of 97.3 mg/g. This represents a 33% increase over Au(III) loading on the micron-sized MST, which ranges from 58.0 mg Au/g MST to 88.6 mg/g, with an average value of 73.3 mg/g. TEM images of the nMST after exchange with Au(III) showed the presence of gold with no observable changes in the particle morphology. We believe that Au(III) is incorporated into the lattice of the micron and nanosize MST by coordinating to the oxygen atoms of titania as was observed in previous studies with MST exchanged with Sr2+ and UO22+.20
<img alt="Figure 1" src="/files/ftp_upload/53248/53248fig1.jpg" /> 
Figure 1. MST and nMST particle size distributions. (A) Particle size distribution of MST, (B) particle size distribution of nMST synthesized using no surfactant after 24 hr, and (C) particle size distribution of nMST synthesized using no surfactant after 48 hr. Reproduced with permission from reference 19. <a href="https://www-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/53248/53248fig1large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 2" src="/files/ftp_upload/53248/53248fig2.jpg" /> 
Figure 2. Typical particle size distribution of nMST. Particle size distribution for monosodium titanate synthesized in the presence of Triton X-100. Reproduced with permission from reference 19. <a href="https://www-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/53248/53248fig2large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 3" src="/files/ftp_upload/53248/53248fig3.jpg" /> 
Figure 3. Size and morphology of nMST and MST. (A, B) Transmission electron microscopy images of nMST; (C) scanning electron microscopy image of nMST, and (D) scanning electron microscopy image of MST. Reproduced with permission from reference 19. <a href="https://www-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/53248/53248fig3large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 4" src="/files/ftp_upload/53248/53248fig4.jpg" /> 
Figure 4. FT-IR absorption spectra of nMST (black) and peroxide-modified nMST (gray). The spectra confirm the formation of the peroxotitanate species as evidenced by the appearance of an absorption band at 883 cm-1 for the peroxide-modified nMST. Reproduced with permission from reference 19. <a href="https://www-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/53248/53248fig4large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>

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Synthesis and Reaction Chemistry of Nanosize Monosodium Titanate

The surfactant mediated sol-gel synthesis of nanosized monosodium titanate is described, along with preparation of the corresponding peroxide modified material. An ion-exchange reaction with Au(III) is also presented.

This paper describes the synthesis and peroxide-modification of nanosize monosodium titanate (nMST), along with an ion-exchange reaction to load the ...

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8.5K 조회수.  Savannah River Consulting, L.L.C.. The surfactant mediated sol-gel synthesis of nanosized monosodium titanate is described, along with preparation of the corresponding peroxide modified material. An ion-exchange reaction with Au(III) is also presented.

비디오: Synthesis and Reaction Chemistry of Nanosize Monosodium Titanate

Preparation and Use of Samarium Diiodide (SmI2) in Organic Synthesis: The Mechanistic Role of HMPA and Ni(II) Salts in the Samarium Barbier Reaction

Although initially considered an esoteric reagent, SmI2 has become a common tool for synthetic organic chemists. SmI2 is generated through the addition of molecular iodine to samarium metal in THF.1,2-3 It is a mild and selective single electron reductant and its versatility is a result of its ability to initiate a wide range of reductions including C-C bond-forming and cascade or sequential reactions. SmI2 can reduce a variety of functional groups including sulfoxides and sulfones, phosphine oxides, epoxides, alkyl and aryl halides, carbonyls, and conjugated double bonds.2-12 One of the fascinating features of SmI-2-mediated reactions is the ability to manipulate the outcome of reactions through the selective use of cosolvents or additives. In most instances, additives are essential in controlling the rate of reduction and the chemo- or stereoselectivity of reactions.13-14 Additives commonly utilized to fine tune the reactivity of SmI2 can be classified into three major groups: (1) Lewis bases (HMPA, other electron-donor ligands, chelating ethers, etc.), (2) proton sources (alcohols, water etc.), and (3) inorganic additives (Ni(acac)2, FeCl3, etc).3
Understanding the mechanism of SmI2 reactions and the role of the additives enables utilization of the full potential of the reagent in organic synthesis. The Sm-Barbier reaction is chosen to illustrate the synthetic importance and mechanistic role of two common additives: HMPA and Ni(II) in this reaction. The Sm-Barbier reaction is similar to the traditional Grignard reaction with the only difference being that the alkyl halide, carbonyl, and Sm reductant are mixed simultaneously in one pot.1,15 Examples of Sm-mediated Barbier reactions with a range of coupling partners have been reported,1,3,7,10,12 and have been utilized in key steps of the synthesis of large natural products.16,17 Previous studies on the effect of additives on SmI2 reactions have shown that HMPA enhances the reduction potential of SmI2 by coordinating to the samarium metal center, producing a more powerful,13-14,18 sterically encumbered reductant19-21 and in some cases playing an integral role in post electron-transfer steps facilitating subsequent bond-forming events.22 In the Sm-Barbier reaction, HMPA has been shown to additionally activate the alkyl halide by forming a complex in a pre-equilibrium step.23
Ni(II) salts are a catalytic additive used frequently in Sm-mediated transformations.24-27 Though critical for success, the mechanistic role of Ni(II) was not known in these reactions. Recently it has been shown that SmI2 reduces Ni(II) to Ni(0), and the reaction is then carried out through organometallic Ni(0) chemistry.28
These mechanistic studies highlight that although the same Barbier product is obtained, the use of different additives in the SmI2 reaction drastically alters the mechanistic pathway of the reaction. The protocol for running these SmI2-initiated reactions is described.

Preparation and Use of Samarium Diiodide SmI2 in Organic Synthesis: The Mechanistic Role of HMPA and NiII Salts in the Samarium Barbier Reaction

A straightforward procedure for the preparation of samarium diiodide (SmI2) in THF is described. The role of two main additives namely hexamethylphosphoramide (HMPA) and Ni(acac)2 in Sm mediated reactions is demonstrated in the Sm-Barbier reaction.

준비와 사마륨 Diiodide 이용 (SMI<sub&gt; 2</sub&gt;) 유기 합성의 : 사마륨 Barbier 반응에 HMPA과 니켈 (II) 소금의 기계론의 역할

Although initially considered an esoteric reagent, SmI2 has become a common tool for synthetic organic chemists. SmI2 is generated through the addition of ...

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Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents

Amide coupling reactions can be used to synthesize bispyridine-based ligands for use as bridging linkers in multinuclear platinum anticancer drugs. Isonicotinic acid, or its derivatives, are coupled to variable length diaminoalkane chains under an inert atmosphere in anhydrous DMF or DMSO with the use of a weak base, triethylamine, and a coupling agent, 1-propylphosphonic anhydride. The products precipitate from solution upon formation or can be precipitated by the addition of water. If desired, the ligands can be further purified by recrystallization from hot water. Dinuclear platinum complex synthesis using the bispyridine ligands is done in hot water using transplatin. The most informative of the chemical characterization techniques to determine the structure and gross purity of both the bispyridine ligands and the final platinum complexes is 1H NMR with particular analysis of the aromatic region of the spectra (7-9 ppm). The platinum complexes have potential application as anticancer agents and the synthesis method can be modified to produce trinuclear and other multinuclear complexes with different hydrogen bonding functionality in the bridging ligand.

This protocol describes the use of amide coupling reactions of isonicotinic acid and diaminoalkanes to form bridging ligands suitable for use in the synthesis of multinuclear platinum complexes, which combine aspects of the anticancer drugs BBR3464 and picoplatin.

이핵 항암제로 플래티넘 비스 피리딘 계 리간드와 이들 착물의 합성 아미드 커플 링 반응

Amide coupling reactions can be used to synthesize bispyridine-based ligands for use as bridging linkers in multinuclear platinum anticancer drugs. ...

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.

기능화의 합성 및 특성 금속 - 유기 프레임 워크

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

Highly Stereoselective Synthesis of 1,6-Ketoesters Mediated by Ionic Liquids: A Three-component Reaction Enabling Rapid Access to a New Class of Low Molecular Weight Gelators

In organic chemistry ionic liquids (ILs) have emerged as safe and recyclable reaction solvents. In the presence of a base ILs can be deprotonated to form catalytically active N-Heterocyclic Carbenes (NHCs). Here we have used ILs as precatalysts in the addition of &#945;,&#946;-unsaturated aldehydes to chalcones to form 1,6-ketoesters, incorporating an anti-diphenyl moiety in a highly stereoselective fashion. The reaction has a broad substrate scope and several functional groups and heteroaromatics can be integrated into the ketoester backbone in generally good yields with maintained stereoselectivity. The reaction protocol is robust and scalable. The starting materials are inexpensive and the products can be obtained after simple filtration, avoiding solvent-demanding chromatography. Furthermore, the IL can be recycled up to 5 times without any loss of reactivity. Moreover, the 1,6-ketoester end product is a potent gelator in several hydrocarbon based solvents. The method enables rapid access to and evaluation of a new class of low molecular weight gelators (LMWGs) from recyclable and inexpensive starting materials.

Ionic liquids (ILs) mediate fast, simple and cheap access to 1,6-ketoesters in high diastereoselectivities and good yields. The reaction protocol is robust and the 1,6-ketoesters can be obtained in gram scale after a simple filtration protocol. Moreover, the 1,6-ketoesters are potent gelators in hydrocarbon solvents.

이온 성 액체에 의해 매개 1,6- Ketoesters의 높은 입체 선택적 합성 : 저 분자량 젤 레이터의 새로운 클래스에 빠른 액세스를 가능하게하는 3 요소 반응

In organic chemistry ionic liquids (ILs) have emerged as safe and recyclable reaction solvents. In the presence of a base ILs can be deprotonated to form ...

Synthesis of Programmable Main-chain Liquid-crystalline Elastomers Using a Two-stage Thiol-acrylate Reaction

This study presents a novel two-stage thiol-acrylate Michael addition-photopolymerization (TAMAP) reaction to prepare main-chain liquid-crystalline elastomers (LCEs) with facile control over network structure and programming of an aligned monodomain. Tailored LCE networks were synthesized using routine mixing of commercially available starting materials and pouring monomer solutions into molds to cure. An initial polydomain LCE network is formed via a self-limiting thiol-acrylate Michael-addition reaction. Strain-to-failure and glass transition behavior were investigated as a function of crosslinking monomer, pentaerythritol tetrakis(3-mercaptopropionate) (PETMP). An example non-stoichiometric system of 15 mol% PETMP thiol groups and an excess of 15 mol% acrylate groups was used to demonstrate the robust nature of the material. The LCE formed an aligned and transparent monodomain when stretched, with a maximum failure strain over 600%. Stretched LCE samples were able to demonstrate both stress-driven thermal actuation when held under a constant bias stress or the shape-memory effect when stretched and unloaded. A permanently programmed monodomain was achieved via a second-stage photopolymerization reaction of the excess acrylate groups when the sample was in the stretched state. LCE samples were photo-cured and programmed at 100%, 200%, 300%, and 400% strain, with all samples demonstrating over 90% shape fixity when unloaded. The magnitude of total stress-free actuation increased from 35% to 115% with increased programming strain. Overall, the two-stage TAMAP methodology is presented as a powerful tool to prepare main-chain LCE systems and explore structure-property-performance relationships in these fascinating stimuli-sensitive materials.

A novel methodology is presented to synthesize and program main-chain liquid-crystalline elastomers using commercially available starting monomers. A wide range of thermomechanical properties was tailored by adjusting the amount of crosslinker, while the actuation performance was dependent on the amount of applied strain during programming.

이단 티올 레이트 반응을 이용하여 프로그래밍 주쇄 액정 엘라스토머의 합성

This study presents a novel two-stage thiol-acrylate Michael addition-photopolymerization (TAMAP) reaction to prepare main-chain liquid-crystalline ...

Synthesis and Characterization of Supramolecular Colloids

Control over colloidal assembly is of utmost importance for the development of functional colloidal materials with tailored structural and mechanical properties for applications in photonics, drug delivery and coating technology. Here we present a new family of colloidal building blocks, coined supramolecular colloids, whose self-assembly is controlled through surface-functionalization with a benzene-1,3,5-tricarboxamide (BTA) derived supramolecular moiety. Such BTAs interact via directional, strong, yet reversible hydrogen-bonds with other identical BTAs. Herein, a protocol is presented that describes how to couple these BTAs to colloids and how to quantify the number of coupling sites, which determines the multivalency of the supramolecular colloids. Light scattering measurements show that the refractive index of the colloids is almost matched with that of the solvent, which strongly reduces the van der Waals forces between the colloids. Before photo-activation, the colloids remain well dispersed, as the BTAs are equipped with a photo-labile group that blocks the formation of hydrogen-bonds. Controlled deprotection with UV-light activates the short-range hydrogen-bonds between the BTAs, which triggers the colloidal self-assembly. The evolution from the dispersed state to the clustered state is monitored by confocal microscopy. These results are further quantified by image analysis with simple routines using ImageJ and Matlab. This merger of supramolecular chemistry and colloidal science offers a direct route towards light- and thermo-responsive colloidal assembly encoded in the surface-grafted monolayer.

A protocol for the synthesis and characterization of colloids coated with supramolecular moieties is described. These supramolecular colloids undergo self-assembly upon the activation of the hydrogen-bonds between the surface-anchored molecules by UV-light.

Control over colloidal assembly is of utmost importance for the development of functional colloidal materials with tailored structural and mechanical ...

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.

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

Epitaxial Growth of Perovskite Strontium Titanate on Germanium via Atomic Layer Deposition

Atomic layer deposition (ALD) is a commercially utilized deposition method for electronic materials. ALD growth of thin films offers thickness control and conformality by taking advantage of self-limiting reactions between vapor-phase precursors and the growing film. Perovskite oxides present potential for next-generation electronic materials, but to-date have mostly been deposited by physical methods. This work outlines a method for depositing SrTiO3 (STO) on germanium using ALD. Germanium has higher carrier mobilities than silicon and therefore offers an alternative semiconductor material with faster device operation. This method takes advantage of the instability of germanium's native oxide by using thermal deoxidation to clean and reconstruct the Ge (001) surface to the 2&#215;1 structure. 2-nm thick, amorphous STO is then deposited by ALD. The STO film is annealed under ultra-high vacuum and crystallizes on the reconstructed Ge surface. Reflection high-energy electron diffraction (RHEED) is used during this annealing step to monitor the STO crystallization. The thin, crystalline layer of STO acts as a template for subsequent growth of STO that is crystalline as-grown, as confirmed by RHEED. In situ X-ray photoelectron spectroscopy is used to verify film stoichiometry before and after the annealing step, as well as after subsequent STO growth. This procedure provides framework for additional perovskite oxides to be deposited on semiconductors via chemical methods in addition to the integration of more sophisticated heterostructures already achievable by physical methods.

This work details the procedures for the growth and characterization of crystalline SrTiO3 directly on germanium substrates by atomic layer deposition. The procedure illustrates the ability of an all-chemical growth method to integrate oxides monolithically onto semiconductors for metal-oxide semiconductor devices.

원자 층 증착을 통해 게르마늄에 페 로브 스카이 스트론튬 티탄의 에피 택셜 성장

Atomic layer deposition (ALD) is a commercially utilized deposition method for electronic materials. ALD growth of thin films offers thickness control and ...

Continuous Flow Chemistry: Reaction of Diphenyldiazomethane with p-Nitrobenzoic Acid

Continuous flow technology has been identified as instrumental for its environmental and economic advantages leveraging superior mixing, heat transfer and cost savings through the &#34;scaling out&#34; strategy as opposed to the traditional &#34;scaling up&#34;. Herein, we report the reaction of diphenyldiazomethane with p-nitrobenzoic acid in both batch and flow modes. To effectively transfer the reaction from batch to flow mode, it is essential to first conduct the reaction in batch. As a consequence, the reaction of diphenyldiazomethane was first studied in batch as a function of temperature, reaction time, and concentration to obtain kinetic information and process parameters. The glass flow reactor set-up is described and combines two types of reaction modules with &#34;mixing&#34; and &#34;linear&#34; microstructures. Finally, the reaction of diphenyldiazomethane with p-nitrobenzoic acid was successfully conducted in the flow reactor, with up to 95% conversion of the diphenyldiazomethane in 11 min. This proof of concept reaction aims to provide insight for scientists to consider flow technology&#39;s competitiveness, sustainability, and versatility in their research.

Continuous Flow Chemistry: Reaction of Diphenyldiazomethane with p-Nitrobenzoic Acid

Flow chemistry carries environmental and economic advantages by leveraging superior mixing, heat transfer and cost benefits. Herein, we provide a blueprint to transfer chemical processes from batch to flow mode. The reaction of diphenyldiazomethane (DDM) with p-nitrobenzoic acid, conducted in batch and flow, was chosen for proof of concept.

P-Nitrobenzoic 산 Diphenyldiazomethane의 연속 흐름 화학: 반응

Continuous flow technology has been identified as instrumental for its environmental and economic advantages leveraging superior mixing, heat transfer and ...

Synthesis and Mass Spectrometry Analysis of Oligo-peptoids

Peptoids are sequence-controlled peptide-mimicking oligomers consisting of N-alkylated glycine units. Among many potential applications, peptoids have been thought of as a type of molecular information storage. Mass spectrometry analysis has been considered the method of choice for sequencing peptoids. Peptoids can be synthesized via solid phase chemistry using a repeating two-step reaction cycle. Here we present a method to manually synthesize oligo-peptoids and to analyze the sequence of the peptoids using tandem mass spectrometry (MS/MS) techniques. The sample peptoid is a nonamer consisting of alternating N-(2-methyloxyethyl)glycine (Nme) and N-(2-phenylethyl)glycine (Npe), as well as an N-(2-aminoethyl)glycine (Nae) at the N-terminus. The sequence formula of the peptoid is Ac-Nae-(Npe-Nme)4-NH2, where Ac is the acetyl group. The synthesis takes place in a commercially available solid-phase reaction vessel. The rink amide resin is used as the solid support to yield the peptoid with an amide group at the C-terminus. The resulting peptoid product is subjected to sequence analysis using a triple-quadrupole mass spectrometer coupled to an electrospray ionization source. The MS/MS measurement produces a spectrum of fragment ions resulting from the dissociation of charged peptoid. The fragment ions are sorted out based on the values of their mass-to-charge ratio (m/z). The m/z values of the fragment ions are compared against the nominal masses of theoretically predicted fragment ions, according to the scheme of peptoid fragmentation. The analysis generates a fragmentation pattern of the charged peptoid. The fragmentation pattern is correlated to the monomer sequence of the neutral peptoid. In this regard, MS analysis reads out the sequence information of the peptoids.

A protocol is described for the manual synthesis of oligo-peptoids followed by sequence analysis by mass spectrometry.

합성 및 올리고 peptoids의 질량 분석 분석

Peptoids are sequence-controlled peptide-mimicking oligomers consisting of N-alkylated glycine units. Among many potential applications, peptoids have ...