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4,6-Dimethoxy-3-substituted-indole-7-carbaldehydes and 4,6-dimethoxy-3-substituted-indole-2-carbaldehydes undergo reaction with dimethyl acetylenedicarboxylate and triphenylphosphine to give the corresponding pyrroloquinolines and pyrroloindoles respectively. In the case of an indole-2,7-dicarbaldehyde, reaction at the 2-carbaldehyde is preferred, giving the related pyrroloindole. In the case of a 6-hydroxy-4-methoxy-3-substituted-indole-7-carbaldehyde formation of a pyrroloquinoline is preferred to cyclisation on to the phenolic group to generate a pyranoindole. The pyrroloquinolines and pyrroloindoles are highly fluorescent. [ABSTRACT FROM AUTHOR]

Allyl triphenylphosphonium bromide based mito-tracker capped silicon quantum dot (Mito-SiQDs) has been synthesized through an inverse micelle process. It was then fully characterized by transmission electron microscopy, energy-dispersive X-ray spectroscopy, dynamic light scattering techniques and X-ray photoelectron spectroscopic method. Energy dispersive X-ray spectroscopy analyses of the quantum dots confirm the presence of carbon, silicon, phosphorous and bromine atoms in Mito-SiQDs. Morphological study by transmission electron microscopy experiment showed the formation of the particles of size 11-12 nm of quantum dot dimension. The high negative zeta potential value of -23.7 mV calculated from dynamic light scattering study indicates the high stability of the circumvent agglomeration of Mito-SiQDs. The mito-tracker capped silicon quantum dot has blue emission at 400 nm wavelength upon excitation at 327 nm. Mito-SiQDs has not shown any significant cytotoxic effect with 10 to 50 µL/mL concentration on HeLa cell line for at least up to 12 h of its treatment. The Mito-SiQDs would be useful a possible fluorescent marker to visualize mitochondrial subcellular compartment in living cell through fluorescence imaging study. [ABSTRACT FROM AUTHOR]

The present work aimed to evaluate the biological activities of the silver (I) complexes, with the formulae [Ag(L)(PPh3)2]+ and [Ag(L)2]+ (L=(E)‐2‐((E)‐3‐phenylallylidene) hydrazine‐1‐carboxamide – CSC and (2E)‐2‐[(3E)‐4‐phenylbut‐3‐en‐2‐ylidene]‐hydrazinecarboxamide – BSC). Four new silver(I) compounds were synthesized and characterized by NMR 1H, 13C‐{1H}, 31P, IR, and UV‐Vis spectroscopies, molar conductivity, and elemental analysis (CNH). High cytotoxicity was found for all complexes being more active than cisplatin in the tested cell lines. The antibacterial assay demonstrated that the compounds without phosphine groups presented high levels of inhibition (80 %) at 70.4 uM against the Gram‐positive and Gram‐negative bacteria strains. The DNA interactions were investigated by UV‐Vis DNA titration, electrophoresis, and circular dichroism experiments. Data showed that the compounds did not interact with DNA in the tested conditions. However, the compounds have provided important information about the structural features that are needed in order to design new silver (I) complexes with biological activities. [ABSTRACT FROM AUTHOR]

The recently reported chemoselective reduction of phosphine oxides with 1,3-diphenyldisiloxane (DPDS) has opened up the possibility of additive-free phosphine oxide reductions in catalytic systems. Herein we disclose the use of this new reducing agent as an enabler of phosphorus redox recycling in Wittig, Staudinger, and alcohol substitution reactions. DPDS was successfully utilized in ambient-temperature additive-free redox recycling variants of the Wittig olefination, Appel halogenation, and Staudinger reduction. Triphenylphosphine-promoted catalytic recycling reactions were also facilitated by DPDS. Additive-free triphenylphosphine-promoted catalytic Staudinger reductions could even be performed at ambient temperature due to the rapid nature of phosphinimine reduction, for which we characterized kinetic and thermodynamic parameters. These results demonstrate the utility of DPDS as an excellent reducing agent for the development of phosphorus redox recycling reactions. [ABSTRACT FROM AUTHOR]

New tripodal 1,2,3-triazole ligands based on triphenylphosphine oxide platform with different linker lengths have been synthesized, and their structure has been determined by elemental analysis, 1H, 13C, and 31P NMR spectroscopy, mass spectrometry, and vibrational (IR and Raman) spectroscopy. The coordination and extraction properties of the new ligands have been studied in the complexation with uranyl nitrate and extraction of micro amounts of uranium(VI) from aqueous phase to 1,2-dichloroethane. [ABSTRACT FROM AUTHOR]

Bisphosphonium salt containing a 1,4-dihydroxynaphthyl-substituted moiety was synthesized in high yield by the reaction of 2-methyl-1,4-naphthoquinone with three equivalents of triphenylphosphine and hydrogen bromide. The structure of the synthesized bisphosphonium salt was determined by NMR spectroscopy and X-ray diffraction. [ABSTRACT FROM AUTHOR]

The alkylation of 5,5′-diaryl-2,2′-biimidazole-1,1′-diols with an equimolar amount of methyl iodide gave the corresponding N-methyl derivatives, and the reaction with 3 equiv of methyl iodide afforded alkylation products at the nitrogen atom and both hydroxy groups. 5,5′-Diaryl-1H,1′H-2,2′-biimidazoles were obtained by treatment of the title compounds with triphenylphosphine. [ABSTRACT FROM AUTHOR]

The synthesis of phosphine‐based functional covalent organic frameworks (COFs) has attracted great attention recently. Herein, we present two examples of triphenylphosphine‐based COFs (termed P‐COFs) with well‐defined crystalline structures, high specific surface areas, and good thermal stability. Furthermore, rhodium catalysts with these P‐COFs as support material show high turnover frequency for the hydroformylation of olefins, as well as excellent recycling performance. This work not only extends the phosphine‐based COF family, but also demonstrates their application in immobilizing homogeneous metal‐based (e.g. Rh‐phosphine) catalysts for application in heterogeneous catalysis. [ABSTRACT FROM AUTHOR]

Solid structures of different shapes, hydrogen chloride, and a small number of liquid products are formed from chloromethanes (CH2Cl2 and CHCl3) and binary systems with triphenylphosphine (CH2Cl2 + PPh3, CHCl3 + PPh3, and CCl4 + PPh3) under the action of a liquid‐phase low‐voltage discharge (60‐V DC). It is observed that triphenylphosphine additives sharply increase the reactivity of CCl4. Besides, a quantum chemical simulation of chloromethane transformation mechanism in the binary systems with triphenylphosphine is conducted, together with the likely mechanism of chloromethane conversion into active particles under the action of a liquid‐phase low‐voltage pulsed discharge. [ABSTRACT FROM AUTHOR]

In the present paper a series of triphenylphosphine complexes containing mixed ligands like 2-aminothiazole (Ath) and 2-aminotriazole (Atz) have been prepared. The complexes are of the formula [MCl3((Pph3)(Ath)2] and [MCl3((Pph3)(Atz)2], [M = Ru(III), Ce(III) and La(III)]. These complexes were characterized by different spectral techniques. Additionally, the computational study has been performed using density functional theory (DFT) and the calculation is used to examine the electronic structure of the synthesized complexes. The biological activities of all the synthesized complexes were evaluated and the comparative account in properties between the triphenylphosphine metal complexes containing 2-aminothiazole and 2-aminotriazole ligands has been made. The DNA-binding property of these metal complexes was investigated using electronic absorption spectroscopy and fluorescence spectroscopy. The antibacterial and antifungal activity against bacterial species (Gram −ve bacteria: Escherichia coli, Salmonella typhi) and (Gram +ve bacteria: (Staphylococcus aureus and Bacillus subtilis) and fungi (Aspergillus niger and Candida albicans). The antioxidant study was carried out against the 2,2-diphenyl-1-picrylhydrazyl radical (DPPH·) which showed that the metal complexes are good antioxidant, as compared to BHT. Further, the in-silico molecular docking study was performed to predict the possible binding sites of the metal complexes. [ABSTRACT FROM AUTHOR]

We present herein an unprecedented allylative dicarbofunctionalization of alkynes with allylic alcohols. This simple catalytic procedure utilizes commercially available Ni(COD)2, triphenylphosphine, and inexpensive reagents, and delivers valuable skipped dienes and trienes with an all‐carbon tetrasubstituted alkene unit in a highly stereoselective fashion. Preliminary mechanistic studies support the reaction pathway of allylnickelation followed by transmetalation in this dicarbofunctionalization of alkynes. [ABSTRACT FROM AUTHOR]

Gold(I) can exhibit a cooperative effect with triphenylphosphine, accelerating the triphenylphosphine-mediated partial hydrogenation of activated alkynes. In this protocol, 3-arylpropiolates are selectively reduced to the Z -isomer when the aryl ring bears an electron-donor substituent, whereas 3-arylpropynones are reduced to the E -isomers. [ABSTRACT FROM AUTHOR]

Substituted imidazoles have wild applications in different area of sciences and industries. In this research, the catalytic activity of PPh3 as a cheap and efficient organocatalyst is reported for synthesis of 2,4,5‐trisubstituted imidazoles. In this method, ultrasonic assisted one‐pot, three‐component reaction of benzil, aldehydes, urea and PPh3 in ethylene glycol as a green solvent at room temperature has been achieved to afford the structurally diverse 2,4,5‐trisubstituted imidazoles in 80–95 %. The effect of different parameters on the reaction progress was also discussed. Utilizing ultrasonic irradiation dramatically improved the reaction in terms of yields and reaction times compared to conventional heating technique. The current protocol offers many advantages such as mild reaction conditions, short reaction time, the use of non‐metallic, harmless, and cheap catalyst, ease of separation and purification, simple work‐up procedure, and the reactivity to all types of aldehydes particularly the aliphatic aldehydes. [ABSTRACT FROM AUTHOR]

A facile one-pot synthesis of highly functionalized dialkyl 1-(5-aryl-1,3,4-thiadiazol-2-yl)-4-ethoxy-5-oxo-2,5-dihydro-1 H -pyrrole-2,3-dicarboxylate derivatives via the reaction between acetylenic esters, triphenylphosphine, and ethyl 2-[(5-aryl-1,3,4-thiadiazol-2-yl)amino]-2-oxoacetate is developed. The structure of the products is confirmed by spectroscopic methods. [ABSTRACT FROM AUTHOR]

In this work, we present an effective strategy to enhance the reactivity and durability of molecular organometallic catalysts by constructing into porous frameworks, as demonstrated by triphenylphosphine (PPh3). Such PPh3 moieties accessible via the porous structures could be partially metalated by Pd species to generate a highly efficient and recyclable heterogeneous catalyst for the Suzuki coupling of aryl chlorides. Site isolation in the rigid framework stabilizes the catalytically active monophosphine‐ligated complex against deactivation into less active assemblies of bisphosphine‐Pd. Meanwhile, the densely populated free ligands inhibit the decomposition of catalytically active sites thereby highlighting the beneficial effects of such a platform. Thus, the tunability of porous polymer synthesis gives great promise to impart numerous organometallic catalysts constituted by readily available ligands with unique reactivity, which are not trivially achievable with traditional systems. [ABSTRACT FROM AUTHOR]

Molecular and crystal structures of three monovalent silver complexes with chelate thiophosphorylthiourea ligands and triphenylphosphine are determined in the context of studying complexing properties of N-thiophosphorylated thioureas, thioamides, and thiosemicarbazides with the general formula RC(S)NHP(S)(Oi-Pr)2 (R = AlkNH, Alk2N, ArNH, PyNH, Ph, PhNHNH, NH2(Et)N) towards copper (I) and silver (I) cations. [ABSTRACT FROM AUTHOR]

The diethyl 6-bromo-2H-chromene-2,3-dicarboxylate (4) was successfully synthesized by the reaction between triphenylphosphine (1), diethyl acetylenedicarboxylate (DEAD, 2) and 5-bromo-2-hydroxybenzaldehyde acid (3) in the presence of dichloromethane. The 2H-chromene's compound were characterized using IR, 1H, 13C, and 31P NMR spectroscopy. The kinetics and mechanism of the reaction were experimentally investigated by stopped-flow technique and UV–vis spectrophotometry. The first step in the proposed five-step mechanism, the reaction between 1 and 2 for the formation of intermediate 1 (I1), was fast. The reaction of I1 and 3 was slow and followed first-order kinetics. The experimental kinetic data proved that the step4 of the proposed mechanism is a rate-determining step. To make a further understanding about the proposed mechanism, theoretical investigations were carried out at the B3LYP/6-31++g(d,p) level of theory. The calculations showed that the step4 (Δ H 4 DEAD 0 = 82.1 kJ/mol) is in terms of energy undesirable and difficult in line with experimental results, and is an endothermic process. It also cleared that why I3 with diethyl groups in step4 tends to convert to the I4 very slowly through a four-member ring formation in comparison with other steps and ultimately it becomes impossible process (step4) when t-But groups are replaced instead of diethyl groups within the structure of I3. The experimental and theoretical data indicated that the overall reaction rate follows second-order kinetics and depends on the concentrations of compounds 1 and 2. [ABSTRACT FROM AUTHOR]

A series of gold(I) complexes of ligand ibuprofen‐alkynyl (but‐3‐yn‐1‐yl 2‐(4‐isobutylphenyl)propanoate, LE) with N‐heterocyclic carbene (LC: 1,3‐dimethylimidazol‐2‐ylidene) and triphenylphosphine (PPh3) ligands with formula (LE)Au (LC) (complex 1) and (LE)Au (PPh3) (complex 2) were synthesized and fully characterized by spectroscopic methods. In order to reveal the cytotoxicity mechanism, the interaction of complex 1 or 2 with cysteine (HCys) has been studied by experimental and density functional theory (DFT) methods. The compounds were investigated for their anticancer activity against MCF‐7, MDAMB 231 breast cancer cells, HT‐29 colon cancer cells and MCF‐10A non‐tumor breast cell line. The results were compared with cisplatin and auranofin as reference drugs. The complex 2 showed more cytotoxic activity than complex 1. The complex 2 was 4.2, 3.7, and 1.7 fold more active than cisplatin against HT‐29, MDA‐MB‐231, MCF‐7 cancer cell lines, respectively. The inhibition of thioredoxin reductase of complexes 1 and 2 including cytosolic (TrxR1) and mitochondrial (TrxR2) thioredoxin reductase and also the inhibition of glutathione reductase (GR) were studied in detail. Moreover, the cellular uptake and reactive oxygen species (ROS) generation of compounds were investigated. Based on the DFT calculations a relationship between the σ‐donor ability of the isolated ligands and cytotoxicity is suggested. [ABSTRACT FROM AUTHOR]

The synthesis of fluorenes by intramolecular Pd-catalyzed C(sp2)–H activation of 2-arylbenzyl chlorides was conducted at room temperature by using commercially available triphenylphosphine and pivalic acid as ligands. The desired reactions proceeded efficiently at room temperature, and various substrates were converted into the corresponding fluorene derivatives in excellent yields. [ABSTRACT FROM AUTHOR]

Hydroperoxides are formed as the primary product during lipid oxidation, being analyzed as the peroxide value to detect the degradation level of oils and fats. As an alternative to the classical titration method according to Wheeler, a 1H‐{31P} decoupled NMR method is developed using triphenylphosphine (TPP) as a tagging agent. TPP reacts with peroxides to form TPP oxides. The quantification of the peroxide value is performed by comparing the amount of reacted TPP oxide and non‐reacted TPP. This approach eliminates the requirement for an additional internal standard. Low‐oxidized oils (peroxide value < 3 meq/kg) and high‐oxidized oils with peroxide values of 150 meq/kg are precisely quantified with an relative standard deviation (RSD) of 4.90% and 0.16%, respectively. A total number of 108 oil samples are examined using the newly‐developed 1H‐{31P} decoupled NMR method, indicating the applicability for vegetable oils and krill oils. Practical Applications: The developed NMR method is applicable for the determination of the peroxide value in vegetable, marine and krill oils presenting a powerful alternative for the Wheeler titration method. [ABSTRACT FROM AUTHOR]

A method was developed for the synthesis of dimethyl {2-[(arylmethylidene)amino]-2H-indazol-3-yl}malonates on the basis of a Knoevenagel condensation between 2-azidobenzaldehyde and dimethyl malonate, followed by treatment of the obtained adduct with aromatic aldehydes in the presence of polymer-supported triphenylphosphine. It was shown that the interaction of the synthesized Schiff bases with Corey ylide provided a route for the synthesis of 2-(aziridin-1-yl)indazoles. [ABSTRACT FROM AUTHOR]

Triphenylphosphine (TPP) surface‐functionalized and F‐108 Pluronic‐stabilized gold nanoparticles (F‐108@TPP‐AuNPs) have been synthesized through a one‐step approach, leading to well‐defined (9.6±1.6 nm) and water‐soluble nanoparticles by microwave heating an aqueous solution of TPP‐AuICl in the presence of a Pluronic polymer under basic conditions. TPP release was negligible under physiological conditions, but enhanced significantly at an acidic pH (5.4) mimicking that of a cancer cell. Laser irradiation (532 nm) raised the temperature of an aqueous solution of F‐108@TPP‐AuNPs to 51.7 °C within 5 min, confirming efficient light‐to‐heat conversion capabilities without significant photodegradation. TEM confirmed intracellular localization of F‐108@TPP‐AuNPs in the cytosol, endosomes and lysosomes of HeLa cells. F‐108@TPP‐AuNPs were well tolerated by HeLa cells and zebrafish embryos at ambient temperatures and became toxic upon heat activation, suggesting synergistic interactions between heat and cytotoxic action by TPP. [ABSTRACT FROM AUTHOR]

A convenient ultrasound-assisted one-pot synthesis of N -acylcyanamides starting from readily available carboxylic acids and sodium cyanamide has been developed. Upon activation in the presence of trichloroisocyanuric acid (TCCA) and triphenylphosphine, a range of carboxylic acids was converted into N -acylcyanamides in good to excellent yields within 10 minutes at room temperature without base. Remarkably, N -acyl-substituted imidazolones were readily accessible through guanylation-cyclization of the in situ generated N -acylcyanamides. [ABSTRACT FROM AUTHOR]

Phosphorus-doped graphene layers have been formed on the surface of nanodiamond (ND) particles by hot pressing of a mixture of purified detonation ND powder and triphenylphosphine (TPP) at 1000 °C and 100 bar. X-ray photoelectron spectroscopy detected about 1.7 at.% of phosphorus in the product, most of which was in the oxidized form. The same treatment conditions of the ND powder without the addition of TPP resulted in the only partial covering of some ND particles by sp2-hybridized carbon layers. The tests in Na-ion half-cells found that the pure carbon sample can reversibly sustain 42 mAh g−1 at a current density of 0.1 A g−1. For the phosphorus-doped sample, this value increases up to 54 mAh g−1 due to mainly accumulation of sodium at various defects created in the graphitic layers as a result of phosphorus incorporation. Taking into account inertness of inner diamond cores, specific capacity values are 417 mAh g−1 for phosphorus-doped graphene layers and 587 mAh g−1 for non-doped ones. [ABSTRACT FROM AUTHOR]

The synthesized thioureas, 1-(3-fluorobenzoyl))-3-(4-(diethyl aminophenyl) thiourea (I1), 1-benzoyl-3-(2-chlorophenyl) thiourea (I2) and 1-(2-fluorobenzoyl)-3-(2-chlorophenyl) thiourea (I3) along with triphenylphosphine were reacted with Cu(I) chloride in mole ratios 1:2:1 by using dry acetone as solvent under nitrogen to get 1–3. The synthesized thioureas and metal derivatives were characterized by spectroscopic techniques such as IR and multinuclear (1H, 13C) NMR. Compound 3 is analyzed by single crystal X-ray analysis and data reveal that the Cu is four coordinate having tetrahedral molecular geometry. The interaction of 1–3 with DNA is ascertained by cyclic voltammetry, determining binding constant, binding energy and diffusion coefficient. The findings suggest that the complexes interact with DNA in an electrostatic mode. The antioxidant activity data show that 3 has the highest free radical scavenging ability having Ic50 value of 10 µg/mL. The synthesized compounds were also screened against various bacterial strains and found some encouraging results. The binding interactions of the metal complexes with a specific protein were further validated by molecular docking studies and the results obtained show their strong interaction with amino acid residue in the binding pocket of the target protein. [ABSTRACT FROM AUTHOR]

Terminal polychlorides of hyperbranched polyester polyol Boltorn H20 were synthesized. Subsequent treatment of the resultant polychlorides with absolute pyridine or triphenylphosphine led to the formation of products of varying degrees of functionalization, containing pyridinium or triphenylphosphonium moieties in terminal positions. [ABSTRACT FROM AUTHOR]

Two metal(I) complexes containing triphenylphosphine (PPh3) and 1-(4-nitrophenyl)thiourea (NPTU) ligands were prepared, namely, [MBr(NPTU)(PPh3)2] (M = Cu (1) and Ag (2)). Both compounds (1) and (2) exhibit a distorted tetrahedral metal coordination environment with two P atoms from two PPh3 ligands, one terminal S atom from the NPTU ligand and a bromide ion. An intramolecular N-H ··· Br hydrogen bond is observed (graph set motif S(6)). Amine and bromide units from neighbouring molecules are linked via bifurcated (N-H)2 ··· Br hydrogen bonds forming 1D zigzag chains along [001] with an R21 (6) graph set motif. Neighbouring chains are connected through C-H···O hydrogen bonds leading to the formation of a three-dimensional network. [ABSTRACT FROM AUTHOR]

3β,28-Diacetoxylup-20(29)-en-30-oic acid (obtained via oxidation of betulin diacetate) enters the addition reaction with P—H-phosphonium salts (triarylphosphonium trifluoroacetates) under mild conditions to afford β-carboxyalkylphosphonium salts. Structure and composition of the resulting compounds were confirmed by NMR and IR spectroscopy, mass spectrometry, and elemental analysis. [ABSTRACT FROM AUTHOR]

• Synthesis of gem ‑bromofluoroolefins utilizing ethyldibromofluoroacetate and triphenyl- phosphine. • The reaction takes place via a Wittig type intermediate. • The reaction goes through a singlet bromofluorocarbene intermediate. • The reaction works with a wide variety of aryl aldehydes. A halon-free method for the synthesis of gem ‑bromofluoroolefins utilizing ethyldibromofluoro-acetate is disclosed via a Wittig type reaction. The reaction system takes advantage of inexpensive and readily available reagents. The method was applied to a wide variety of aryl aldehydes. Both electron donating and electron withdrawing moieties on the aryl ring were tolerated and the desired olefin products were obtained in good to excellent yields. [Display omitted] [ABSTRACT FROM AUTHOR]

Triphenylphosphine (TPP) shows stereo pyramidal configuration and has been considered as a poor electron-donor and fluorophore. Here, seven TPP-based compounds (o -TPPs 3a – 3e and p -TPPs 3f/g) introducing simple non-aromatic electron-withdrawing (EW) groups at the ortho - and para -position of P atom have been synthesized to understand the inherent optical properties of TPP. All TPPs show aggregation-induced emission (AIE): non-emissive in solutions but emissive upon aggregation. Unexpectedly, lower conjugative o -TPPs possess much higher fluorescence quantum yields (43 and 65 %) than those (1 and 29 %) of their corresponding position isomers, p -TPPs; these achiral pyramidal TPPs in crystals exist as racemic M - and P -enantiomers, with all o -TPPs showing unique MP -paired flower-like arrangements; and the pyramidal TPP moiety could form an excellent electron delocalization system via through-space conjugation. This work proves that TPP could act as an excellent electron-donor and AIEgen by reasonable design, opens a new window to the application of pyramidal TPPs or other pyramidal compounds and affords a new strategy to design strong AIE fluorophores. Triphenylphosphine (TPP)-based fluorophores (o-TPPs 3a-3e and p-TPPs 3f/g), which could be synthesized by Knoevenagel condensation reaction in excellent yields, show strong aggregation-induced emission (AIE). Unexpectedly, lower conjugative o-TPPs possess much higher fluorescence quantum yields; all these achiral TPPs exist as racemic M - and P -enantiomers; and pyramidal TPP moiety could form an excellent electron delocalization system via through-space conjugation. [Display omitted] • Seven simple TPPs have been designed and synthesized in excellent yields. • They show aggregation-induced emission characteristics. • Lower conjugative o-TPPs have much higher fluorescence quantum yields. • Achiral TPPs exist as racemic M - and P -enantiomers. • Pyramidal TPP could form an excellent conjugation system through space. [ABSTRACT FROM AUTHOR]

[Display omitted] • Phosphorus doped ordered mesoporous carbon (POMC) is prepared over metal free support. • POMCs show ferromagnetic behavior without the help of metals. • POMC prepared at 900 °C show a highest specific capacitance of 312 Fg−1. • Two electrode based symmetric device shows the specific capacitance of 170 Fg−1. • POMC 900 shows highest cyclic stability even after 5000 cycles. In this work, chemical vapor deposition (CVD) using SBA-15 as the template at different temperatures (750 - 1000 °C) was used for the fabrication of phosphorus-doped ordered mesoporous carbons (POMCs) for high-performance supercapacitors. The structural formation of the template and POMCs was confirmed using various characterization techniques. Furthermore, the magnetic characteristics of the POMCs were explored using room-temperature field-dependent magnetization studies. Moreover, the supercapacitor performance of the POMCs was evaluated through electrochemical analyses, such as cyclic voltammetry (CV), galvanostatic charge–discharge (GCD), and electrochemical impedance spectroscopy (EIS) in a 1 M H 2 SO 4 electrolyte medium. Among all POMCs, POMC 900 exhibited a high specific capacitance of 312 Fg−1 at a current density of 0.5 Ag−1 due to a higher Phosphorus content. Furthermore, the symmetric device fabricated using POMC 900 showed 90.8 % coulombic efficiency with 97.5 % capacitance retention after 5000 cycles at 2 Ag−1 of the current density as well. Thus, the CVD synthesis of POMC materials is a highly promising electrode material for cheap and high-performance supercapacitors. [ABSTRACT FROM AUTHOR]

A new route to synthesis of discrete rhenium octahedral telluride cluster complexes with organic ligands is described. The complexes with N – and P- donor ligands, specifically triphenylphosphine and pyrazole have been obtained by reaction in melt of pro-ligand at 200 °C for 48 h. The complexes' luminescent properties were described. [Display omitted] A new path to synthesize Re 6 Te 8 cluster complexes with organic ligands is described. Two new telluride octahedral rhenium cluster complexes with N- and P-donor ligands were obtained by the reaction of [{Re 6 Te 8 }(TeI 2) 6 ]I 2 ·[{Re 6 Te 8 }(TeI 2) 4 (TeI 3) 2 ]·I 2 with pyrazole or triphenylphosphine at 200 °C for 48 h. Under these conditions, substitution of all terminal telluroiodide ligands and formation of [{Re 6 Te 8 }L 6 ]I 2 (L = pyrazole or triphenylphosphine) were achieved. Both compounds were characterized by elemental analysis, IR- and NMR-spectroscopy, HR-ESI-MS, and solid-state luminescence measurements. Both obtained compounds exhibit luminescence typical for octahedral rhenium cluster complexes in the red and near-IR spectra. In addition, single crystal structural analysis was performed for the cluster complex with pyrazole. [ABSTRACT FROM AUTHOR]

It has been shown for a wide range of epoxy compounds that their interaction with triphenylphosphonium triflate occurs with a high chemoselectivity and leads to the formation of (2-hydroxypropyl)triphenylphosphonium triflates 3 substituted in the 3-position with an alkoxy, alkylcarboxyl group, or halogen, which were isolated in a high yield. Using the methodology for the disclosure of epichlorohydrin with alcohols in the presence of boron trifluoride etherate, followed by the substitution of iodine for chlorine and treatment with triphenylphosphine, 2-hydroxypropyltriphenylphosphonium iodides 4 were also obtained. The molecular and supramolecular structure of the obtained phosphonium salts was established, and their high antitumor activity was revealed in relation to duodenal adenocarcinoma. The formation of liposomal systems based on phosphonium salt 3 and L-α-phosphatidylcholine (PC) was employed for improving the bioavailability and reducing the toxicity. They were produced by the thin film rehydration method and exhibited cytotoxic properties. This rational design of phosphonium salts 3 and 4 has promising potential of new vectors for targeted delivery into mitochondria of tumor cells.

A simple and efficient synthesis of some polyfunctionalized pyrrole derivatives by a triphenylphosphine-promoted condensation reaction between dialkyl acetylenedicarboxylates, arylglyoxals, and ammonium acetate is described. This present method carries several advantages, such as good yields, a simple procedure, non-hazardous reaction conditions and starting from easily accessible substrates

A novel biodegradable amphiphilic triblock copolymer, polyphosphate, polyethylene glycol, and polylactic acid (PAEEP-PEG-PLLA), was synthesized by twice ring-opening polymerization and triphenylphosphine (TPP) was grafted onto the block copolymer to synthesize a carrier material TPP-PAEEP-PEG-PLLA, which was identified by 1 H-nuclear magnetic resonance ( 1 H-NMR) spectroscopy. The TPP-PAEEP-PEG-PLLA nanoparticles encapsulated with ursolic acid (UA) were prepared by the emulsion-solvent evaporation method and characterized by dynamic light scattering. The mitochondrial targeting ability of fluorescently labeled nanoparticles was evaluated by laser confocal microscopy. The average particle size and surface charge of the UA -loaded nanoparticle solution were 180.07 ± 1.67 nm and +15.57 ± 1.33 mV, respectively. The biocompatibility of nanoparticles was briefly evaluated by erythrocyte hemolysis assay. In vitro cell proliferation assay and scratch migration assay were performed to compare the difference in anti-tumor effect between UA and UA nanoparticles. The results showed that TPP-modified triblock copolymers had good mitochondrial targeting and improved the low bioavailability of UA, and UA nanoparticles exhibited more pronounced anti-tumor capabilities. In summary, the results suggested that our UA nanoparticles were a promising drug-targeted delivery system for the treatment of tumors., (© 2024 IOP Publishing Ltd.)

branewiththenegativechargeestablishedbythemitochondrialmembranepotential.The fluorescent spectra and the fluorescent imaging experiments indicate that the probe is suit­able for targeted labeling and fluorescent imaging of intracellular mitochondria.Mitochondria are the primary sites for energy metabolism in eukaryotic cells. They are of great significance in cell physiology. Visual imaging of mitochondria based on the tar¬ geted fluorescent molecules is a powerful tool for the researches on mitochondrial morpholo¬gy and functions. In this paper,a novel fluorescent probe HF-Mito for intracellular mitochon¬dria targeted imaging was synthesized with the 3-hydroxyflavone fluorophore and a mito- chondria-targeting group triphenylphosphine. The excited-state intramolecular proton trans¬fer (ESIPT) effect of the 3-hydroxyflavone moiety endowed it with excellent spectral proper¬ties. At the same time?the probe can be used to detect pH due to the influence of proton sol¬vent on its ESIPT process and fluorescence performance. The triphenylphosphine moiety is lipophilic and positively charged, which can specifically bind to the mitochondrial inner mem- brane with the negative charge established by the mitochondrial membrane potential. The fluorescent spectra and the fluorescent imaging experiments indicate that the probe is suit¬able for targeted labeling and fluorescent imaging of intracellular mitochondria. [ABSTRACT FROM AUTHOR]

The labelling and imaging of mitochondria and nucleolus have attracted great attention because of the involvement of these cellular organelles in critical cellular activities. Therefore, a large number of mitochondria- or nucleolus-labelling probes have been developed throughout the world. However, in the current study, we successfully developed two pyrazole-based, copper-linked triphenylphosphine-coupled emissive metallo-complexes (C1 and C2) for the simultaneous visualization of mitochondria and nucleolus in a single run. These complexes were very inexpensive and could be synthesized by a simple one-pot multicomponent reaction scheme. The complexes were very specific, and only a small concentration of 5 μM was found to be sufficient to probe both the organelles efficiently. Additionally, even under a shorter incubation period (half hour), the fluorescence intensity from the cells was appreciable. Also, both the compounds were found to be photostable when torched with 10% of a 100 mW laser for up to 10 min. All these results indicate that both the complexes may contribute towards the future development of cell imaging tools. To the best of our knowledge, this is the first report on the development of multifunctional live cell imaging tools for simultaneous mitochondria and nucleolus imaging and within the shortest incubation time of about 30 minutes. [ABSTRACT FROM AUTHOR]

For over half a century, thousands of tons of triphenylphosphine oxide Ph3P(O) have been produced every year from the chemical industries as a useless chemical waste. Here we disclose efficient transformations of Ph3P(O) with cheap resource-abundant metallic sodium finely dispersed in paraffin oil. Ph3P(O) can be easily and selectively transformed to three reactive organophosphorus intermediates—sodium diphenylphosphinite, sodium 5H-benzo[b]phosphindol-5-olate and sodium benzo[b]phosphindol-5-ide—that efficiently give the corresponding functional organophosphorus compounds in good yields. These functional organophosphorus compounds are difficult to prepare but highly industrially useful compounds. This may allow Ph3P(O) to be used as a precious starting material for highly valuable phosphorus compounds. As a byproduct of organic syntheses including the Wittig, Staudinger, and Mitsunobu reactions, triphenylphosphine oxide is often not recycled. Here a transformation of the waste product with metallic sodium to three organophosphorous compounds is presented. [ABSTRACT FROM AUTHOR]

New mixed ligand complexes of nickel(II) were synthesized by using dibasic H/5-bromo-/5-chloro-/4-hydroxy-2-hydroxybenzophenone-thiosemicarbazones (L1–4H2) and [Ni(PPh3)2Cl2]. The ligands and complexes were characterized by cyclic voltammetry, infrared, 1H and 31P NMR spectroscopy techniques. Crystallographic analyses of the 5-bromo-substituted (2) and 5-chloro-substituted (3) complexes as representatives were performed and so confirmed the ONS chelate structure and presence of PPh3 as co-ligand in the complexes. To reveal the antioxidant properties of the compounds, TEAC values (by CUPRAC method) were determined along with free radical-scavenging activity (by DPPH method). The compounds bearing 4-hydroxy substituent, L4H2 and complex 4 were the most effective compounds. The relationship between structure and antioxidant capacity in the context of benzophenone substituents and nickel(II) center was evaluated. Electrochemical results revealed that all complexes displayed metal-centered and ligand-centered redox processes. The antioxidant capacities of complexes were well correlated to electrochemical parameters. [ABSTRACT FROM AUTHOR]

Oxygen reduction reaction (ORR) plays a vital role in various fields, such as combustion, corrosion and fuel cell applications. Herein, we report the production of phosphorus-doped reduced graphene oxide (P-RGO) using triphenyl phosphine as a phosphorus source and graphene oxide in supercritical fluid method. The ratio of phosphorus source and graphene oxide has been varied to obtain optimum P-doping. P-RGO materials are characterized through X-ray diffractometer, Raman, field emission scanning electron microscopy and X-ray photoelectron spectroscopy techniques. The electrocatalytic activity of P-RGO materials are studied using linear sweep voltammetry and their ORR performance are evaluated using linear sweep voltammetry-rotating ring disk electrode studies in 0.1 M KOH electrolyte. Among the three different P-RGO materials, RGO with phosphorus doping (2:1) delivered the best ORR performance (0.75 A mg−1) compared to commercial HiSPEC Pt/C (0.12 A mg−1) catalyst. The enhanced ORR activity could be ascribed to the existence of surface-active phosphorous sites over the RGO sheet surface. [ABSTRACT FROM AUTHOR]

We herein report a modified approach for the synthesis of some pharmacologically relevant oxazole derivatives linked with amides under mild conditions. The utilization of polymer-supported triphenylphosphine (poly-TPP) as a phosphine ligand for generating the key iminophosphorane intermediate was found to be vital for achieving the synthesis of oxazole in room temperature. This alternative approach relying on the cyclization reaction of readily available phenacyl azide and phenyl isothiocyanate rendered the oxazole derivative 3a in excellent yield. This methodology has been applied for the synthesis of a more decorated oxazole derivative 3b having ester functionality and was further converted to different amides under microwave irradiation in good to excellent yields in the later stage. [ABSTRACT FROM AUTHOR]

In this study, new six Pd-based complexes containing mixture N-heterocyclic carbene (NHC) and triphenylphosphine (PPh3) ligands were synthesized from the reaction of the (NHC)PdI2(pyridine) with PPh3. The new (NHC)PdI2(PPh3) complexes were characterized using FTIR, 1H-NMR, 13C-NMR, and 31P-NMR spectroscopy and elemental analyses techniques. These spectra are consistent with the proposed formula. Molecular and crystal structure of two complexes was obtained using single-crystal X-ray diffraction method. Based on the crystal results, a cis geometry was assigned to all the complexes. These new complexes have been examined as the catalyst in the Sonogashira cross-coupling reaction. The catalytic conversions of the complexes were obtained between 71 and 99% from the reaction of phenylacetylene and aryl bromides. Also, these new complexes have been examined as the catalyst in the Mizoroki–Heck cross-coupling reaction. The catalytic conversions of the complexes were obtained between 80 and 100% from the reaction of styrene and aryl bromides. [ABSTRACT FROM AUTHOR]

A dehydroxylative Csp3–N coupling reaction assisted by triphenylphosphine has been developed through electrochemical oxidation. The reaction proceeds via anodic oxidation of triphenylphosphine to generate its corresponding radical cation, followed by reacting with hydroxyl groups to form alkoxy triphenylphosphonium ions, which are trapped by azoles or amides to construct C–N bonds. This method provides an efficient electrochemical strategy of activating hydroxyl groups to form C–N bonds under mild conditions. [ABSTRACT FROM AUTHOR]

The boracarboxylation of vinyl arenes catalyzed by copper(I) is an alkene difunctionalization reaction that provides synthetically useful β‐boryl‐α‐aryl propanoic acid derivatives. Drawbacks of the original reaction methodology are high catalyst loading and vinyl arene scope limited largely to electron‐rich systems. Herein, we demonstrate that catalytic additives, specifically triphenylphosphine or electron‐rich styrene, leads to improved catalyst efficiency and broadening of substrate scope. With the addition of PPh3, comparable yields of previously reported boracarboxylated substrates as well as two novel β‐boronated non‐steroidal anti‐inflammatory drugs (bora‐fenoprofen and bora‐flurbiprofen) were achieved at lower catalyst loading. Boracarboxylation of electron‐deficient substrates could be achieved through superstoichiometric addition of vinyl arene or addition of secondary phosphine ligand. Reactivity optimization and competition experiments have provided preliminary insights into the ability of PPh3 to aid in the catalytic cycle, specifically carboxylation of electron‐rich benzyl‐copper(I) intermediate. Additional competition studies revealed that a catalytic amount of an electron‐rich vinyl arene could be used in addition to the copper(I) catalyst to promote boracarboxylation of an electron‐deficient styrene derivative. [ABSTRACT FROM AUTHOR]

The boracarboxylation of vinyl arenes catalyzed by copper(I) is an alkene difunctionalization reaction that provides synthetically useful β‐boryl‐α‐aryl propanoic acid derivatives. Drawbacks of the original reaction methodology are high catalyst loading and vinyl arene scope limited largely to electron‐rich systems. Herein, we demonstrate that catalytic additives, specifically triphenylphosphine or electron‐rich styrene, leads to improved catalyst efficiency and broadening of substrate scope. With the addition of PPh3, comparable yields of previously reported boracarboxylated substrates as well as two novel β‐boronated non‐steroidal anti‐inflammatory drugs (bora‐fenoprofen and bora‐flurbiprofen) were achieved at lower catalyst loading. Boracarboxylation of electron‐deficient substrates could be achieved through superstoichiometric addition of vinyl arene or addition of secondary phosphine ligand. Reactivity optimization and competition experiments have provided preliminary insights into the ability of PPh3 to aid in the catalytic cycle, specifically carboxylation of electron‐rich benzyl‐copper(I) intermediate. Additional competition studies revealed that a catalytic amount of an electron‐rich vinyl arene could be used in addition to the copper(I) catalyst to promote boracarboxylation of an electron‐deficient styrene derivative. [ABSTRACT FROM AUTHOR]

A new tetrazole tripodal ligand, tris[2-(tetrazol-5-ylmethoxy)phenyl]phosphine oxide, has been obtained. Its structure in crystal and solutions has been elucidated by X-ray diffraction analysis as well as IR, Raman, and multinuclear (1H, 13C, 31P) NMR spectroscopy. Coordination properties of the polydentate ligand have been studied as exemplified by the complexation with lanthanum(III). [ABSTRACT FROM AUTHOR]

Bioengineering immune cells via gene therapy offers treatment opportunities for currently fatal viral infections. Also cell therapeutics offer most recently a breakthrough technology to combat cancer. These primary human cells, however, are sensitive to toxic influences, which make the utilization of optimized physical transfection techniques necessary. The otherwise commonly applied delivery agents such as LipofectamineⓇ or strongly cationic polymer structures are not only unsuitable for in vivo experiments, but are also highly toxic to immune cells. This study aimed to improve the design of polymeric carrier systems for small interfering RNA, which would allow efficient internalization into CD8+ T -cells without affecting their viability and thereby removing the current limitations in the field. Here, two new carrier systems for small interfering RNA were tested. One is a cationic diblock copolymer, in which less than 10% of the monomers were modified with triphenylphosphonium cations. This moiety is lipophilic, promotes uptake and it is mostly known for its mitotropic properties. Furthermore, cationic nanohydrogel particles were synthesized in exceedingly small sizes (R h < 14 nm). After full physicochemical characterization of the two carriers, extensive cytotoxicity studies were performed and the concentration dependent uptake into CD8+ T -cells was tested in correlation to incubation time and protein content of the surrounding medium. Both carriers facilitated efficient complexation of siRNA as well as significant internalization into primary human cells in less than three hours of incubation. In addition, neither of the delivery systems reduced cell viability making them good candidates to transport siRNA into CD8+ T -cells efficiently. This study provides insights into the design of polymeric delivery agents as the method of choice for overcoming the limitations of cell manipulation. Until now, CD8+ T -cells, which have become a treatment tool for currently fatal diseases, have not yet been made accessible for gene silencing by polymeric siRNA carrier systems. Choosing appropriate modification approaches for two chemically different polymer structures, we were, in both cases, able to achieve significant uptake in these cells even at low concentrations and without inducing cytotoxicity. These results remove current limitations and pave the way for bioengineering via gene therapy. Image, graphical abstract [ABSTRACT FROM AUTHOR]

In order to study the complexation properties of N-thiophosphorylated thioureas, thioamides, and thiosemicarbazides with the general formula RC(S)NHP(S)(OPri)2 (R = AlkNH, Alk2N, ArNH, PyNH, Ph, PhNHNH, NH2(Et)N) towards copper(I) and silver(I) cations, the molecular and crystal structures of silver(I) (triphenylphosphine-P)[N-(diisopropoxythiophosphoryl)thiobenzamide-S,S′] and silver(I) bis-(triphenylphosphine-P)[N-(diisopropoxythiophosphoryl)thiobenzamide-S,S′] are determined. [ABSTRACT FROM AUTHOR]