Hydroxypropyl Research Articles

Poly(2-(dimethylamino) ethyl methacrylate)-b-poly (hydroxy propyl methacrylate) nanoparticles for guided delivery of MCL-1 CRISPR-Cas9 plasmid and doxorubicin to non-small cell lung cancer

Combining gene therapy with other therapeutic methods, such as chemotherapy, using nanocarriers can lead to higher therapeutic effects through different mechanisms. In the current study, poly(2-(dimethylamino) ethyl methacrylate)-b-poly (hydroxy propyl methacrylate) (PDMAEMA-b-PHPMA) copolymer was synthesized in order to encapsulate either doxorubicin (DOX) or MCL-1 CRISPR.Cas9 plasmid (NP/DOX and NP/CRISPR.Cas9 plasmid). Then, for site-specific targeting against non-small cell lung cancer (SKMES-1 and A549 cell lines) overexpressing nucleolin receptors, AS1411 aptamer was attached to the surface of the prepared platforms through electrostatic interactions. The developed system was extensively evaluated for its transfection efficiency, cellular toxicity, and effectiveness in treating SKMES-1 tumor-bearing C57BL/6 nude mice. The results indicated that the targeted NP/DOX+NP/CRISPR.Cas9 plasmid complex enhanced cellular uptake into target cells, SKMES-1 and A549, through receptor- mediated endocytosis. Furthermore, comparative in vitro cytotoxicity results showed that the cells were exposed to the combination of NP/DOX and NP/CRISPR.Cas9 plasmid complex caused significantly enhanced cytotoxicity compared to treatment with each of them alone. In vivo study revealed that the AS1411-tagged nanoparticles (Apt-NP/DOX+Apt-NP/CRISPR.Cas9 plasmid) had a more pronounced inhibitory effect on tumor growth compared to non-targeted nanoparticles (NP/DOX+NP/CRISPR.Cas9 plasmid), moreover, co-treatment with MCL-1 sgRNA CRISPR.Cas9 plasmid and DOX increased the drug sensitivity of SKMES-1 cells towards DOX, which enhanced the therapeutic effects in mice receiving treatment with Apt-NP/DOX in combination with Apt-CRISPR.Cas9 plasmid nanocomplex. In conclusion, the findings indicated that the combination of common chemotherapy such as DOX and genome editing for MCL-1 through CRISPR.Cas9 system would provide a potential and safe method for treating non-small cell lung cancer which has excellent capacity for the clinical translation.

Enhanced catalytic performance for gas phase epoxidation of propylene with H2 and O2 by multiple pretreated Au/TS-1 catalysts

Direct epoxidation of propylene (C3H6) with hydrogen (H2) and oxygen (O2) over Au/TS-1 catalyst was promising way for the synthesis of propylene oxide (PO). However, high selectivity of PO (>95 %) and conversion of C3H6 (>5 %) cannot be achieved at the same time. The industrialization process was severely restricted. In this paper, Au/TS-1 catalysts were synthesized by deposition precipitation method with alkali metal promoter. And alkaline gases and silane coupling post-treatment were performed to promote the catalytic activity. The prepared samples exhibited a much better C3H6 conversion (6.5 %) and PO selectivity (95.1 %) compared with general catalyst using normal synthetic technology. Cs2CO3 was beneficial to increasing Au nanoparticles uptake efficiency. Both NH3 and triethoxyvinylsilane post-treatment were good for smaller and more uniform loading of Au nanoparticles. The decreasing in surface hydroxyl density effectively alleviated the occurrence of PO ring opening isomerization. The increased hydrophobicity of TS-1 surface was conducive to the rapid desorption of generated PO and significantly increased PO selectivity. Multiple pretreatment was also favorable for extending the lifetime of Au/TS-1 catalyst.

Theoretical Investigation of Propylene Epoxidation Using H2 and O2 Over Titanosilicate-Supported Au Catalysts

Titanosilicate-supported Au-cluster catalysts can be used to selectively synthesize propylene oxide from propylene using O2 and H2. However, the details of the catalytic reaction mechanism have not yet been elucidated. Thus, the reaction mechanism was investigated using density functional theory calculations. The calculation results revealed that active Ti-OOH forms on the surface Ti site, which is active as an oxidant and acts as an anchorage site for Au nanoclusters. The rate-determining step of propylene oxide synthesis on Au/titanosilicate is O insertion into propylene, with an activation energy of 1.37 eV. The propylene involved in this reaction is activated by adsorption on Au nanoclusters. Moreover, it was also found that the formation of Ti-OOH on Au/titanosilicate requires an activation energy of 0.48 eV, while it is barrierless on Au/anatase-TiO2. However, the decomposition energy of Ti-OOH on Au/titanosilicate is −0.16 eV, which is smaller than that on Au/anatase-TiO2 (−1.12 eV). The results indicate that Ti-OOH decomposes more readily on Au/titanosilicate than on Au/anatase-TiO2 but is easily regenerated because the reaction energy is significantly smaller than that on Au/anatase-TiO2. Therefore, these calculations are qualitatively in good agreement with the experimental results for Au/titanosilicate, which exhibited high catalytic activity at high temperatures.Graphical

Metal-Free Ring-Opening Polymerization of Propylene Oxide: Synthesis and Characterization of Polyether in the Undergraduate Organic Chemistry Laboratory

Metal-Free Ring-Opening Polymerization of Propylene Oxide: Synthesis and Characterization of Polyether in the Undergraduate Organic Chemistry Laboratory

Reactive Carbon Capture: Cooperative and Bifunctional Adsorbent-Catalyst Materials and Process Integration for a New Carbon Economy.

ConspectusTo say the least, releasing CO2 into the atmosphere is reaping undue environmental consequences given the ever-present increase in severe global weather events over the past five years. However, it can be argued that-at least in the confines of current technological capabilities-the atmospheric release of CO2 is somewhat unavoidable given that even shifting toward clean energy sources-such as solar, nuclear, wind, battery, or H2 power-incurs an initial carbon requirement by way of manufacturing the very production abilities through which "clean" energy is generated. Even years from now, experts agree that energy production will be diversified and-as the global population continues to drive the growth of global energy consumption-thermal power derived from carbon combustion is likely to remain one intrinsic energetic source, of which CO2 will always be a byproduct. In this context, it is the responsibility of the scientific community to devise improved pathways of carbon management such that (i) the consequences of combustion on the global environment are reduced and (ii) carbon fuels can be leveraged in a sustainable fashion.In this Account, we discuss a pivotal perspective shift on CO2 emissions derived from a considerable breakthrough in material science from our work at Missouri University of Science and Technology. This account details the development of materials which no longer vilify CO2 emissions as a valueless combustion byproduct, instead providing a path for them to become a potential feedstock. In more specific terms, this work details the development of structured, cooperative "bifunctional" materials (BFMs) comprised of (i) a high-temperature adsorbent and (ii) a heterogeneous catalyst that enable single-bed CO2 capture and utilization in oxidative ethane dehydrogenation (ODHE), oxidative propane dehydrogenation (ODHP), and dry methane reforming (DMR) processes. This Account begins with the conceptual development of the BFMs in the powdered state, followed by detailing the first-ever reports of structuring the materials into facile honeycomb contactors by 3D printing. The Account then summarizes the impressive performance of the 3D-printed BFMs, specifically focusing on how their catalysts (metal oxides and perovskites) influence their reactive CO2 capture performances in ODHE, ODHP, and DMR processes. Such promise of CO2-as-fuel offers a glimpse into the future of a diversified energy economy, in which CO2/fuel looping can play an important role. A major factor in achieving this future is, of course, developing an appropriately active catalyst; an account of whose first breakthroughs in material science are detailed herein.

The fabrication of potassium ion modification on Cu2O(111) for enhanced propylene oxide selectivity: Insights from density functional theory

Utilizing the alkali metal effect to enhance catalyst performance is an effective approach in the development of highly efficient catalysts. Herein, we report a K+ ion-modification strategy on Cu-based catalysts for the direct epoxidation of propylene (DEP) using molecular oxygen, a reaction deemed as one of the “dream reactions” in heterogeneous catalysis. By elaborately engineering of K+-modified Cu2O(111) catalyst, we unveil the versatile roles played by K+ ions in promoting catalytic performance for DEP. Firstly, K+ ions stabilize the surface coordination structures of Cu2O(111). Secondly, K+ ions make the dissociation of adsorbed O2* less likely, thus facilitating the reaction of propylene with O2*. Furthermore, both K+ and two-coordinated Cu+ serve as active centers in this reaction. Lastly, K+ ions create unique surface coordination structures favorable for propylene oxide (PO) formation. The density functional theory (DFT) calculations demonstrate that the effective utilization of the alkali metal effect can engineer highly efficient Cu-based catalysts for DEP.

Suppressed Active Site Loss by Y-Doped ZnO/Silicalite-1 for Superior CO2 Oxidative Propane Dehydrogenation Performance by Microwave Catalysis

Suppressed Active Site Loss by Y-Doped ZnO/Silicalite-1 for Superior CO₂ Oxidative Propane Dehydrogenation Performance by Microwave Catalysis

Efficient Regioselective Copolymerization of Carbonyl Sulfide and Propylene Oxide with a Tolerant Iron Complex-Based Binary Catalyst

Efficient Regioselective Copolymerization of Carbonyl Sulfide and Propylene Oxide with a Tolerant Iron Complex-Based Binary Catalyst

Multiple Traces of Families of Epoxy Derivatives as New Inhibitors of the Industrial Polymerization Reaction of Propylene.

In this study, the impact of ethylene oxide, propylene oxide, 1,2-butene oxide, and 1,2-pentene oxide on the polymerization of propylene at an industrial level was investigated, focusing on their influence on the catalytic efficiency and the properties of polypropylene (PP) without additives. The results show that concentrations between 0 and 1.24 ppm of these epoxides negatively affect the reaction's productivity, the PP's mechanical properties, the polymer's fluidity index, and the PP's thermal properties. Fourier transform infrared spectroscopy (FTIR) revealed bands for the Ti-O bond and the Cl-Ti-O-CH2 bonds at 430 to 475 cm-1 and 957 to 1037 cm-1, respectively, indicating the interaction between the epoxides and the Ziegler-Natta catalyst. The thermal degradation of PP in the presence of these epoxides showed a similar trend, varying in magnitude depending on the concentration of the inhibitor. Sample M7, with 0.021 ppm propylene oxide, exhibited significant mass loss at both 540 °C and 600 °C, suggesting that even small concentrations of this epoxide can markedly increase the thermal degradation of PP. This pattern is repeated in samples with 1,2-butene oxide and 1,2-pentene oxide. These results highlight the need to strictly control the presence of impurities in PP production to optimize both the final product's quality and the polymerization process's efficiency.

Kinetic modeling of the effect of the conditions of conjugate oxidation of propane and ethylene on the yield of propylene

The study of the oxidation of propane-ethylene mixtures by numerical kinetic modeling allowed us to establish that in the range of 400–600 oC with an increase in the conversion of propane with an increase in temperature, the selectivity of propylene formation passes through a maximum, the position of which depends on the concentration of ethylene in the initial mixture. The addition of ethylene to the initial mixture leads to a reduction in propane consumption and an increase in the selectivity of propylene formation. The conditions under which ethylene introduced into the initial mixture is not consumed during the process are determined, so formally it can be considered as a catalyst, and the process of propane oxidation as proceeding in a pseudo-catalytic regime.

Ga2O3/La2O3-γAl2O3 catalysts for CO2-assisted propane oxidative dehydrogenation to propylene

Novel Ga2O3/La2O3-γAl2O3 was investigated for ODH of propane to propylene using CO2 as a mild oxidant in a batch scale fluidized CREC Riser Simulator. La2O3 in the catalysts provided a control of both the reducibility and acidity, as shown by H2-TPR and NH3-TPD, respectively. The propane conversion and products selectivity were strong function of La2O3 content in the Ga2O3/La2O3-γAl2O3 catalysts. With increasing La2O3 content in the catalyst, propane conversion dropped slightly but the propylene selectivity and yields increased. It was proposed that the presence of La2O3 reduced the non-selective sites and the acidity of the catalysts, that contributed towards deep oxidation of propane and propylene. The improved activity and selectivity with CO2 addition implied that the as-synthesized catalyst possesses CO2 activation capability required for ODH reactions. Among the investigated catalysts, Ga2O3/La2O3-γAl2O3(1:1) exhibited the highest propane conversion (92 %) and propylene yield (56 %) at 600 ℃ in the presence of CO2.

Direct Epoxidation of Hexafluoropropene Using Molecular Oxygen over Cu-Impregnated HZSM-5 Zeolites

This study explores a novel method of directly epoxidizing hexafluoropropene with molecular oxygen under gaseous conditions using a Cu/HZSM-5 catalytic system (Cu/HZ). An in-depth investigation was conducted on the catalytic performance of Cu-based catalysts on various supports and Cu/HZ catalysts prepared under different conditions. Cu/HZ catalysts exhibited better catalytic performance than other porous medium-supported Cu catalysts for the epoxidation of hexafluoropropene by molecular oxygen. The highest propylene oxide yield of 35.6% was achieved over the Cu/HZ catalyst prepared under conditions of 350 °C with a Cu loading of 1 wt%. By applying characterization techniques including XRD, BET, NH3-TPD, and XPS to different catalyst samples, the relationship between the interaction of Cu2+ and HZSM-5 and the reactivity of the catalyst was studied, thereby elucidating the influence of calcination temperature and loading on the reactivity. Finally, we further proposed the possible mechanism of how isolated Cu2+ and acid sites improve catalytic performance.

Refining Metal–Support Interactions via Surface Modification of Irreducible Oxide Support for Enhanced Complete Propane Oxidation

Refining Metal–Support Interactions via Surface Modification of Irreducible Oxide Support for Enhanced Complete Propane Oxidation

Synthesis of a green functional carbon dioxide‐based polycarbonate using bio‐based monomers

AbstractA PPC‐dodecyl glucoside (PPC‐APG) polymer was synthesized by the terpolymerization of carbon dioxide (CO2), propylene oxide (PO), and the bio‐based monomer APG for the first time. The thermal stability and mechanical properties of PPC‐APG were significantly improved compared with those of conventional polypropylene carbonate (PPC), and its glass transition temperature (Tg) was increased by 14°C compared with that of PPC. The 5% heat loss temperature (Td,−5%) and total heat loss temperature (Td,max) of PPC‐APG were increased by 89.1 and 92.1°C, respectively, compared with those of PPC. The tensile strength of PPC‐APG was increased to 25.6 MPa, its elongation at break was decreased to 125.1%, and its thermal elongation and permanent deformation were reduced to 97.2% and 62.9%, respectively, which improved the processability of the material. In addition, the introduction of bio‐based monomers also rendered PPC‐APG functional, and its surface tension reached a maximum of 61.3 mN/m at a concentration of 0.05 g/mL, with a good degradability. The higher surface tension and enhanced degradability of PPC‐APG indicate its potential for application as a plastic printing substrate.

Insight into the Mechanism of CO2 Chemical Fixation into Epoxides by Windmill-Shaped Polyoxovanadate and n-Bu4NX (X = Br, I).

Carbon dioxide (CO2) coupled with epoxide to generate cyclic carbonate stands out in carbon neutrality due to its 100% atom utilization. In this work, the mechanism of CO2 cycloaddition with propylene oxide (PO) cocatalyzed by windmill-shaped polyoxovanadate, [(C2N2H8)4(CH3O)4VIV4VV4O16]·4CH3OH (V8-1), and n-Bu4NX (X = Br, I) was thoroughly investigated using density functional theory (DFT) calculations. The ring-opening, CO2-insertion, and ring-closing steps of the process were extensively studied. Our work emphasizes the synergistic effect between V8-1 and n-Bu4NX (X = Br, I). Through the analysis of an independent gradient model based on Hirshfeld partition (IGMH), it was found that the attack of n-Bu4NX (X = Br, I) on Cβ of PO triggers a distinct attractive interaction between the active fragment and the surrounding framework, serving as the primary driving force for the ring opening of PO. Furthermore, the effect of different cocatalysts was explored, with n-Bu4NI being more favorable than n-Bu4NBr. Moreover, the role of V8-1 in the CO2 cycloaddition reaction was clarified as not only acting as Lewis acid active sites but also serving as "electron sponges". This work is expected to advance the development of novel catalysts for organic carbonate formation.

Microwave Spectroscopy of Chiral Astrochemical Candidate Vinyloxirane: The Missing Gauche Conformer.

The recent detection of a chiral molecule, propylene oxide, in the interstellar medium provides impetus for investigation of related analogues as candidates for discovery of a second chiral species. Vinyloxirane (VO) shares many of the characteristics of propylene oxide that favored its remote detection such as modest size, appreciable dipole moment and modest adsorption to water ice. The microwave spectrum of vinyloxirane at room temperature has been studied in the 18 - 26 GHz region. Rotational transitions of the previously undetected gauche-1 conformer have been assigned and fitted. The quantum number range of anti conformer transitions has been greatly expanded, providing improved molecular constants. Vibrational satellite transitions were assigned and fitted for the lowest frequency ν27 torsion mode, for 2ν27, and for the ν26 C=CC bend of anti VO, along with ν27 satellites of gauche-1. The rovibrational analyses were assisted by anharmonic vibrational calculations at B3LYP-D3/aug-cc-PVTZ, B2PLYPD3/cc-pVTZ, and DSDPBEP86/cc-pVTZ levels. Experimental peak intensities provide a population ratio Ngauche-1/Nanti of 0.36 ± 0.06, corresponding to a Gibbs free energy difference of 2.5 ± 0.4 kJ mol-1 in favor of the anti conformer, in agreement with the density functional theory results. In the gauche-1 conformer, the torsional angle between vinyl group and oxirane ring, τC=CCM, is optimized at -35° to favor an intramolecular CvinylH11...O interaction. The gauche-2 conformer with τC=CCM of + 74° suffers from CvinylH11...HCcyclopropyl repulsion so that it is calculated to be 8-9 kJ mol-1 higher than gauche-1. Reinterpretation of earlier Raman spectra suggests that the gauche-2 conformer had not been observed as reported.

Demulsification of steam-assisted gravity drainage (SAGD) emulsions under high temperature and high pressure: Effects of emulsion breaker and reverse emulsion breaker dosages

Effective treatment of complex emulsions formed during steam-assisted gravity drainage (SAGD) production is crucial for oil/water separation and subsequent processing. However, it remains challenging due to the complexity of SAGD emulsions, and there are only very limited studies on demulsification under simulated SAGD conditions. This study systematically characterized the comprehensive properties of a fresh field SAGD emulsion with about 84.6 % water and 15.4 % bitumen, and then achieved effective demulsification under a simulated SAGD condition at 135 °C and 60 psi via adding a poly(ethylene oxide)-poly(propylene oxide) (PEO-PPO) copolymer (as a model emulsion breaker or EB) combined with a branched polyethylenimine (PEI, as a model reverse emulsion breaker or REB) in a bench-scale bottle test setup. The effects of EB and REB dosages on the demulsification of the SAGD emulsion were evaluated based on the properties of the separated phases. Dynamic interfacial tension, zeta potential, and coalescence time were measured to reveal the demulsification mechanisms of EB and REB. The highly interface-active EB facilitated oil dehydration by displacing the natural interface-active species at the interfaces, disrupting the rigid interfacial films and promoting water droplet coalescence, while the cationic REB aided water de-oiling by neutralizing oil droplet surface charges, disrupting the rigid interfacial films and promoting the approach and coalescence of oil droplets in aqueous media. This work has improved the understanding of SAGD emulsion characteristics, the effects of EB and REB dosages on the demulsification performance, and the underlying demulsification mechanisms in SAGD operations. The results provide useful insights for developing effective and cost-efficient chemical approaches to address challenging emulsion issues in oil production.

ZIF-8 membranes for efficient C3H6 recovery from the Hydrogen Peroxide to propylene oxide process

The ZIF-8 membrane has emerged as a promising candidate for C3H6/C3H8 separation. However, the feasibility of ZIF-8 membranes for applications has rarely been investigated with gas provided directly by the industry sector. Herein, the C3H6/C3H8 mixture collected from the backend of the Hydrogen Peroxide to Propylene Oxide (HPPO) process was applied as feed gas to examine the separation performance of tubular ZIF-8 membranes. The membranes exhibited excellent separation performance and long-term stability under 9 bar and 50 °C. Noticeably, upon scaling up to a membrane area of 452.16 cm2 by connecting six three-channel modules in series (multi-step membrane), its separation performance satisfied the C3H6 circulation requirements during the HPPO process (purity ≥97.5 % and recovery rate ≥85 %). Furthermore, a simulation of membrane operation under industrial working conditions (22 bar and 56.3 °C) was performed. By fixing the separation factor at 15, a minimum membrane area of 800 m2 met the requirements at the cost of membrane permeance with 120 GPU. The corresponding economic calculation indicated a maximum of 91.8 % annual capital cost saving compared with the distillation process, paving the way for the practical application of membranes.

Formulation, Optimization, and Evaluation of Non-Propellent Foam-Based Formulation for Burn Wounds Treatment

Burn injuries worldwide pose significant health risks due to frequent microbial infections, which worsen complications and increase mortality rates. The conventional antimicrobial formulations are available in the form of ointments and creams. These formulations are very greasy and stick to the clothes. The applications of these formulations by finger or applicator produce pain in the affected area and incur the possibility of microbial infection. To overcome these hurdles, authors developed a novel non-propellent foam (NPF) based formulation containing chlorhexidine for effective topical delivery. Initially, NPF containing Labrasol® (26.7%), sodium lauryl sulfate (1.2%), hydroxy propyl methyl cellulose (0.56%), butylated hydroxytoluene (0.1%), ethanol (1%), and distilled water was prepared and assessed for its consistency, and ability to form foam. The NPF was statistically optimized using the Box-Behnken design to determine the effect of polymer and surfactants on the critical foam properties. The optimized formulation showed a collapse time of 45 s with a unique nature of collapsing upon slight touch which is highly beneficial for burn patients with microbial infection. The diffusion study showed that more than 90% of the drug was released within 6 h. The skin permeation study showed that 23% of the total drug permeated through the skin after 6 h with 7.64 µg/cm2/h permeation flux. The developed formulation showed good antibacterial activity. The minimum inhibitory concentration of prepared NPF was found to be 2.5 µg/mL, 2.5 µg/mL, and 5.0 µg/mL against E. coli (MTCC-1687), P. aeruginosa (MTCC-1688), and S aureus (MTCC-737) respectively. The developed NPF formulation showed quick collapse time, excellent spreadability, good anti-bacterial activity, and a non-sticky nature representing a promising avenue for burn wound treatment without using any applicator.

General negative pressure annealing approach for creating ultra-high-loading single atom catalyst libraries

Catalyst systems populated by high-density single atoms are crucial for improving catalytic activity and selectivity, which can potentially maximize the industrial prospects of heterogeneous single-atom catalysts (SACs). However, achieving high-loading SACs with metal contents above 10 wt% remains challenging. Here we describe a general negative pressure annealing strategy to fabricate ultrahigh-loading SACs with metal contents up to 27.3–44.8 wt% for 13 different metals on a typical carbon nitride matrix. Furthermore, our approach enables the synthesis of high-entropy single-atom catalysts (HESACs) that exhibit the coexistence of multiple metal single atoms with high metal contents. In-situ aberration-corrected HAADF-STEM (AC-STEM) combined with ex-situ X-ray absorption fine structure (XAFS) demonstrate that the negative pressure annealing treatment accelerates the removal of anionic ligand in metal precursors and boosts the bonding of metal species with N defective sites, enabling the formation of dense N-coordinated metal sites. Increasing metal loading on a platinum (Pt) SAC to 41.8 wt% significantly enhances the activity of propane oxidation towards liquid products, including acetone, methanol, and acetic acid et al. This work presents a straightforward and universal approach for achieving many low-cost and high-density SACs for efficient catalytic transformations.