The 2,2,6,6-tetramethyl-1-piperidinyloxy Research Articles

Rate-Limited Reaction in TEMPO/Laccase/O2 Oxidation of Cellulose.

The environment-friendly oxidation of cellulose by the 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO)/laccase/O2 system is an alternative route with huge potential to prepare cellulose nanofibers. It is found that the concentration of TEMPO significantly affects the oxidation efficiency. An effective method for improving the oxidation effect is to increase the TEMPO concentration and prolong the oxidation time. To clarify the rate-limited step of TEMPO/laccase/O2 oxidation of cellulose, the academically accepted oxidation process is divided into individual pathways. A series of experiments is conducted with laccase and the three forms of organocatalyst (TEMPO, oxoammonium (TEMPO+), and hydroxylamine (TEMPOH)) to simulate individual reactions and calculate the reaction rates. The concentrations of TEMPO and oxoammonium are monitored by EPR spectroscopy. The oxidation rate of TEMPO by laccase varies at different pH conditions, and laccase activity is much higher at pH 4.5. Other reactions without laccase involved express a higher reaction rate when the pH value increased. TEMPO is mainly regenerated through a comproportionation reaction between oxoammonium and hydroxylamine. The acceleration of TEMPO regeneration by laccase is not obvious. The results indicate that the rate-limited reaction in TEMPO/laccase/O2 oxidation is cellulose oxidation by TEMPO+.

Synthesis and characterisation of redox hydrogels based on stable nitroxide radicals.

The principle of encapsulation/release of a guest molecule from stimuli responsive hydrogels (SRHs) is mainly realised with pH, temperature or light stimuli. However, only a limited number of redox responsive hydrogels have been investigated so far. We report here the development of a SRH that can release its guest molecule upon a redox stimulus. To obtain this redox hydrogel, we have introduced into the hydrogel the 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) stable nitroxide radical, which can be reversibly oxidized into an oxoammonium cation (TEMPO+). Water solubility is provided by the presence of the (oligoethyleneglycol)methacrylate (OEGMA) comonomer. Electrochemical and mechanical characterization showed that those gels exhibit interesting physicochemical properties, making them very promising candidates for practical use in a wide range of applications.

Effect of NaClO dosage on the structure of degummed hemp fibers by 2,2,6, 6-tetramethyl-1-piperidinyloxy-laccase degumming

In this study, different dosages of NaClO were used in the 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO)-laccase degumming system to remove non-cellulosic materials, and their effects on the structure of hemp fibers were analyzed and discussed. A scanning electron microscope was used to depict the surface morphology of fibers after oxidative degumming under various dosages of NaClO in the TEMPO-laccase degumming system. Chemical composition analysis was used to determine the content changes of the different components. Meanwhile, the content of functional groups was also discussed. Fourier transfer infrared spectroscopy, nuclear magnetic resonance spectroscopy, and X-ray diffraction were employed to evaluate the microstructural changes of degummed hemp fibers obtained from the degumming processes with different dosages of NaClO. The results showed that after the TEMPO-laccase system degumming process with a NaClO dosage of 16%, the cleanest and smoothest surface of degummed fibers could be observed and the non-cellulosic materials were significantly removed without any crystalline transformation or damage in the cellulose. This research could shed light on determining favorable operation parameters for hemp oxidation degumming and increasing the degumming efficiency, as well as in the oxidation control and quality assurance of hemp fibers for textile downstream end uses.

Synthetic strategy for selective N-modified and O-modified PEGylated chitosan derivatives

A series of PEGylated chitosan derivatives were synthesized using protection group strategy. N-mPEG chitosan derivatives were synthesized by two different synthetic routes - either by direct substitution at the amino group or using a spacer with the help of 3,6-O-diTBDMS-protected chitosan as a precursor. The use of TBDMS protection on both the hydroxyl groups of chitosan allowed modification selectively at the amino functionality. N,N,N-trimethyl chitosan (TMC) homopolymer was synthesized and utilized for the 2,2,6,6-Tetramethyl-1-piperidinyloxy (TEMPO) oxidation of the C-6-hydroxyl group. This oxidation step was optimized using various reaction conditions to obtain the 100% oxidized product N,N,N-trimethyl-O-6-carboxy chitosan. The oxidized product was then further used for selective PEGylation at the hydroxyl group of TMC by esterification. Characterization of the synthesized chitosan derivatives was carried out by 1H and COSY NMR and IR spectroscopy.

Enhancing adsorption of heavy metal ions onto biobased nanofibers from waste pulp residues for application in wastewater treatment

Biobased nanofibers are increasingly considered in purification technologies due to their high mechanical properties, high specific surface area, versatile surface chemistry and natural abundance. In this work, cellulose and chitin nanofibers functionalized with carboxylate entities have been prepared from pulp residue (i.e., a waste product from the pulp and paper production) and crab shells, respectively, by chemically modifying the initial raw materials with the 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) mediated oxidation reaction followed by mechanical disintegration. A thorough investigation has first been carried out in order to evaluate the copper(II) adsorption capacity of the oxidized nanofibers. UV spectrophotometry, X-ray photoelectron spectroscopy and wavelength dispersive X-rays analysis have been employed as characterization tools for this purpose. Pristine nanofibers presented a relatively low content of negative charges on their surface thus adsorbing a low amount of copper(II). The copper adsorption capacity of the nanofibers was enhanced due to the oxidation treatment since the carboxylate groups introduced on the nanofibers surface constituted negative sites for electrostatic attraction of copper ions (Cu2+). The increase in copper adsorption on the nanofibers correlated both with the pH and carboxylate content and reached maximum values of 135 and 55 mg g−1 for highly oxidized cellulose and chitin nanofibers, respectively. Furthermore, the metal ions could be easily removed from the contaminated nanofibers through a washing procedure in acidic water. Finally, the adsorption capacity of oxidized cellulose nanofibers for other metal ions, such as nickel(II), chromium(III) and zinc(II), was also demonstrated. We conclude that TEMPO oxidized biobased nanofibers from waste resources represent an inexpensive and efficient alternative to classical sorbents for heavy metal ions removal from contaminated water.

Supercapacitor-battery hybrid energy storage devices from an aqueous nitroxide radical active material

A hybrid electrochemical energy storage device was fabricated in aqueous NaOH with the 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) nitroxide radical as the active material, hydroquinone as the counter electrode active material, and an OH−-selective separating membrane. The working principle of this device was investigated and it can be considered as a supercapacitor-battery hybrid energy storage system. Device performance was characterized by cyclic voltammetry and galvanostatic charge-discharge testing. When using multi-walled carbon nanotubes (MWCNTs) as electrode support materials, a high pseudo-capacitance of 1280 F g−1 was obtained with the TEMPO nitroxide radical as the active material at a 1 mV s−1 scan rate. This was ∼33 times larger than the inherent double layer capacitance of MWCNTs. The electrode material and active material dissolved in solution could potentially be substituted with similar materials. This simple design provides a new approach for fabricating high performance supercapacitor-battery hybrid energy storage devices.

Electrochemical properties of new organic radical materials for lithium secondary batteries

The use of ionic liquid (IL)-supported organic radicals as cathode-active materials in lithium secondary batteries is reported in this article. Two different types of IL-supported organic radicals based on the 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) radical and imidazolium hexafluorophosphate IL were synthesized. The first type is a mono-radical with one unit of TEMPO and the second is a symmetrical di-radical with 2 U of TEMPO; both are viscous liquids at 25 °C. The radicals exhibit electrochemical activity at ∼3.5 V versus Li/Li + as revealed in the cyclic voltammetry tests. The organic radical batteries (ORBs) with these materials as the cathode, a lithium metal anode and 1 M LiPF 6 in EC/DMC electrolyte exhibited good performance at room temperature during the charge–discharge and cycling tests. The batteries exhibited specific capacities of 59 and 80 mAh g −1 at 1 C-rate with the mono- and di-radicals as the cathodes, respectively, resulting in 100% utilization of the materials. The performance degradation with increasing C-rate is very minimal for the ORBs, thus demonstrating good rate capability.

Synthesis of star-like random copolymers from resorcinarene-based octa-functional alkoxyamine initiatorvia nitroxide mediated free radical polymerization

An octa-functional alkoxyamine initiator, with the 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) free radical, was synthesized based on resorcinarene, with its efficiency to initiate the nitroxide-mediated free radical copolymerization of styrene and methyl methacrylate (MMA) described. A difunctional analogue of this initiator was also synthesized, using resorcinol as the core molecule. The structures of the resulting initiators were confirmed by homolysis studies based on electron spin resonance spectroscopy and molecular modeling. The polymerization behavior and characteristics of the polymers obtained using these two initiators were also compared. Well-defined star-shaped and linear random copolymers, with low polydispersities and controlled molecular weights, were prepared. The efficiencies of these initiators towards copolymerization, as well as the parameters permitting the formation of well-defined polymers, were also investigated. The reactivity ratios werer a = 0.42 (a = styrene) andr b = 0.33 (b = MMA) for the octa-functional initiator system andr a = 0.45 andr b = 0.39 for the difunctional initiator system.

Nitroxyl free radical binding to Si(1 0 0): a combined scanning tunneling microscopy and computational modeling study

The ultra-high vacuum scanning tunneling microscope (UHV-STM) was used to investigate the addition of the 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) radical to the Si(1 0 0) surface. Room temperature studies performed on clean Si(1 0 0)-2 × 1 confirm the proposed binding of the unpaired valence electron associated with the singly occupied molecular orbital (SOMO) of the molecule with a Si dangling bond. A strong bias dependence in the topography of isolated molecules was observed in the range of −2.0 to +2.5 V. Semiempirical and density functional calculations of TEMPO bound to a three-dimer silicon cluster model yield occupied state density isosurfaces below the highest occupied (HOMO) and unoccupied state densities isosurfaces above the lowest unoccupied molecular orbital (LUMO) which trend in qualitative agreement with the bias dependent STM topography. Furthermore, the placement of TEMPO molecules on dangling bonds was controlled with atomic precision on the monohydride Si(1 0 0) surface via electron stimulated desorption of H, demonstrating the compatibility of nitroxyl free radical binding chemistries with nanopatterning techniques such as feedback controlled lithography.

Mobility of the spin‐labeled side chains of some novel antifolate inhibitors in their complexes with dihydrofolate reductase

Four spin-labeled inhibitors of dihydrofolate reductase (DHFR) have been synthesized, each of which has the 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) reporting group at a different distance from the 2,4-diaminopyrimidine moiety by which the inhibitors are anchored and oriented in the active site. Inhibitors in which the TEMPO group is attached by a short side chain are weakly bound to DHFR from bacteria (Streptococcus faecium and Lactobacillus casei), to the bovine enzyme and to recombinant human DHFR. However, binding is sufficiently tight, especially in the ternary complexes with NADPH, for recording of the EPR spectra of the bound ligands. The spectra indicate that when these inhibitors are bound to the enzyme the TEMPO group is highly immobilized with correlation time, tau c, 4-20ns. Inhibitors that have the reporter group attached to the glutamate moiety of methotrexate bind to all four DHFRs more tightly than the inhibitors with shorter side chains by factors of up to 10(6). However, in most complexes formed by the inhibitors with longer side chains immobilization of the TEMPO group is slight (tau c 0.2-4 ns). These results are in general agreement with predictions from X-ray crystallographic results including thermal factors but there are some unanticipated differences between some results for bacterial and eukaryotic enzymes. Three of the splin-labeled inhibitors would provide good probes for distance measurements in and around the active site of mammalian DHFR.