Cl Atoms Research Articles

Atmospheric degradation of 2-Isopropoxyethanol: Reactions with Cl, OH and NO3

The use of glycol ethers as solvents and chemical intermediates has increased markedly in recent years. Once released into the atmosphere, they can undergo degradation processes mainly by reactions with the atmospheric oxidants that can have significant effects on the environment. In this work, the kinetic and products study of reactions of 2-isopropoxyethanol (2-iPE, (CH3)2CHOCH2CH2OH) with OH and NO3 radicals and Cl atoms have been performed using FTIR (Fourier Transform Infrared Spectroscopy) and GC-MS (Gas Chromatography/Mass Spectrometry) as detection techniques. The rate coefficients obtained were (units cm3 molecule−1 s−1): (2.18 ± 0.15) × 10−10, (1.88 ± 0.10) × 10−11 and (3.16 ± 0.45) × 10−15 for Cl, OH· and NO3· reactions, respectively. The kinetic results obtained have been included in comparison tables of the general reactivity of hydroxy ethers to extract conclusions of the atmospheric behaviour of this type of compounds. The main products detected and quantified have been isopropyl formate, formaldehyde, 2-hydroxyethyl acetate and, in the case of NO3· reactions, nitrated compounds. A reaction mechanism has been proposed according to the reaction products obtained. The calculated lifetimes have been determined and Global Warming Potential (GWP) and Photochemical Ozone Creation Potential (POCPE) have been estimated, concluding, first, that the reaction with OH radicals is the main pathway of degradation of this and others glycol ethers in the atmosphere, second, that these compounds have GWP negligible and third, that they could have influence on ozone generation at local and regional level.

Anisotropies in electronic densities and electrostatic potentials of Halonium Ions: focus on Chlorine, Bromine and Iodine.

Why are the halonium cations so effective in forming strongly-bound complexes? We directed our research to address this question and we present electrostatic potential data for the valence-state halogen atoms X and halonium cations X+, where X = Cl, Br, I. The electron densities and electrostatic potentials of the halonium cations show considerably greater anisotropy than do the valence state halogens. The distances from the electrostatic potential surface maxima to the halogen nuclei are about 0.5Åsmaller than the distances from the electrostatic potential surface minima to the nuclei, giving the halonium cations each a more disk-like shape than the corresponding neutral valence state halogens. Their surface electrostatic potentials are totally consistent with the directionalities of halonium cations in complexes and the strengths of theirinteractions. To add perspective to this brief report, we have included calculations of the isotropic cation K+ and noble gas Kr. The calculations of the electrostatic potentials of the valence states of the halogen atoms Cl, Br and I and the halonium cations Cl+, Br+ and I+, as well as K+ and Kr, on 0.001 au contours of their electronic densities were carried out with Gaussian O9 and the Wave Function Analysis - Surface Analysis Suite (WFA-SAS) at the M06-2X/6-31 + G(d,p) and M06-2X/3-21G* levels.

Effect of bandgap tunability on the physical attributes of potassium-based K2CuBiX6 (X = I, Br, Cl) double perovskites for green technologies

Potassium-based perovskites hold significant potential to revolutionize renewable technology by enabling more cost-effective and sustainable energy devices. The DFT incorporated in the Wein2K interface is used to provide an extensive investigation of the structural, mechanical, electrical, optical, and thermoelectric behavior of double perovskites K2CuBiX6 (X = I, Br, Cl). Structural stability is confirmed through optimization curves, tolerance factor and octahedral tilting. Mechanical properties support the ductile character of K2CuBiX6 (X = I, Br, Cl). Electronic band structures reveal that perovskite K2CuBiI6 initially possesses a bandgap of 0.6 eV. This bandgap is increased to 0.97 eV when (I) atom is replaced with (Br) atom. Furthermore, a prominent shift in the bandgap value occurs when the bromine (Br) atom is replaced with a chlorine (Cl) atom, resulting in a bandgap of 1.3 eV. The Kramer-Kronig equations are used to evaluate the optical characteristic, which shows significant absorption in the visible range for all structures, allowing them to be utilized in optoelectronics. Numerous thermoelectric characteristics are calculated using the Boltzmann semi-classical theory. The perovskites exhibit substantial potential for renewable energy applications, as they demonstrate significant ZT values, along with elevated Seebeck coefficients and electrical conductivities, which enhance their suitability for utilization in clean energy technologies.

New mechanistic insight into catalytic decomposition of dioxins over MnOx-CeO2/TiO2 catalysts: A combined experimental and density functional theory study

Elucidation of the catalytic decomposition mechanism of dioxins is pivotal in developing highly efficient dioxin degradation catalysts. In order to accurately simulate the whole molecular structure of dioxins, two model compounds, o-dichlorobenzene (o-DCB) and furan, were employed to represent the chlorinated benzene ring and oxygenated central ring within a dioxin molecule, respectively. Experiments and Density Functional Theory (DFT) calculations were combined to investigate the adsorption as well as oxidation of o-DCB and furan over MnOx-CeO2/TiO2 catalyst (denoted as MnCe/Ti). The results indicate that competitive adsorption exists between furan and o-DCB. The former exhibits superior adsorption capacity on MnCe/Ti catalyst at 100 °C - 150 °C, for it can adsorb on both surface metal atom and surface oxygen vacancies (Ov) via its O-terminal; while the latter adsorbs primarily by anchoring its Cl atom to surface Ov. Regarding oxidation, furan can be completely oxidized at 150 °C - 300 °C with a high CO2 selectivity (above 80 %). However, o-DCB cannot be totally oxidized and the resulting intermediates cause the deactivation of catalyst. Interestingly, the pre-adsorption of furan on catalyst surface can facilitate the catalytic oxidation of o-DCB below 200 °C, possibly because the dissociated adsorption of furan may form additional reactive oxygen species on catalyst surface. Therefore, this work provides new insights into the catalytic decomposition mechanism of dioxins as well as the optimization strategies for developing dioxin-degradation catalysts with high efficiency at low temperature.

Electronic Properties of F, Cl and H Atoms Adsorbed on CsPbI3(110) Surface

The electronic properties of the CsPbI3 surface are calculated by using first-principles calculations. Through calculating adsorption energy of CsPbI3 passivated by Cl, F and H atoms, it is found that adsorption energy values of CsPbI3 (110) surface passivated by H atoms fluctuate less, they are less sensitive to the adsorption position, and the adsorption is stable. Through calculating surface states of passivation system, it is found that F and H atoms have quite good passivation effect, and the Fermi level of passivation system increases and enters the forbidden band, indicating that the passivation effect is relatively ideal. Passivation effect of Cl atoms are poor, a new shallow acceptor defect states appeared at the bottom of the conduction band. This defect level could trap carriers and weaken the carrier migration ability, which is a disadvantage of Cl passivation system. Through the charge density difference and Bader charges, it is found that the F and H atoms get more electrons from the I atom, which is beneficial to the passivation of the surface states.

Synthesis and herbicidal activities of 2-((3-pyridinyl-2-oxo-2,3-dihydrobenzo[d]thiazol-6-yl)oxy)propionates.

The discovery of lead compounds is fundamental to herbicide innovation, yet the limited availability of valuable lead compounds has impeded their progress in recent years. The study presents a novel molecular scaffold that exhibits remarkably potent herbicidal activity. Through a scaffold-hopping strategy, a highly potent lead compound for herbicides, namely 3-(2-pyridinyl)-benzothiazol-2-one, was unexpectedly discovered during attempts to structurally modify haloxyfop, a commercial aryl-oxy-phenoxy-propionate herbicide. To investigate the structure-activity relationship (SAR) of the newly discovered herbicidal chemicals, a series of 2-(2-oxo-3-(pyridin-2-yl)-2,3-dihydrobenzo[d]thiazol-6-yloxy)propanoic acid derivatives, I-01 ~ I-27, were designed and synthesized. SAR analysis revealed that trifluoromethyl at the 5-position of pyridine is crucial for herbicidal activity, whereas additional fluorine or Cl atom at the 3-position of pyridine significantly enhances activity. Carboxylic ester derivatives exhibit superior herbicidal activity compared with amide derivatives. Moreover, the activity of carboxylic ester derivatives decreases with C chain extension, but the introduction of O atoms in the side chain benefits activity enhancement. Pot experiments conducted in a glasshouse demonstrated that I-01 and I-09 exhibited potent postemergence herbicidal activity against broadleaf weeds, and completely inhibited growth of Amaranthus retroflex, Abutilon theophrasti and Portulaca oleracea at a dosage of 75 g ha-1. Despite the initial goal of scaffold-hopping not being achieved, we have successfully identified a novel molecular scaffold exhibiting exceptional herbicidal activity, thereby presenting innovative prospects for herbicide development. © 2024 Society of Chemical Industry.

(S)-(+)-1-(4-Bromophenyl)-N-[(4-methoxyphenyl)methylidene]ethylamine and bis{(S)-(+)-1-(4-bromophenyl)-N-[(4-methoxyphenyl)methylidene]ethylamine-κN}dichloridopalladium(II)

The (S)-(+)-1-(4-bromophenyl)-N-[(4-methoxyphenyl)methylidene]ethylamine ligand, C16H16BrNO, (I), was synthesized through the reaction of 4-methoxyanisaldehyde with (S)-(−)-1-(4-bromophenyl)ethylamine. It crystallizes in the orthorhombic space group P212121 belonging to the Sohncke group, featuring a single molecule in the asymmetric unit. The refinement converged successfully, achieving an R factor of 0.0508. The PdII complex bis{(S)-(+)-1-(4-bromophenyl)-N-[(4-methoxyphenyl)methylidene]ethylamine-κN}dichloridopalladium(II), [PdCl2(C16H16BrNO)2], (II), crystallizes in the monoclinic space group P21 belonging to the Sohncke group, with two molecules in the asymmetric unit. The central atom is tetracoordinated by two N atoms and two Cl atoms, resulting in a square-planar configuration. The imine moieties exhibit a trans configuration around the PdII centre, with average Cl—Pd—N angles of approximately 89.95 and 90°. The average distances within the palladium complex for the two molecules are ∼2.031 Å for Pd—N and ∼2.309 Å for Pd—Cl.

Combustion synthesized boron carbide powders by different organic carbon sources and microwave absorbing properties

AbstractBoron carbide powders were synthesized by combustion synthesis using organics chitosan, dextrin, cellulose, starch, and polyvinyl chloride (PVC) as carbon sources. The microwave absorbing properties of boron carbide powders synthesized by different carbon sources were investigated. The results showed that the powders synthesized using organic compounds containing Cl and N atoms as carbon sources have better absorbing properties. The peak value of reflection loss of boron carbide powder prepared with chitosan as carbon source is −46.41 dB at 2.1 mm thickness, with an effective absorption range of 9.21–12.30 GHz and an effective absorption bandwidth of 3.09 GHz. The small and uniform boron carbide grains and residual carbon with multiple morphologies enhance the interface polarization and electronic polarization in the material, which leads to multiple reflections and losses of the microwave. Additionally, the lattice defects and surface holes caused by Cl, N, and other atoms in chitosan and PVC increase the energy storage sites of the material, which makes the materials obtain excellent microwave absorbing properties. Boron carbides fabricated from an organic carbon source provide a potential for the preparation of high‐temperature resistant absorber.

Synthesis, structures and properties of two new nitrate optical materials: Rb3ZnNO3Cl4 and Rb5Na(NO3)4Cl2

Two new nitrates Rb3ZnNO3Cl4 and Rb5Na(NO3)4Cl2 have been synthesized by hydrothermal method, and they are crystallized in orthorhombic space group Pnma (no. 62) and tetragonal space group P4/mnc (no. 128), respectively. ZnCl4 and RbO3Cl6 polyhedron, NaO4Cl2 and RbO8Cl2 polyhedron are connected by sharing O or Cl atoms to construct three-dimensional (3D) frameworks with trigonal plane NO3 units as pseudo-layers, in which different types of channels are presented. In addition, Rb5Na(NO3)4Cl2 exhibits a perovskite-related framework, and Rb3ZnNO3Cl4 crystals is grown with dimensions up to 5×4.5×1 mm3. Notably, these two compounds have short UV cut-off edge (below 222 nm and 238 nm, respectively). Theoretical calculations indicate that the birefringence enhancement is mainly derived from π-conjugated NO3 units.

Effect of pyrolytic temperatures on the 2,4-dichlorophenol adsorption performance of biochar derived from Populus nigra.

To investigate the correlation between the physicochemical properties of biochar and its adsorption performance for 2,4-dichlorophenol (2,4-DCP), Populus nigra was subjected to oxygen-limited pyrolysis at temperatures ranging from 300 to 600 ℃. The experimental results showed that as the pyrolysis temperature increased, the specific surface area and degree of graphitization of the resultant biochar increased, but the amount of oxygen-containing functional groups decreased. Populus nigra biochar produced at 450 ℃ exhibits the best adsorption performance for 2,4-DCP due to its excellent physicochemical properties and greater electron exchange capability. The removal of 2,4-DCP is a multi-step adsorption process dominated by chemisorption, which involved oxygen-containing functional groups-mediated hydrogen bonding, as well as π-π electron donor-acceptor (EDA) interaction between the aromatic rings and Cl atoms. The study highlights the potential of Populus nigra residues for producing biochar as an affordable and effective adsorbent for 2,4-DCP removal.

Specific and sequential detection of hydrogen sulfide and hypochlorous acid based on a ring-forming reaction and self-assembly

Some biological small molecules such as hydrogen sulfide (H2S) and hypochlorous acid (HClO), play pivotal roles in numerous biological and pathological processes and are associated with various diseases. The detection and monitoring them is of continued research interest. Here we report a sequential detection mode fluorescence probes that allow for the sensing of HS– and ClO–. The mixture of P and HS– constructs a specific sensing system S for ClO–. The substitution product S is stable in air, which also could be used independently. Mechanism studies demonstrate that HS– substitutes the Cl atom in P. Furthermore, the addition of ClO– facilitates a ring-forming reaction, resulting in the formation of a thiofuran ring within the product (T). Interestingly, P has a highly ordered steric packing and could self-assemble into a rice-spike-like structure. Upon the addition of HS–, the assemblies decompose into free molecules. After interaction with ClO–, these molecules further transform to T with strong assembled capacity, featuring a larger number of nanosheets. This study provides a novel mechanism for sensing HS– and ClO–, cell and living animal imaging further indicating the good application prospects of these probes in biosensing and bioimaging.

A novel fluorescent probe for cascade detection of hydrogen sulfide and hypochlorous acid and its application in bioimaging

Herein we developed a cascade detection mode for the detection of HS− and ClO− by the novel probe NM-Cl bearing a conjugating naphthalene-dicyanoisophorone unit. The probe displayed sensitive and remarkable fluorescent enhancement in response to HS−, but not to other analytes. The mixture of probe and HS− constructed a specific sensing system for ClO− by fluorescent quenching response. The mechanism studies indicated that the successive reacting of HS− substitution Cl atom in probe and then addition of ClO− facilitation a thiofuran ring-forming induced differentiated fluorescence emission. This study provides a novel mechanism for the detection of HS− and ClO−, the imaging of cell and living animal further indicating the good application prospects of the probe in biosensing and bioimaging.

Photocatalytic activity enhancement of g-C3N4 nanosheets through simultaneous inter- and intra-layer charge separation using a facile mechano-thermal method

Herein, a novel mechano-thermal approach has been proposed to tune the electronic structure and enhance the photocatalytic performance of g-C3N4 nanosheets. According to the results, the high-energy ball-milling method modified the role of the ammonium chloride from the blowing agent to the doping agent, leading to the introduction of the interstitial and substitutional Chlorine (Cl) atoms into the nanosheet structure. Such a modification not only promoted electron-hole separation through the inter- and intra-layer of the g-C3N4 nanosheets, but it also led to the band gap energy reduction and higher oxidation capability of the photogenerated holes. These key improvements have been reflected in the optimized sample with a high-energy ball-milling time of 15 min (g-C3N4–15). Compared to the sample without the ball-milling process, g-C3N4–15 exhibited simultaneous intra- and inter-layer charge separation, reduction in the band gap energy from 2.82 to 2.76 eV, and positive shift in the valence band. Furthermore, these modifications in the electronic structure of the nanosheets contributed to the outstanding photocatalytic performance of the g-C3N4–15 towards methylene blue (MB) photodegradation. Among the samples with different ball-milling times, g-C3N4–15 demonstrated the highest MB photodegradation rate constant (0.0125 min−1), approximately 9 times greater than the sample without the ball-milling process. Additionally, the proposed photodegradation pathway suggested that the positive shift in the valence band of g-C3N4–15 could activate hydroxyl radicals (.OH) and promote demethylation and ring-opening of MB dyes.

Hybrid simulation of radio frequency biased inductively coupled Ar/O<sub>2</sub>/Cl<sub>2</sub> plasmas

In the etching process, a bias source is usually applied to the substrate of the inductively coupled plasma (ICP) to realize independent modulation of the ion energy and ion flux. In this work, a hybrid model, i.e. a global model combined bi-directionally with a fluid sheath model, is employed to investigate the plasma properties and ion energy distribution function (IEDF) in biased inductively coupled Ar/O<sub>2</sub>/Cl<sub>2</sub> plasmas. The results indicate that at a bias frequency of 2.26 MHz, the Cl<sup>–</sup> ion density and ClO<sup>+</sup> ion density first increase with bias voltage rising, and then they decrease, and finally they rise again, which is different from the densities of other charged species, such as O and Cl atoms. At the bias frequency of 13.56 MHz and 27.12 MHz, except Cl<sup>–</sup> and <inline-formula><tex-math id="M3">\begin{document}$ {\text{Cl}}_2^ + $\end{document}</tex-math><alternatives><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="4-20231369_M3.jpg"/><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="4-20231369_M3.png"/></alternatives></inline-formula> ions, the evolutions of other species densities with bias voltage are similar to the results at lower bias frequency. The evolution of the species densities with bias frequency depends on the bias voltage. For instance, in the low bias voltage range (< 200 V), the densities of charges species, O and Cl atoms increase with bias frequency increasing due to a significant increase in the heating of the plasma by the bias source. However, when the bias voltage is high, say, higher than 300 V, except <inline-formula><tex-math id="M4">\begin{document}$ {\text{Cl}}_2^ + $\end{document}</tex-math><alternatives><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="4-20231369_M4.jpg"/><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="4-20231369_M4.png"/></alternatives></inline-formula> and Cl<sup>–</sup> ions, the densities of other charged species, O and Cl atoms first decrease with bias frequency increasing and then they increase due to a decrease and then an increase in the heating of the plasma by the bias source. In addition, as the bias frequency increases, the peak separation of IEDF becomes narrow, the high energy peak and low energy peak approach each other and they almost merge into one peak at high bias frequency. The results obtained in this work are of significant importance in improving the etching process.

Theoretical study on the mechanisms, kinetics and risk assessment of OH radicals and Cl atom initiated transformation of HCFC-235fa in the atmosphere.

Hydrochlorofluorocarbons (HCFCs) are important greenhouse gases and ozone-depleting substances. Thus, a thorough understanding of their atmospheric fate is essential for preventing and controlling atmospheric pollution. Herein, the atmospheric transformation mechanism of CF3CH2CClF2 (HCFC-235fa) by the OH radical and the Cl atom was carried out at the dual-level of CCSD(T)/aug-cc-pVTZ//M06-2X/6-311+G(d,p). The reaction rate coefficients were calculated using the multistructural canonical variational transition state theory with small curvature tunneling (MS-CVT/SCT) at 200-1000 K. The kMS-CVT/SCT(CF3CH2CClF2 + OH) and kMS-CVT/SCT(CF3CH2CClF2 + Cl) values are 9.05 × 10-15 and 1.95 × 10-17 cm3 molecule-1 s-1 at 297 K, respectively. The results show that the role of OH is more important than Cl in the degradation of CF3CH2CClF2. The atmospheric lifetimes (83 days-77.93 years), ozone destruction potential (0.001-0.023), and global warming potentials (GWP100 = 21.06-5157.35) of CF3CH2CClF2 were assessed, and these results indicate that CF3CH2CClF2 is atmospherically persistent and environmentally unfriendly. The evolution mechanisms of CF3C·HCClF2, CF3C(OO˙)HCClF2, and CF3C(O˙)HCClF2 in the presence of O2, HO2˙, and NO were investigated and discussed. The resulting products of CF3CH2CClF2 are mostly highly oxidized multi-functional compounds in the forms of aldehydes, ketones, and organic nitrates. A computational assessment of acute and chronic toxicities was performed at three levels of nutrition in order to improve the understanding of the potential toxicity of CF3CH2CClF2 and its degradation products to the aquatic environment. The acidification potential of CF3CH2CClF2 was calculated to be 1.141 and presumed to contribute to the formation of acid rain. The results may contribute to describing HCFCs' atmospheric fate, persistence, and environmental risks.

ClO-driven degradation of graphene oxide: new insights from DFT calculations.

We present an extensive investigation using density functional theory (DFT) calculations on various model graphene oxide (GO) nanostructures interacting with chlorine monoxide ClO, aiming to understand the role of this highly oxidizing species in C-C bond breakage and the formation of significant holes on GO sheets. During its function, the myeloperoxidase (MPO) enzyme abundantly generates chlorine-oxygen-containing species and their presence has been identified as the cause of degradation in carbon nanotubes of diverse sizes, morphologies, and chemical compositions, both in in vivo and in vitro samples. Notably, Kurapati et al. (Small, 2015, 11, 3985-3994) demonstrated efficient degradation of single GO monolayers through MPO catalysis, though the exact degradation mechanism remains unclear. In our study, we discover that breaking C-C bonds in a single graphene oxide sheet is achievable through a simple mechanism involving the dissociation of two ClO molecules that are chemically attached as nearest neighbor species but bonded to opposite sides of the GO layer (up/down configuration). Two new carbonyl oxygens appear on the surface and the Cl atoms can be transferred to the carbon layer or as physisorbed species near the GO surface. Relatively small energy barriers are associated with these molecular events. Continuing this process on neighboring sites leads to the presence of larger holes on the GO surface, accompanied by an increase in carbonyl species on the carbon network, consistent with X-ray photoelectron spectroscopy measurements. Indeed, the distribution of oxygen functionalities is found to be crucial in defining the damage pattern induced in the carbon layer. We emphasize the important role played by the local charge distribution in the stability or instability of chemical bonds, as well as in the energy barriers and reaction pathways. Finally, we explore the possibility of achieving chlorination of GO following MPO exposure. The here-reported predictions could be the root cause of the experimentally observed low stability of individual GO sheets during the MPO catalytic cycle.

Orbital electron delocalization of axial-coordinated modified FeN4 and structurally ordered PtFe intermetallic synergistically for efficient oxygen reduction reaction catalysis.

Regulating the chemical environment of materials to optimize their electronic structure, leading to the optimal adsorption energies of intermediates, is of paramount importance to improving the performance of electrocatalysts, yet remains an immense challenge. Herein, we design a harmonious axial-coordination Pt x Fe/FeN4CCl catalyst that integrates a structurally ordered PtFe intermetallic with an orbital electron-delocalization FeN4CCl support for synergistically efficient oxygen reduction catalysis. The obtained Pt2Fe/FeN4CCl with a favorable atomic arrangement and surface composition exhibits enhanced oxygen reduction reaction (ORR) intrinsic activity and durability, achieving a mass activity (MA) and specific activity (SA) of 1.637 A mgPt -1 and 2.270 mA cm-2, respectively. Detailed X-ray absorption fine spectroscopy (XAFS) further confirms the axial-coupling effect of the FeN4CCl substrate by configuring the Fe-N bond to ∼1.92 Å and the Fe-Cl bond to ∼2.06 Å. Additionally, Fourier transforms of the extended X-ray absorption fine structure (FT-EXAFS) demonstrate relatively prominent peaks at ∼1.5 Å, ascribed to the contribution of the Fe-N/Fe-Cl, further indicating the construction of the FeN4CCl moiety structure. More importantly, the electron localization function (ELF) and density functional theory (DFT) further determine an orbital electron delocalization effect due to the strong axial traction between the Cl atoms and FeN4, resulting in electron redistribution and modification of the coordination surroundings, thus optimizing the adsorption free energy of OHabs intermediates and effectively accelerating the ORR catalytic kinetic process.

Rational design of chloride ion transport channels in an open borate framework

La-doped Ca2B5O9Cl exhibits one-dimensional chloride-ion transport defined by the dimensionality of the borate framework. Theoretical calculations indicate an unusual interstitialcy mechanism involving complex association between Cl and La atoms.

Visible-light-induced copper-catalyzed oxidative esterification of α-azidoketones with diazoacetates: access to α-acyloxyacetates.

A copper(II)-catalyzed 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU)-mediated synthesis of α-acyloxyacetates from α-azidoketones and diazoacetates under visible light at room temperature is described. This reaction involves an oxidative esterification process, leading to the formation of two new C-O bonds with the elimination of dinitrogen molecules in the overall process. 20 examples of α-acyloxyacetates were synthesized in high yields (70-86%) by coupling various α-azidoketones with diazoacetates. α-Azidoketones containing electron-donating groups (Me, MeO), electron-withdrawing groups (CN, NO2), halogen atoms (Cl, Br), and other aryl groups are compatible with various substituted diazoacetates (ethyl, tertiary butyl, benzyl), resulting in the formation of α-acyloxyacetates.

A versatile tumor-targeted drug-delivery system based on IR808-modified nanoparticles, its co-loading with PTX and R848 and its extraordinary antitumor efficacy.

Nearly all antitumor drugs can benefit greatly from effective tumor-targeted delivery for improved therapeutic efficacy and reduced toxic side effects. However, the vast majority of tumor-targeting ligands can only target specific tumor cells that highly express the corresponding receptors and thus are only applicable to limited tumor types. Heptamethine cyanines with medium cyclohexene and medium Cl atoms, such as IR780 and IR808, have shown an unusual ability to indiscriminately accumulate into virtually all tumor types. In this study, IR808 was conjugated with DSPE-mPEG2000-NH2, and the resultant DSPE-PEG2000-IR808 (DP-IR808) in combination with TPGS successfully encapsulated paclitaxel (PTX) and immunomodulator R848 into nanoparticles with a small particle size of 150.20 nm, negative charge of -16.50 mV, rod-like morphology, and PTX loading content of 31.6%. The obtained DP-IR808@PTX-R848 NPs rapidly accumulated in 4T1 tumors with a tumor/liver fluorescence ratio of 1.71, and it demonstrated a significant photothermal effect and could be directly used for NIR imaging. The DP-IR808@PTX-R848 NPs achieved a high tumor inhibition rate of 94%, a mean survival time of >90 d, and a tumor-free survival percentage of 57%. To the best of our knowledge, this was the first time that nanoparticles were modified with heptamethylcyanine molecules. The nanoparticles system based on DSPE-PEG-IR808, which integrates tumor-targeted drug delivery, in vivo infrared imaging and photothermal therapy, is expected to become a versatile drug-delivery platform for tumor therapy.