Showing papers on "Benzophenone published in 2016"
TL;DR: The "forbidden" and excitation-activated world of photoinduced covalent attachment of BP photophores is explored by touring a colorful palette of recent examples, and it is hoped that both novice and expert photolabelers will be inspired by the breadth and depth of possibilities.
Abstract: The widespread applications of benzophenone (BP) photochemistry in biological chemistry, bioorganic chemistry, and material science have been prominent in both academic and industrial research. BP photophores have unique photochemical properties: upon n−π* excitation at 365 nm, a biradicaloid triplet state is formed reversibly, which can abstract a hydrogen atom from accessible C–H bonds; the radicals subsequently recombine, creating a stable covalent C–C bond. This light-directed covalent attachment process is exploited in many different ways: (i) binding/contact site mapping of ligand (or protein)–protein interactions; (ii) identification of molecular targets and interactome mapping; (iii) proteome profiling; (iv) bioconjugation and site-directed modification of biopolymers; (v) surface grafting and immobilization. BP photochemistry also has many practical advantages, including low reactivity toward water, stability in ambient light, and the convenient excitation at 365 nm. In addition, several BP-conta...
150 citations
TL;DR: The photochemistry of benzophenone, a paradigmatic organic molecule for photosensitization, was investigated by means of surface-hopping ab initio molecular dynamics and established the existence of a kinetic equilibrium between the two triplet states, never observed before.
Abstract: The photochemistry of benzophenone, a paradigmatic organic molecule for photosensitization, was investigated by means of surface-hopping ab initio molecular dynamics. Different mechanisms were found to be relevant within the first 600 fs after excitation; the long-debated direct (S1 → T1) and indirect (S1 → T2 → T1) mechanisms for population of the low-lying triplet state are both possible, with the latter being prevalent. Moreover, we established the existence of a kinetic equilibrium between the two triplet states, never observed before. This fact implies that a significant fraction of the overall population resides in T2, eventually allowing one to revisit the usual spectroscopic assignment proposed by transient absorption spectroscopy. This finding is of particular interest for photocatalysis as well as for DNA damages studies because both T1 and T2 channels are, in principle, available for benzophenone-mediated photoinduced energy transfer toward DNA.
83 citations
TL;DR: Using donor-substituted aromatic ketones, such as 4,4'-bis(diphenylamino)benzophenone (DPA-BP), PINO radicals are efficiently produced and subsequently utilized to functionalize olefins to afford a new class of alkyl hydroperoxides.
Abstract: A metal-free protocol to generate phthalimide-N-oxyl (PINO) radicals from N-hydroxyphthalimide (NHPI) via a photoinduced proton-coupled electron transfer process is reported. Using donor-substituted aromatic ketones, such as 4,4′-bis(diphenylamino)benzophenone (DPA-BP), PINO radicals are efficiently produced and subsequently utilized to functionalize olefins to afford a new class of alkyl hydroperoxides. The DPA-BP/NHPI/O2 photocatalytic system exhibits high efficiency toward the aerobic oxidation of β-O-4 lignin models.
56 citations
TL;DR: In this paper, a cross-linked microporous polyimide network using hexafluoroisopropylidene, diphenyl, benzophenone and biphenyl as linking struts and tetraphenylmethane and tetrahenyladamantane as net nodes was synthesized under well controlled polymerization conditions.
Abstract: Highly cross-linked microporous polyimide networks using (hexafluoroisopropylidene)diphenyl, benzophenone and biphenyl as linking struts and tetraphenylmethane and tetraphenyladamantane as net nodes were synthesized under well controlled polymerization conditions. The resultant polyimides show initial decomposition temperatures over 500 °C and BET surface areas up to 781 m2 g−1 with quite uniform pore sizes at around 0.5 nm. It is found that the presence of a high density of trifluoromethyls gives rise to a simultaneously larger CO2 uptake (13.5 wt%, 273 K/1 bar) and CO2/N2 selectivity (53.5, IAST method), while the introduction of benzophenone groups enhances the interaction between the CO2 molecules and polymer skeleton, thereby leading to a high heat of adsorption (33.3 kJ mol−1) and selectivities of CO2/N2 (59.2) and CO2/CH4 (15.8). The polyimides exhibit large adsorption capacities for organic vapors such as benzene (104.9 wt%) and cyclohexane (60.2 wt%) at 298 K and P/Po = 0.8. In addition, the low-surface-energy trifluoromethyls significantly decrease the water uptake in the fluorinated polyimide compared to the non-fluorinated samples. The improved hydrophobicity is advantageous for the practical application of porous adsorbents in CO2 capture from flue gas and natural gas.
53 citations
TL;DR: A quaternary ammonium compound that exhibits excellent antimicrobial activity and can be permanently grafted to substrates containing C-H bonds to form a durable polymeric film within 1 min is investigated.
Abstract: In this work, we have investigated a quaternary ammonium compound that exhibits excellent antimicrobial activity and can be permanently grafted to substrates containing C–H bonds to form a durable polymeric film within 1 min. The compound consists of a biocidal component, dodecyl-alkylated quaternary ammonium, and a benzophenone moiety that, under mild UV irradiation, generates a densely cross-linked network and covalently attaches to a variety of substrates, including plastics, fabrics, and alkyl-modified glass surfaces. The surface attachment is 1 order of magnitude faster than that of previously reported benzophenone-associated cross-linkers, due to the electron-withdrawing effect of quaternary ammonium on the benzophenone chromophore. The modified surfaces are nonleaching and exhibit contact-killing and highly effective antimicrobial activity against Staphylococcus aureus (Gram-positive) and Escherichia coli (Gram-negative) using cell count and live/dead staining methods. The charged ammonium group al...
51 citations
Abstract: Acyl–aryl Hiyama coupling of acyl halides with arylsilanes has been achieved by employing a palladium/phosphine catalyst system. A variety of acyl chlorides and fluorides can be applied for coupling with arylsilicon reagents, and unsymmetrical benzophenone derivatives can be prepared using this protocol.
47 citations
TL;DR: Rhodium-catalyzed highly regio- and enantioselective hydroamination of allenes is reported in liquid chromatography for the determination of Na6(CO3)(SO4)2, Na2SO4, and Na2CO3.
Abstract: Rhodium-catalyzed highly regio- and enantioselective hydroamination of allenes is reported. Exclusive branched selectivities and excellent enantioselectivities were achieved applying a rhodium(I)/Josiphos catalyst. This method permits the practical synthesis of valuable α-chiral allylic amines using benzophenone imine as ammonia carrier.
44 citations
TL;DR: A series of new nontoxic polymeric UV-absorbers through covalently attaching a benzophenone derivative onto the main chain of poly(vinyl chloride) (PVC) via mild and quantitative click chemistry, which displayed great resistance to photoaging without degradation while exposed to UV irradiation.
Abstract: In this article, we developed a series of new nontoxic polymeric UV-absorbers through covalently attaching a benzophenone derivative onto the main chain of poly(vinyl chloride) (PVC) via mild and quantitative click chemistry. Azide groups were firstly introduced into the backbone of PVC via a nucleophilic reaction without affecting polymeric skeleton. Copper-catalyzed Husigen-Click cycloaddition reaction was performed between the pendant azide groups of PVC and alkynyl of (2-hydroxy-4-(prop-2-ynyloxy)phenyl)(phenyl)methanone at ambient temperature for affording the desired PVC-based UV-absorbers (PVC-UV) with different amounts of benzophenone moieties, which displayed great resistance to photoaging without degradation while exposed to UV irradiation. These polymeric UV-absorbers also showed good solubilities in common organic solvents and no cytotoxicity vs. HaCat cell. Small amounts of PVC-UV were homogeneously mixed with PVC as additive for stabilizing PVC against UV-photoaging without degradation and releasing small molecule even after 200 h while keeping thermal stability. This route of polymeric additive clearly paved an efficient way for solving the puzzle of separation of small molecule additive.
43 citations
TL;DR: In this article, transient absorption spectroscopy revealed that a deactivation pathway of the benzophenone triplet (3BP*) is via its reaction with the methanol solvent.
Abstract: Iodoperfluooralkylation of terminal alkenes and alkynes is effectively photo-promoted by benzophenone 2 (BP) or the photoreducible copper(II) complex 1. In particular, BP at 1 mol% in methanol upon 365 nm irradiation with a low-pressure mercury lamp (type TLC=thin layer chromatography, 6 W) results in a fast reaction with excellent reaction yields. Complex 1 and BP 2 exhibited very similar reactivity, suggesting that the reactions involving 1 are likely to be governed by the benzophenone photoactivation processes, rather than copper(I)/(II) redox processes. Mechanistic investigations using transient absorption spectroscopy revealed that a deactivation pathway of the benzophenone triplet (3BP*) is via its reaction with the methanol solvent. We propose that the generated radicals, in particular .CH2OH, play a key role in the initiation step forming Rf. by reacting with RfI, Rf. then entering a radical chain cycle. 1H NMR studies provided evidence that a substantial amount (∼7% NMR yield) of the hemiacetal CH3OCH2OH is formed, i.e., the possible by-product of the reaction between .CH2OH and RfI. Finally, DFT calculations indicate that a triplet-triplet energy transfer (TTET) process from 3BP* to perfluorooctyl iodide (C8F17I) is unlikely or should be rather slow under the reaction conditions, consistent with the transient absorption studies.
42 citations
TL;DR: Three novel host materials, i.e., BP2-BP4, which contain benzophenone as the active triplet sensitizing molecular component are designed and synthesized and it is shown that their high band gap and triplet energies permit their applicability as universal host materials for blue, green, yellow, and red phosphors.
Abstract: Despite the fact that benzophenone has traditionally served as a prototype molecular system for establishing triplet state chemistry, materials based on molecular systems containing the benzophenone moiety as an integral part have not been exploited as generic host materials in phosphorescent organic light-emitting diodes (PhOLEDs). We have designed and synthesized three novel host materials, i.e., BP2–BP4, which contain benzophenone as the active triplet sensitizing molecular component. It is shown that their high band gap (3.91–3.93 eV) as well as triplet energies (2.95–2.97 eV) permit their applicability as universal host materials for blue, green, yellow, and red phosphors. While they serve reasonably well for all types of dopants, excellent performance characteristics observed for yellow and green devices are indeed the hallmark of benzophenone-based host materials. For example, maximum external quantum efficiencies of the order of 19.2% and 17.0% were obtained from the devices fabricated with yellow...
40 citations
TL;DR: In this paper, a series of thermally activated delayed fluorescence materials based on benzophenone derivatives have been synthesized by Ullmann coupling reaction, and the optical, electrochemical and thermal properties of benzphenone derivatives were systematically characterized.
TL;DR: A light induced, transition-metal-free C-C coupling reaction of 2-chlorobenzazoles with aliphatic carbamates, alcohols, and ethers is presented.
Abstract: A light induced, transition-metal-free C-C coupling reaction of 2-chlorobenzazoles with aliphatic carbamates, alcohols, and ethers is presented. Inexpensive reagents, namely sodium acetate, benzophenone, water, and acetonitrile, are employed in a simple reaction protocol using a cheap and widely available 25 W energy saving UV-A lamp at ambient temperature.
TL;DR: It was shown that the transformation products of ketoprofen 3-ethylbenZophenone and 3-acetylbenzophenone were formed under environmental conditions when ketop rofen was exposed to natural sunlight, and that photosensitizers present in natural waters significantly affect the photolytic behaviour of the investigated compounds.
TL;DR: In this paper, 25 benzophenone semicarbazones and 27 thiosemicarazones were synthesized starting from benzophenones via hydrazones treated with different aryl isocyanates and isothiocyantes under reflux.
Abstract: Twenty-five benzophenone semicarbazones and thiosemicarbazones 3–27 were synthesized starting from benzophenones via hydrazones treated with different aryl isocyanates and isothiocyantes under reflux. All synthetic derivatives were evaluated for their urease inhibitory potential. Good to moderate inhibition trend against urease was observed with the IC50 values in the range of 8.7–119.5 µM, when compared with the standard thiourea (IC50 = 21.2 ± 1.3 µM). Compound 15 showed better inhibition than the standard having the IC50 value of 8.7 ± 0.6 µM. Compounds 3, 4, 8, 11–14, 16, and 17 with the IC50 values within the range of 26.1 to 43.6 µM, demonstrated good to moderate activities while compound 9 (IC50 = 119.5 ± 1.6 µM) displayed very weak activity. The enzyme kinetic studies on the most active compounds 15 and 17 were performed to deduce their modes of inhibition and dissociation constants K
i.
TL;DR: In this article, a method for preparing photo-crosslinkable cellulose nanofibrils (CNF) was investigated, which resulted in a reduction of carboxyl group content together with an increase of the number density of amide linkages.
Abstract: A method for preparing photo-crosslinkable cellulose nanofibrils (CNF) was investigated. Benzophenone (BP), a UV-radical crosslinker, was chemically grafted to TEMPO-oxidized wood fibers in water/DMSO medium. This resulted in a reduction of carboxyl group content together with an increase of the number density of amide linkages. The BP-functionalized fibres were then microfluidized into TEMPO-oxidized CNF (TOCNF). As evidence of the crosslinking performance, the films of BP-activated TOCNF displayed improved water resistance upon UV curing (even under high energy sonication). In addition to improving wet strength the method is suitable for further modification of CNF, either by utilizing the remaining free carboxyl groups or via photochemical grafting of other substances onto the CNF structure.
TL;DR: A strong dependence of the H-abstraction with the non-covalent BP-DNA interaction mode is evidence, and a reaction that is less favorable when embedded in DNA than for the isolated system.
Abstract: We report a computational investigation of the hydrogen abstraction (H-abstraction) induced by triplet benzophenone (3BP) on thymine nucleobase and backbone sugar. The chemical process is studied using both high level multiconfigurational perturbation and density functional theory. Both methods show good agreement in predicting small kinetic barriers. Furthermore the behavior of benzophenone in DNA is simulated using molecular dynamics and hybrid quantum mechanics/molecular mechanics methods. The accessibility of benzophenone to the labile hydrogens within B-DNA is demonstrated, as well as the driving force for this reaction. We evidence a strong dependence of the H-abstraction with the non-covalent BP–DNA interaction mode, and a reaction that is less favorable when embedded in DNA than for the isolated system.
TL;DR: In this article, the synthesis of a photoreactive polyether and its subsequent photochemical attachment to various substrates is described, which allows the generation of one-component polymer coatings from standard commodity polymers under very simple process conditions, which can be lithographically structured and covalently attached to a broad spectrum of substrates, comprising even chemically rather inert materials.
Abstract: In this work, the synthesis of a photoreactive polyether and its subsequent photochemical attachment to various substrates is described. Poly(bisphenol A-co-epichlorohydrin) is chosen as an example for a technologically important class of polymers and modified in a polymeranalogous reaction with photoreactive benzophenone units. During brief UV activation, benzophenone forms reactive intermediates, which are able to formally insert into any aliphatic C,H bond, eventually forming a crosslinked polymer film. During the formation process the emerging polyether networks additionally bind to (practically) any organic molecule present at the substrate surface. This way in one reaction step directly a surface-attached polymer network is obtained. The examples, which are shown, include silane-covered oxidic surfaces and unmodified polyolefins. When appropriate masks are used, brief UV irradiation is sufficient to generate crosslinked, surface-attached polyether microstructures on a broad spectrum of substrate materials. The described strategy allows the generation of one-component polymer coatings from standard commodity polymers under very simple process conditions, which can be lithographically structured and covalently attached to a broad spectrum of substrates, comprising even chemically rather inert materials.
TL;DR: Experimental results, combined with results from density functional theory calculations, reveal the effects of solvent and substituents on the properties, relative energies, and chemical reactivities of the nπ* and ππ* triplets of two benzophenone and two anthraquinone derivatives.
Abstract: The excited nπ* and ππ* triplets of two benzophenone (BP) and two anthraquinone (AQ) derivatives have been observed in acetonitrile, isopropanol, and mixed aqueous solutions using time-resolved resonance Raman spectroscopic and nanosecond transient absorption experiments. These experimental results, combined with results from density functional theory calculations, reveal the effects of solvent and substituents on the properties, relative energies, and chemical reactivities of the nπ* and ππ* triplets. The triplet nπ* configuration was found to act as the reactive species for a subsequent hydrogen atom transfer reaction to produce a ketyl radical intermediate in the isopropanol solvent, while the triplet ππ* undergoes a proton-coupled electron transfer (PCET) in aqueous solutions to produce a ketyl radical intermediate. This PCET reaction, which occurs via a concerted proton transfer (to the excited carbonyl group) and electron transfer (to the excited phenyl ring), can account for the experimental observ...
TL;DR: In this article, the alkylation reaction of diethyl N-(diphenylmethylene)aminomethylphosphonate (6) with alkyl dihalides under phase-transfer catalysis followed by hydrolysis of the benzophenone imine moiety and subsequent cyclization provides a simple and convenient method for the synthesis of known and new cyclic α-aminophosphonates 1−5 in moderate to good yields.
TL;DR: The oxidation of guanine by triplet benzophenone in the presence of lysine has been shown to produce mono- and dilysine-substituted spiroiminodihydantion products, 8-Lys-Sp and 5,8-diLYS-Sp, in agreement with the experimental observations.
Abstract: The oxidation of guanine by triplet benzophenone in the presence of lysine has been shown to produce mono- and dilysine-substituted spiroiminodihydantion products, 8-Lys-Sp and 5,8-diLys-Sp. The potential energy surfaces for C8, C5, and C4 nucleophilic addition have been mapped out using the B3LYP/aug-cc-pVTZ//B3LYP/6-31+G(d,p) level of density functional theory with the SMD solvation model and employing methylamine as a model for the side chain of lysine. Enthalpies, barrier heights, pKa’s, and reduction potentials were calculated for intermediates to find the lowest energy paths. For neutral methylamine plus guanine radical and neutral methylamine radical plus guanine, the barrier for addition at C8 is ca. 10 kcal/mol lower than that for addition at C5 and C4. The barriers for water addition at C8, C5, and C4 of guanine radical are 13–20 kcal/mol higher than that for methylamine addition at C8. Further oxidation and loss of a proton leads to 8-methylaminoguanine, the methylamino analogue of 8-oxo-7,8-di...
TL;DR: P-CPh3 substituted oxaphosphirane complexes 3 were prepared using Li/Cl phosphinidenoid complexes 2 (M = Cr, Mo, W) and benzaldehyde and resulted in the formation of oxaph phospholane complexes 4 and 5, the former bearing a benzo[c]-1,2-oxaphospholane and the latter a novel pentacyclic P-ligand.
Abstract: P-CPh3 substituted oxaphosphirane complexes 3 were prepared using Li/Cl phosphinidenoid complexes 2 (M = Cr, Mo, W) and benzaldehyde. Employing 2 and benzophenone resulted in the formation of oxaphospholane complexes 4 and 5, the former bearing a benzo[c]-1,2-oxaphospholane and the latter a novel pentacyclic P-ligand. According to DFT studies the latter P-heterocycle arises from formal dimerization of a transient benzofused 2-phosphafurane complex 8, one of the fragments undergoing water-catalyzed [1,3]H shift (4) and the other (11) formed via elimination of HCPh3.
TL;DR: In this paper, the authors describe the preparation of organically modified TiO2-supported Pd catalyst originated from the new benzophenone imine-derived CN-palladacycle.
Abstract: The present work describes the preparation of organically modified TiO2-supported Pd catalyst originated from the new benzophenone imine-derived CN-palladacycle. The heterogeneous organic–inorganic hybrid catalyst system has been characterized by FT-IR, XRD, SEM, EDX, TEM and XPS techniques and exhibited good catalytic activity in the Sonogashira cross-coupling reactions of phenylacetylene with aryl halides under copper-, amine- and phosphine-free conditions, in conjunction with the ultra low catalyst Pd-loading. Significantly, the heterogeneous Pd catalyst allowed the reaction of phenylacetylene with aryl iodides to improve in excellent yields under very mild conditions using green solvent. Finally, the reusability of the supported Pd-complex was investigated by multiple reuses of the supported catalyst in subsequent Sonogashira cross-couplings.
TL;DR: The triplet state of benzophenone functionalized with a Brønsted acid (3 *BP-COOH) showed a more powerful oxidation capability over the simple tripletstate of benz phenophenone (3 *.BP).
Abstract: The reactivity, and even reaction pathway, of excited states can be tuned by proton-coupled electron transfer (PCET). The triplet state of benzophenone functionalized with a Bronsted acid (3*BP-COOH) showed a more powerful oxidation capability over the simple triplet state of benzophenone (3*BP). 3*BP-COOH could remove an electron from benzene at the rate of 8.0×105 m−1 s−1, in contrast to the reactivity of 3*BP which was inactive towards benzene oxidation. The origin of this great enhancement on the ability of the excited states to remove electrons from substrates is attributed to the intramolecular Bronsted acid, which enables the reductive quenching of 3*BP by concerted electron–proton transfer.
TL;DR: Thermal volatility analysis has shown that these complexes have the potential to be used as simple isolable sodium or potassium hydride surrogates, which is confirmed in test reactions with benzophenone.
Abstract: The straightforward metathesis of 1-lithio-2-tbutyl-1,2-dihydropyridine using metal tert-butoxide (Na/K) has resulted in the first preparation and isolation of a series of heavier alkali metal dihydropyridines. By employing donors, TMEDA, PMDETA and THF, five new metallodihydropyridine compounds were isolated and fully characterised. Three distinct structural motifs have been observed; a dimer, a dimer of dimers and a novel polymeric dihydropyridylpotassium compound, and the influence of cation π-interactions therein has been discussed. Thermal volatility analysis has shown that these complexes have the potential to be used as simple isolable sodium or potassium hydride surrogates, which is confirmed in test reactions with benzophenone.
TL;DR: In this paper, a triptycene scaffold with an imbedded benzophenone chromophore was used as a host material for organic photochemistry. But the authors only evaluated the performance of two simple devices fabricated with yellow and green dopants, namely PO-01 and Ir(ppy)3 respectively.
Abstract: Benzoyltriptycene (TRP-BP) – accessed readily by Fridel–Crafts benzoylation reaction – represents a molecular system with an imbedded benzophenone chromophore. The concave features inherent to a triptycene scaffold impart amorphous properties, which is an important consideration in OLEDs. Due to very weak homoconjugation in TRP-BP, the high triplet energy of the parent benzophenone chromophore (ca. 2.99 eV) is conserved. This in conjunction with a high band gap (3.80 eV) permits application of TRP-BP as a universal host material for blue, green, yellow and red dopants. An external quantum efficiency of 19.8% and the brightness of 11 800 cd m−2 were elicited from the simple devices fabricated with yellow and green dopants, namely, PO-01 and Ir(ppy)3 respectively. Ready synthetic access and impressive device performance results make TRP-BP an important addition to the scantily explored host materials based on benzophenone, which has traditionally served as a prototype carbonyl compound in the development of organic photochemistry in general to delineate the triplet-excited state properties.
TL;DR: A Bronsted acid controlled Diels-Alder reaction of 3-vinylchromones with arynes has been developed in this paper, where different kinds and amounts of acid, 9-aryl-9H-xanthen-9-ols or ortho-hydroxybenzophenones could be controllably furnished in good yields in an atom and step-economic manner.
TL;DR: The involvement of the puckered singlet diradical resolves the mechanistic puzzle of stereoselective denitrogenation of diazabicycloheptane-type azoalkanes.
Abstract: Versatile transformations of azo compounds are utilized not only in synthetic organic chemistry but also in materials science. In this study, a hitherto unknown stereoselectivity was observed by low-temperature in situ NMR spectroscopy for the photochemical denitrogenation of a cyclic azoalkane (2,3-diazabicyclo[2.2.1]heptane) derivative. Direct (singlet) photodenitrogenation at 188 K afforded two products, the configurationally retained ring-closed compound (ret-CP) and the inverted compound (inv-CP), in a ratio of 82/18 (±3) (ret-CP/inv-CP), with an overall yield of >95%. Triplet-sensitized denitrogenation at 199 K using benzophenone (3BP*) or xanthone (3Xan*) selectively produced inv-CP, with a ret-CP/inv-CP ratio of 7/93 (±3). Thermal isomerization of inv-CP into ret-CP was observed by low-temperature NMR spectroscopy. Transient absorption spectroscopy revealed that two distinct singlet diradicals are involved in the formation of CP during direct photodenitrogenation, that is, puckered puc-1DR and pla...
TL;DR: The current study demonstrates that the benzophenone derivatives are promising anticancer agents by targeting tubulin by exhibiting much better than that of the two leading compounds.
Abstract: Inspired by the potent inhibition activity of phenstatin and millepachine against cancer cell growth, a series of new benzophenone derivatives were synthesized and evaluated as tubulin polymerization inhibitors. Among them, compound 10a exhibited 0.029–0.062 μM of IC50 for five human cancer cell lines, which is much better than that of the two leading compounds. Flow cytometric analysis showed that 10a induces G2/M phase arrest and apoptosis in A549 cells. Cellular studies revealed that the induction of apoptosis by 10a was associated with the collapse of the mitochondrial membrane potential (MMP). Overall, the current study demonstrates that the benzophenone derivatives are promising anticancer agents by targeting tubulin.
TL;DR: Photophysical properties of the new rhodafluors found sensitive towards change in the pH of media and thus can be used as efficient pH sensors and thus the new fluorophores are investigated for their photophysical properties in various microenvironments and systematically characterized by means ofdensity functional theory and time dependent density functional theory.
Abstract: An efficient protocol for the synthesis of new rhodol derivatives has been developed. The synthesis involves condensation of 2-hydroxy benzophenone derivatives with 1, 3-dihydroxy benzene derivatives in solvents such as ionic liquid (N-methyl-2-pyrrolidonium hydrogen sulfate) and methane sulphonic acid. Both ionic liquid and methane sulphonic acid were found to be promising self-catalyzed solvents to bring out the conversion to form desired rhodols in excellent yields. In N-methyl-2-pyrrolidonium hydrogen sulfate reaction proceeds faster compared to methane sulphonic acid. The new fluorophores are investigated for their photophysical properties in various microenvironments and systematically characterized by means of density functional theory and time dependent density functional theory. Photophysical properties of the new rhodafluors found sensitive towards change in the pH of media and thus can be used as efficient pH sensors.
TL;DR: Treatment of benzophenone adduct 2 with a bulky aryloxide salt results in formation of (PNP)Ti[double bond, length as m-dash]O(OAr) (3) (OAr- = 2,6-bis(diphenylmethyl)-4-tert-butylphenoxide), concurrent with salt elimination and displacement of the Benzophenone.
Abstract: We report the synthesis and structure of a titanium(IV) benzophenone adduct bearing a terminal oxo ligand, (PNP)Ti = O(OTf)(OCPh2) (PNP− = N[2-PiPr2-4-methylphenyl]2) (2). Complex 2 is readily synthesized in 71% yield from the previously reported titanium alkylidene (PNP)TiCHtBu(OTf) (1) and two equivalents of benzophenone, by extruding the olefin Ph2CCHtBu. Treatment of benzophenone adduct 2 with a bulky aryloxide salt results in formation of (PNP)TiO(OAr) (3) (OAr− = 2,6-bis(diphenylmethyl)-4-tert-butylphenoxide), concurrent with salt elimination and displacement of the benzophenone. Complexes 2 and 3 were characterized by single-crystal X-ray diffraction and a variety of spectroscopic techniques, including NMR, UV-Vis-NIR spectroscopies, and TD-DFT calculations.