Search

The document is a contents list for the journal "Dalton Transactions: An International Journal of Inorganic Chemistry," published by The Royal Society of Chemistry. It includes various articles on topics such as metal-organic frameworks, luminescence, optical limiting applications, and catalytic studies. The journal aims to connect the world with the chemical sciences and invest profits back into the chemistry community. [Extracted from the article]

The document is a contents list for the journal "Chemical Communications." It includes the ISSN, CODEN, and date of publication. The contents list features various articles and communications on topics such as photocatalytic decarboxylation, visible-light-induced difunctionalization, supramolecular chemical biology, enzymatic approaches for diversifying bioproducts, and more. The journal is published by The Royal Society of Chemistry, a leading chemistry community, and is part of the EES family. It is a registered charity and focuses on exceptional research in solar energy and photovoltaics. [Extracted from the article]

In this study, we retrospectively analysed the efficacy and safety of three treatment models, namely, short-course radiotherapy sequential XELOX chemotherapy, neoadjuvant mFOLFOX6 concurrent radiotherapy and long-course concurrent radiotherapy with total mesorectal excision (TME) after treatment of locally advanced rectal cancer with high-risk factors. We collected clinical data on 177 patients with locally advanced rectal cancer (cT3-4 and/or cN+) who were treated at the Department of Abdominal Oncology of the Affiliated Cancer Hospital of Guizhou Medical University from December 2017 to December 2022. All patients were associated with 2-3 risk factors [T4b, N2, Extramural Vascular Invasion (EMVI), Mesorectal Fascia (MRF) positivity], positive lateral lymph nodes. Among them, there were 45 cases in the short course radiotherapy sequential XELOX chemotherapy group (RT + XELOX group); 64 cases in the neoadjuvant mFOLFOX6 concurrent radiotherapy group (mFOLFOX6 + CRT group); and 68 cases in the long course concurrent radiotherapy group (CRT group). The RT + XELOX group and mFOLFOX6 + CRT group completed radiotherapy and 4 cycles of neoadjuvant chemotherapy, respectively, and then rested for 1-2 weeks before TME surgery; the CRT group completed concurrent radiotherapy and then rested for 6-8 weeks before TME surgery.Adjuvant chemotherapy was conducted after surgery in each of the three groups: 2 cycles of adjuvant chemotherapy with XELOX regimen in the RT + XELOX group, 4-6 cycles of adjuvant chemotherapy with mFOLFOX6 in the mFOLFOX6 + CRT group, and 8-12 cycles of adjuvant chemotherapy with mFOLFOX6 in the CRT group.The pathological complete response rate (pCR rate), tumour downstage rate, tumour complete resection rate (R0 resection rate), local recurrence rate, distant metastasis rate, overall survival rate, incidence of adverse reactions, surgical complications and completion rate of perioperative systemic chemotherapy were compared among patients in the three groups of cases after TME. The pCR rate (21.95% vs 17.24% vs 5.00%, p = 0.034) and and tumour downstage rate (78.05% vs 68.97% vs 53.33%, p = 0.029) were higher in the RT + XELOX group and mFOLFOX6 + CRT group compared to the CRT group. The RT + XELOX group had a lower 3-year distant metastasis rate (14.63% vs 36.67%, p = 0.048) and improved 3-year overall survival (76.57% vs 48.56%, p < 0.001) compared to the CRT group. There was no significant reduction in the 3-year distant metastasis rate in the mFOLFOX6 + CRT group versus the CRT group (27.59% vs 36.67%, p = 0.719), and the 3-year overall survival was similar (51.23% vs 48.56%, p = 0.35). Multi-logistic regression analysis and stratified analysis showed that patients in the RT + XELOX group and mFOLFOX6 + CRT group were more likely to achieve pCR than the CRT group (RT + XELOX group: OR 7.3, 95% CI [2.6-20.8], p < 0.001; mFOLFOX6 + CRT group OR 2.9, 95% CI [1.1-7.9], p = 0.036). The completion rates of perioperative systemic chemotherapy in the RT + XELOX, mFOLFOX6 + CRT, and CRT groups were 82.93% vs. 84.48% vs. 61.67% (χ2=9.95, p = 0.007), respectively. And there were significant differences in grade 3-4 leukopenia and thrombocytopenia (incidence of leukopenia: 15.50% vs. 7.81% vs. 1.47%, p = 0.045; incidence of thrombocytopenia: 13.33% vs 7.81% vs 1.47%, p = 0.027). There was no significant difference in the incidence of intraoperative and postoperative complications among the three groups (p > 0.05). RT + XELOX group and mFOLFOX6 + CRT group significantly improved the near-term outcome (e.g., pCR rate) in patients with locally advanced rectal cancer with high-risk factors compared with CRT group. The RT + XELOX group also reduced the 3-year distant metastasis rate, increased the 3-year overall survival rate, and did not increase the incidence of perioperative surgical complications. It provides an effective means for the comprehensive treatment of locally advanced rectal cancer and has important clinical guidance and application value. [ABSTRACT FROM AUTHOR]

Two N-alkyloxy-N′-phenylimidazolium proligands and the corresponding platinum(II) cyclometalated N-alkyloxyimidazol-2-ylidene complexes with β-diketonate auxiliary ligands, [(CNOHC^C*)Pt(L∩L)] (L∩L = acetyacetonate (acac) or 1,3-bis(2,4,6-trimethylphenyl)-propane-1,3-dionato (mesacac)) were synthesized and fully characterized. In addition, a Au(I) monocarbene complex was synthesized, isolated and characterized. Solid-state structures of two cyclometalated platinum(II) NOHC complexes and the Au(I) NOHC complex were obtained providing structural proof. [ABSTRACT FROM AUTHOR]

Collision‐induced dissociation (CID) of the mass‐selected cation [(bipy)Pt(CH3)2(CH2SCH3)]+ in an ion‐trap mass‐spectrometer results in the losses of the neutrals ethane, ethene, dimethyl sulfide, methane, ethyl methyl sulfide, and propane. The generation of the first four neutrals is also observed, when the isolated, dimeric complex [(bipy)Pt(CH3)2(CH2SCH3)]2[SbF6]2 is heated in the condensed phase. While the product distribution is very similar regardless of whether the complex is heated in the solid state or in solution, ethane loss, i. e. the quite rare event of an sp3‐sp3 C−C reductive elimination from a platinum(IV) complex, dominates in the gas‐phase experiment. However, when the counter anion [SbF6]− is exchanged by the more weakly coordinating anion [BAr4F]−, the amounts of ethane and ethene are increased also in the condensed phase. These sum of observations indicates the similarities of the fragmentation of [(bipy)Pt(CH3)2(CH2SCH3)]+ in both phases. Thus, a correlation of processes in both environments is possible for selected systems (and particularly for unimolecular processes), but the choice of the proper conditions is crucial for a meaningful comparison. [ABSTRACT FROM AUTHOR]

Collision‐induced dissociation (CID) of the mass‐selected cation [(bipy)Pt(CH3)2(CH2SCH3)]+ in an ion‐trap mass‐spectrometer results in the losses of the neutrals ethane, ethene, dimethyl sulfide, methane, ethyl methyl sulfide, and propane. The generation of the first four neutrals is also observed, when the isolated, dimeric complex [(bipy)Pt(CH3)2(CH2SCH3)]2[SbF6]2 is heated in the condensed phase. While the product distribution is very similar regardless of whether the complex is heated in the solid state or in solution, ethane loss, i. e. the quite rare event of an sp3‐sp3 C−C reductive elimination from a platinum(IV) complex, dominates in the gas‐phase experiment. However, when the counter anion [SbF6]− is exchanged by the more weakly coordinating anion [BAr4F]−, the amounts of ethane and ethene are increased also in the condensed phase. These sum of observations indicates the similarities of the fragmentation of [(bipy)Pt(CH3)2(CH2SCH3)]+ in both phases. Thus, a correlation of processes in both environments is possible for selected systems (and particularly for unimolecular processes), but the choice of the proper conditions is crucial for a meaningful comparison. [ABSTRACT FROM AUTHOR]

Three organoplatinum(II) complexes bearing natural aryl­olefin and quinoline derivatives, namely, [4-meth­oxy-5-(2-meth­oxy-2-oxoeth­oxy)-2-(prop-2-en-1-yl)phen­yl](quinolin-8-olato)platinum(II), [Pt(C13H15O4)(C9H6NO)], (I), [4-meth­oxy-5-(2-oxo-2-propoxyeth­oxy)-2-(prop-2-en-1-yl)phen­yl](quinoline-2-carboxy­l­ato)platinum(II), [Pt(C15H19O4)(C10H6NO2)], (II), and chlorido­[4-meth­oxy-5-(2-oxo-2-propoxyeth­oxy)-2-(prop-2-en-1-yl)phen­yl](quinoline)­plat­inum(II), [Pt(C15H19O4)Cl(C9H7N)], (III), were synthesized and structurally characterized by IR and 1H NMR spectroscopy, and by single-crystal X-ray diffraction. The results showed that the cyclo­platinated arylolefin coordinates with PtII via the carbon atom of the phenyl ring and the C=Colefinic group. The deprotonated 8-hy­droxy­quinoline (C9H6NO) and quinoline-2-carb­oxy­lic acid (C10H6NO2) coordinate with the PtII atom via the N and O atoms in complexes (I) and (II) while the quinoline (C9H7N) coordinates via the N atom in (III). Moreover, the coordinating N atom in complexes (I)–(III) is in the cis position compared to the C=Colefinic group. The crystal packing is characterized by C—H⋯π, C—H⋯O [for (II) and (III)], C—H⋯Cl [for (III) and π–π [for (I)] inter­actions. [ABSTRACT FROM AUTHOR]

Background Our previous work indicated that the addition of lobaplatin to combined therapy with taxane and anthracycline can improve the pathological complete response rate of neoadjuvant therapy for triple-negative breast cancer (TNBC) and lengthen long-term survival significantly, but the therapeutic markers of this regimen are unclear. Methods Eighty-three patients who met the inclusion criteria were included in this post hoc analysis. We analyzed the association between platelet-to-lymphocyte ratio (PLR) and neutrophil-to-lymphocyte ratio (NLR) before neoadjuvant chemotherapy with the efficacy and prognosis after treatment with docetaxel, epirubicin, and lobaplatin neoadjuvant chemotherapy regimen. χ2 test and Cox regression were used to analyze the association between PLR and NLR with total pathologic complete response (tpCR), as well as the association between PLR and NLR with event-free survival (EFS) and overall survival (OS), respectively. Results The tpCR rate in the PLR− group was 49.0% (25/51), which was significantly higher than that in the PLR+ group (25.0% [8/32], P  = .032). The tpCR rate in the NLR− group was 49.1% (26/53), which was significantly higher than that in the NLR+ group (23.3% [7/30], P  = .024). The tpCR rate of the PLR−NLR− (PLR− and NLR−) group was 53.7% (22/41), which was significantly higher than that of the PLR+/NLR+ (PLR+ or/and NLR+) group (26.1% [11/42]; P  = .012). EFS and OS in the NLR+ group were significantly shorter than those in the NLR− group (P  = .028 for EFS; P  = .047 for OS). Patients in the PLR−NLR− group had a longer EFS than those in the PLR+/NLR+ group (P  = .002). Conclusion PLR and NLR could be used to predict the efficacy of neoadjuvant therapy with the taxane, anthracycline, and lobaplatin regimen for patients with TNBC, as patients who had lower PLR and NLR values had a higher tpCR rate and a better long-term prognosis. [ABSTRACT FROM AUTHOR]

In this work, the geometrical, optical, and phosphorescence properties of four complexes with general formula [dRpypy—C(OCH3)R′—dRpypy]Pt, with Pt-1 (R = F, R′ = methyl), Pt-2 (R = F, R′ = hexyl), Pt-3 (R = methoxy, R′ = methyl) and Pt-4 (R = methoxy, R′ = hexyl), were studied using the B3PW91 and TD-B3PW91 methods. The effect of the double substitution R and R′ on the electronic properties of the four complexes has been investigated. Replacing the two fluorine atoms with the two methoxy groups modifies the shape of the UV–vis spectra and red shift the phosphorescence spectra, while the substituents on the linker R′ do not induce changes in both absorption and phosphorescence spectra. Normal modes involved in the vibronic structure were identified and analyzed using adiabatic Hessian approaches according to the Franck–Condon approximation. The computed phosphorescence wavelengths agree with the observed ones and indicate that the fluorinated complexes exhibit a bright light blue color, while the methoxy complexes display a light spring green color. Further, temperature effects on simulated phosphorescence spectra were studied. [ABSTRACT FROM AUTHOR]

The current paper describes the formation of a new series of platinum(II) complexes with 5,7-di-tert-butyl-2-(thiophen-2-yl)benzo[d]oxazole (btbo) ligand. This study has focused on synthesis methods of some organoplatinum(II) complexes containing btbo ligand from two different reagents under different conditions. Furthermore, a detailed computational study was performed to identify the thermodynamic parameter's behavior. The synthesis was initiated from some complexes including cis-[PtCl2(dmso)2], R1, [PtCl2(COD)], R2 and a benzoxazole derivative as organic ligand 5,7-di-tert-butyl-2-(thiophen-2-yl)benzo[d]oxazole, (btbo). Implementation of the 1H NMR analysis procedure on products reveals two isomers' existence. Moreover, the thermodynamic parameters, (ΔH°, ΔG°, ΔS°), were quantified to achieve a more precise understanding. The energy diagram examination and considering the quantified parameters present the stability and instability of each product which is in notable agreement with the experimental data. [ABSTRACT FROM AUTHOR]

The title compound, (C4H12N)[V(C12H8N4O2)O2]H2O, was synthesized via aerial oxidation on refluxing picolinohydrazide with ethyl picolinate followed by addition of VIVO(acac)2 and diethylamine in methanol. It crystallizes in the triclinic crystal system in space group P.... In the complex anion, the dioxido-vanadium(V) moiety exhibits a distorted square-pyramidal geometry. In the crystal, extensive hydrogen bonding links the water molecule to two complex anions and one diethylammonium ion. One of the CH2 groups in the diethyl-amine is disordered over two sets of sites in a 0.7:0.3 ratio. [ABSTRACT FROM AUTHOR]

We describe a family of cationic methylstannylene and chloro‐ and azidosilylene organoplatinum(II) complexes supported by a neutral, binucleating ligand. Methylstannylenes MeSn:+ are stabilized by coordination to PtII and are formed by facile Me group transfer from dimethyl or monomethyl PtII complexes, in the latter case triggered by concomitant B−H, Si−H, and H2 bond activation that involves hydride transfer from Sn to Pt. A cationic chlorosilylene complex was obtained by formal HCl elimination and Cl− removal from HSiCl3 under ambient conditions. The computational studies show that stabilization of cationic methylstannylenes and cationic silylenes is achieved through weak coordination to a neutral N‐donor ligand binding pocket. The analysis of the electronic potentials, as well as the Laplacian of electron density, also reveals the differences in the character of Pt−Si vs. Pt−Sn bonding. We demonstrate the importance of a ligand‐supported binuclear Pt/tetrel core and weak coordination to facilitate access to tetrylium‐ylidene Pt complexes, and a transmetalation approach to the synthesis of MeSnII:+ derivatives. [ABSTRACT FROM AUTHOR]

The cationic platinum(II) organometallic complex [Pt(terpy)Me]+ (terpy = 2,2′:6′,2″-terpyridine) at mild acidic pH interacts with poly(L-glutamic acid) (L-PGA) in its α-helix conformation, affording chiral supramolecular adducts. Their kinetics of formation have been investigated in detail as a function of the concentrations of both reagents and changing pH, ionic strength, the length of the polymeric scaffold and temperature. After a very fast early stage, the kinetic traces have been analyzed as three consecutive steps, suggesting a mechanism based on the electrostatic fast formation of a not-organized aggregate that subsequently evolves through different rearrangements to form the eventual supramolecular adduct. A model for this species has been proposed based on (i) the attractive electrostatic interaction of the cationic platinum(II) complexes and the polyelectrolyte and (ii) the π-stacking interactions acting among the [Pt(terpy)Me]+ units. [ABSTRACT FROM AUTHOR]

The organoplatinum chemistry of the ligands 2-C5H4N-CH2-NH-C6H3-2-OH-5-X (L1, X = H; L3, X = NO2) and 2-C5H4N-CH=N-C6H3-2-OH-5-X (L2, X = H; L4, X = NO2), which contain an appended phenol substituent, is described. Comparisons are made between the ligands with amine or imine groups (L1, L3 vs. L2, L4) and ligands with X = H or NO2 (L1, L2 vs. L3, L4), and major differences are observed. Thus, on reaction with the cycloneophylplatinum(II) complex [{Pt(CH2CMe2C6H4)(μ-SMe2)}2], ligands L1, L2 and L4 give the corresponding platinum(II) complexes [Pt(CH2CMe2C6H4)(κ2-N,N′-L)], containing a Pt··HO hydrogen bond, whereas L3 gives a mixture of isomeric platinum(IV) hydride complexes [PtH(CH2CMe2C6H4)(κ3-N,N′,O-L3-H)], which are formed by oxidative addition of the phenol O-H bond and which react further with oxygen to give [Pt(OH)(CH2CMe2C6H4)(κ3-N,N′,O-L3-H)]. The differences in reactivity are proposed to be due to the greater acidity of the nitro-substituted phenol groups in L3 and L4 and to the greater ability of the deprotonated amine ligand L3 over L4 to stabilize platinum(IV) by adopting the fac-κ3-N,N′,O-L3-H coordination mode. [ABSTRACT FROM AUTHOR]

Terpyridine (TPY) platinum(II) chloride with a triphenylamine (TPA) group was successfully synthesized. The strong intramolecular Donor(TPA)-Acceptor(TPY) interaction induced the low-energy absorption band, mixing the spin-allowed singlet dπ(Pt)→π*(TPY) metal-to-ligand charge transfer (MLCT) with the chloride ligand-to-metal charge transfer (LMCT) and chloride ligand-to-ligand (TPY) charge transfer (LLCT) transitions, to bathochromically shift to λmax = 449 nm with significant enhancement and broadening effects. Using the cyclic voltammetry method, its oxidative electropolymerization (EP) films on working Pt disk and ITO electrodes were produced with tunable thickness and diffusion controlled redox behavior, which were characterized by the SEM, EDS, FT-IR, and AC impedance methods. Upon applying +1.4 V voltage, the sandwich-type electrochromic device (ECD) with ca. 290 nm thickness of the EP film exhibits a distinct color transformation from red (CIE coordinates: L = 50.75, a = 18.58, b = 5.69) to dark blue (CIE coordinates: L = 45.65, a = −1.35, b = −12.49). Good electrochromic (EC) parameters, such as a large optical contrast (ΔT%) of 78%, quick coloration and bleaching response times of 2.9 s and 1.1 s, high coloration and bleaching efficiencies of 278.0 and 390.5 C−1·cm2, and good cycling stability (maintains 70% of the initial ΔT% value after 3200 voltage switching cycles), were obtained. [ABSTRACT FROM AUTHOR]

We employed a dual strategy that combines experimental and computational analyses of two copper(II) coordination complexes with σ-donating acylpyrazolone ligands. HLIIIB, [Cu(HLIIIB)2] and [Cu(HLI)2] have been characterized using a variety of physicochemical methods and density functional theory (DFT) calculations using the B3LYP level of theory and 6-31 G basis set. Single crystal X-ray diffraction studies revealed monoclinic and triclinic crystal systems for [Cu(HLI)2] and [Cu(HLIIIB)2], respectively, with square planar geometries for both complexes. Both complexes exhibit quasi-reversible behavior in their cyclic voltammograms in DMSO. ESR spectroscopy was performed to determine the magnetic behaviorof the two complexes. The intermolecular interactions of the complexes were further investigated using Hirshfeld surface analysis. The compounds showed promising cytotoxicities when tested against cancer cell lines of lung carcinoma, hepatocellular carcinoma, and neuroblastoma. Notable apoptotic cell death was observed with [Cu(HLI)2], supported by gene expression changes, indicating induction of apoptosis. The findings suggest the potential of copper complexes as effective agents against neuroblastoma and highlight their superiority to cisplatin. [ABSTRACT FROM AUTHOR]

[PtCl2{Te(CH2)6}2] (1) was synthesized from the cyclic telluroether Te(CH2)6 and cis-[PtCl2(NCPh)2] in dichloromethane at room temperature under the exclusion of light. The crystal structure determination showed that in the solid state, 1 crystallizes as yellow plate-like crystals of the cis-isomer 1cis and the orange-red interwoven needles of 1trans. The crystals could be separated under the microscope. NMR experiments showed that upon dissolution of the crystals of 1cis in CDCl3, it isomerizes and forms a dynamic equilibrium with the trans-isomer 1trans that becomes the predominant species. Small amounts of cis-trans-[Pt3Cl6{Te(CH2)6}4] (2) and cis-trans-[Pt4Cl8{Te(CH2)6}4] (3) were also formed and structurally characterized. Both compounds show rare bridging telluroether ligands and two different platinum coordination environments, one exhibiting a cis-Cl/cis-Te(CH2)6 arrangement and the other a trans-Cl/trans-Te(CH2)6 arrangement. Complex 2 has an open structure with two terminal and two bridging telluroether ligands, whereas complex 3 has a cyclic structure with four Te(CH2)6 bridging ligands. The bonding and formation of the complexes have been discussed through the use of DFT calculations combined with QTAIM analysis. The recrystallization of the mixture of the 1:1 reaction from d6-DMSO afforded [PtCl2{S(O)(CD3)2}{Te(CH2)6}] (4) that could also be characterized both structurally and spectroscopically. [ABSTRACT FROM AUTHOR]

A trigonal luminescent metallacage was constructed by the coordination-driven self-assembly of m-pyridine-modified tetraphenylene ligands with organic Pt(II) acceptors, which exhibited excellent Aggregation-Induced Emission (AIE) properties. An efficient artificial light-harvesting system was successfully constructed by selecting the metallacage as the donor and the hydrophobic fluorescent dye Nile Red (NiR) as the donor molecule in a system of acetone/water (1/9, v/v), The absorption spectra of NiR and the emission spectra of the metallacage showed considerable overlap, achieving energy transfer from the metallacage to NiR. [ABSTRACT FROM AUTHOR]

A series of four binuclear complexes of general formula [(C^C)Au(Cl)(L^L)(Cl)Au(C^C)], where C^C is 4,4'‐diterbutylbiphenyl and L^L is either a bridging diphosphine or 4,4'‐bipyridine, are synthetized with 52 to 72 % yield and structurally characterized by X‐ray diffraction. The use of the chelating 1,2‐diphenylphosphinoethane ligand in a 1 : 2 (P^P):Au stoichiometry leads to the near quantitative formation of a gold double‐complex salt of general formula [(C^C)Au(P^P)][(C^C^)AuCl2]. The compounds display long‐lived yellow‐green phosphorescence with λem in the range of 525 to 585 nm in the solid state with photoluminescence quantum yields (PLQY) up to 10 %. These AuIII complexes are tested for their antiproliferative activity against lung adenocarcinoma cells A549 and results show that compounds 2 and 5 are the most promising candidates. The digold salt 5 shows anticancer activity between 66 and 200 nM on the tested cancer cell lines, whereas derivative 2 displays concentration values required to reduce by 50 % the cell viability (IC50) between 7 and 11 μM. Reactivity studies of compound 5 reveal that the [(C^C)Au(P^P)]+ cation is stable in the presence of relevant biomolecules including glutathione suggesting a structural mechanism of action. [ABSTRACT FROM AUTHOR]

A platinum(IV) prodrug, cis,cis,trans-[Pt(NH3)2Cl2(biotin)(L)] (1), derived from cisplatin, where HL is the PEGylated red-light active boron-dipyrromethene (BODIPY) ligand, was synthesized, characterized and its photocytotoxicity evaluated. The complex showed a near-IR absorption band at 653 nm (ε ∼9.19 × 104 M−1 cm−1) in dimethyl sulfoxide and Dulbecco's phosphate-buffered saline (1 : 1 v/v) at pH 7.2. When excited at 630 nm, it showed an emission band at 677 nm in DMSO with a fluorescence quantum yield of 0.13. The 1,3-diphenylisobenzofuran titration experiment gave a singlet oxygen quantum yield (ΦΔ) of ∼0.32. A mechanistic DNA photocleavage study revealed singlet oxygen as the reactive oxygen species (ROS). The complex with biotin and PEGylated-distyryl-BODIPY showed significantly higher cellular uptake in A549 cancer cells as compared to non-cancerous Beas-2B cells from flow cytometry, indicating selectivity towards cancer cells. A dichlorodihydrofluorescein diacetate assay showed cellular ROS generation. Confocal images revealed predominant internalization in the mitochondria. The prodrug showed remarkable photodynamic therapy (PDT) activity in cancerous A549 and multidrug-resistant MDA-MB-231 cells with a high photocytotoxicity index value (half-maximal inhibitory concentration (IC50): 0.61–1.54 μM in red light), while being non-toxic in the dark. The chemo-PDT activity was significantly less in non-tumorigenic lung epithelial cells (Beas-2B). The prodrug effectively triggered cellular apoptosis, which was confirmed by the Annexin V-FITC/propidium iodide assay, and the alteration of the mitochondrial membrane potential was substantiated by the JC-1 dye assay. The β-tubulin immunofluorescence assay confirmed that incubating the cells with a light-treated complex resulted in the rapture of the cytoskeletal structure and the formation of apoptotic bodies. The results demonstrate that the prodrug triggered apoptosis via DNA damage, a reduction in mitochondrial function and disruption of the cytoskeletal framework. [ABSTRACT FROM AUTHOR]

A series of platinum(II) bipyridine complexes with two rhodamine-like alkynyl (Rhodyne) ligands were developed to show chemo-induced "ON–OFF" switching capabilities with exceptional near-infrared phosphorescence and delayed fluorescence. This study contributes to the design of versatile photosensitizers with multiple functionalities, including metal ion and biomolecule sensing, photodynamic therapy, and optoelectronics. [ABSTRACT FROM AUTHOR]

The structure of a platinum(II) complex containing (R)‐(dimethylamino)ethylnapthyl and bis(diphenylphosphanyl)methane monosulfide ligands, namely, {(R)‐1‐[1‐(dimethylamino)ethyl]napthyl‐κ2N,C2}[(diphenylphosphanylmethyl)diphenylphosphine sulfide‐κ2P,S]platinum(II) hexafluoridoantimonate dichloromethane monosolvate, [Pt(C14H16N)(C25H22P2S)][SbF6]·CH2Cl2, was determined. The structural features are compared with analogous platinum bis(diphenylphosphanyl)methane monoxide [dppm(O)] and bis(diphenylphosphanyl)methane monoselenide [dppm(Se)] complexes in relation to their potential hemilability and stereochemical nonrigidity. [ABSTRACT FROM AUTHOR]

In this structural study, structural data are classified and analyzed for almost seventy complexes of the general formula Pt(η3–P1X1P2)(Y) (X1 = O, N, C, S, Si) and (Y = various monodentate ligands), in which the respective η3–P1X1P2 ligand forms a pair of five-membered metallocyclic rings with a common X1 atom of the P1C2X1C2P2 type. The present complexes crystallize in five crystal systems: trigonal (1×), tetragonal (1×), orthorhombic (11×), triclinic (18×), and monoclinic (39×). In 69 complexes, a η3 ligand with monodentate Y constructs a distorted square planar geometry around each Pt(II) atom. There is only one complex in which Pt(η3–P1Si1P2)(P3Ph3) constructs a trigonal–pyramidal geometry around a Pt(II) atom. The three P atoms construct a trigonal plane, and the Si atom occupies a pyramid. The structural data are discussed from various points of view, including the covalent radii of the atoms, the degree of distortion, and trans-influence. The trans-effect on the Pt-L bond distance also affects the L-PT-L bond angles, as well as the distortion of square planar geometry around Pt(II) atoms. [ABSTRACT FROM AUTHOR]

Background Treatment options for pancreatic ductal adenocarcinoma (PDAC) are limited and checkpoint blockade inhibitors have been disappointing in this disease. Pegilodecakin has demonstrated single agent anti-tumor activity in immune-sensitive tumors. Phase 1 and preclinical data indicate synergy of pegilodecakin with 5-FU and platins. We assessed the safety and activity of pegilodecakin+FOLFOX in patients with PDAC. Methods IVY (NCT02009449) was an open-label phase 1b trial in the United States. Here we report on all enrolled patients from cohort C. Heavily pretreated patients were treated with pegilodecakin (self-administered subcutaneously daily at 2.5, 5, or 10 μg/kg) + 5-flurouracil/leucovorin/oxaliplatin (FOLFOX), dosed per manufacturers prescribing information, until tumor progression. Eligible patients had measurable disease per immune-related response criteria (irRC), were ≥ 18 years of age, and had ECOG performance status of 0 or 1. Patients were evaluated for primary(safety) and secondary (tumor response per irRC) endpoints. Results From 5 August 2014-12 July 2016, 39 patients enrolled in cohort C. All patients were evaluable for safety. In this advanced population, regimen had manageable toxicities with no immune-related adverse events (irAEs) greater than grade 1. The most common grade 3/4/5 TEAEs were thrombocytopenia (21[53.8%] of 39) and anemia (17[43.6%] of 39). In evaluable PDAC patients, the best overall response of pegilodecakin+FOLFOX was 3(14%) with CRs in 2(9%) patients. Conclusions Pegilodecakin+FOLFOX had an acceptable tolerability profile in PDAC, with no substantial irAEs seen, and promising efficacy with the combination yielding a 2-year OS of 24% (95% CI 10-42). These data led to the phase 3 study with pegilodecakin+FOLFOX as second-line therapy of PDAC (SEQUOIA).

BackgroundPancreatic cancer has a poor prognosis and few choices of therapy. For patients with adequate performance status, FOLFIRINOX or gemcitabine plus nab-paclitaxel are preferred first-line treatment. 5-Fluorouracil (5-FU)-based therapy (e.g. FOLFIRI, OFF, or FOLFOX) are often used in patients who previously received gemcitabine-based regimens. A systematic review was conducted of the safety and efficacy of FOLFOX for metastatic pancreatic cancer following prior gemcitabine-based therapy. A Bayesian fixed-effect meta-analysis with adjustment of patient performance status (PS) was conducted to evaluate overall survival (OS) and compare outcomes with nanoliposomal irinotecan combination therapy.MethodsPubMed.gov , FDA.gov , ClinicalTrials.gov , congress abstracts, Cochrane.org library, and EMBASE database searches were conducted to identify randomized controlled trials of advanced/metastatic disease, prior gemcitabine-based therapy, and second-line treatment with 5-FU and oxaliplatin. The database search dates were January 1, 1990-June 30, 2019. Endpoints were OS and severe treatment-related adverse events (TRAEs). Trial-level PS scores were standardized by converting Karnofsky grade scores to Eastern Cooperative Oncology Group (ECOG) Grade, and overall study-weighted PS was calculated based on weighted average of all patients.ResultsOf 282 studies identified, 11 randomized controlled trials (N = 454) were included in the meta-analysis. Baseline weighted PS scores predicted OS in 10 of the 11 studies, and calculated PS scores of 1.0 were associated with a median OS of 6.3 months (95% posterior interval, 5.4-7.4). After adjusting for baseline PS, FOLFOX had a similar treatment effect profile (median OS, range 2.6-6.7 months) as 5-FU/leucovorin plus nanoliposomal irinotecan therapy (median OS, 6.1 months; 95% confidence interval 4.8-8.9). Neutropenia and fatigue were the most commonly reported Grade 3-4 TRAEs associated with FOLFOX.ConclusionsBaseline PS is a strong prognostic factor when interpreting the efficacy of 5-FU and oxaliplatin-based therapy of pancreatic cancer after progression on first-line gemcitabine-based regimens. When baseline PS is considered, FOLFOX has a similar treatment effect as 5-FU and nanoliposomal irinotecan therapy and a comparable safety profile. These findings suggest that 5-FU and oxaliplatin-based therapies remain an acceptable and alternative second-line treatment option for patients with pancreatic cancer and adequate PS (e.g. ECOG 0-1) following gemcitabine treatment.

Propargylic amines are versatile synthetic intermediates in organic synthesis and can be readily accessed through a catalytic three-component coupling of aldehydes, alkynes, and amines, termed the "A SP 3 sp coupling". [33] Moreover, reactions of propargylic amine substrates B 1n b and B 1o b bearing alternative amine moieties also proceeded smoothly (Scheme 3). Keywords: 2-boryl allylboronates; propargylic amines; platinum catalysis; bimetallic synergistic effect; diborylation EN 2-boryl allylboronates propargylic amines platinum catalysis bimetallic synergistic effect diborylation 1573 1576 4 07/31/23 20230815 NES 230815 Graph Organoboron compounds play essential roles in organic synthesis and in the pharmaceutical industry. [Extracted from the article]

Macrocyclic molecule‐based host–guest systems, which provide contributions for the design and construction of functional supramolecular structures, have gained increasing attention in recent years. In particular, platinum(II) metallacycle‐based host–guest systems provide opportunities for chemical scientists to prepare novel materials with various functions and structures due to the well‐defined shapes and cavity sizes of platinum(II) metallacycles. However, the research on platinum(II) metallacycle‐based host–guest systems has been given little attention. In this article, we demonstrate the host–guest complexation between a platinum(II) metallacycle and a polycyclic aromatic hydrocarbon molecule, naphthalene. Taking advantage of metallacycle‐based host–guest interactions and the dynamic property of reversible Pt coordination bonds, a [2]rotaxane is efficiently prepared by employing a template‐directed clipping procedure. The [2]rotaxane is further applied to the fabrication of an efficient light‐harvesting system with multi‐step energy transfer process. This work comprises an important supplement to macrocycle‐based host–guest systems and demonstrates a strategy for efficient production of well‐defined mechanically interlocked molecules with practical values. [ABSTRACT FROM AUTHOR]

Syntheses of five (1–5) cationic organometallic complexes bearing two platinum (II) centers are being reported. Compounds 1 and 2 have a flexible molecular backbone and are isomeric. Compounds 3, 4, and 5 are structural isomers with a rigid structural framework and containing pyrimidine/pyrazine in the center and two pendant arms bearing the alkynyl–ditopic platinum units. Compounds 1–5 were systematically characterized using FT‐IR, NMR [1H, 31P{1H}, and 13C{1H}], and HRMS. The antiproliferative activity of these compounds was examined against HeLa cancer cell line, and results were compared with that of cisplatin. "Live/dead" cell death assay was performed to ratify the superior antiproliferative activities of some of these organometallic complexes with respect to cisplatin. [ABSTRACT FROM AUTHOR]

Optically-pure triptycene-based metallomacrocycles are, for the first time, synthesized by the coordination-driven self-assembly of enantiopure triptycene-derived ladder-type bis(benzo[f]isoquinoline) ligands with a cis-platinum(II) complex. A pair of enantiomeric homochiral metallomacrocycles is also produced by the coordination-driven homochiral self-sorting of the corresponding racemic ligands, which relies on the shape-persistent nature of the ladder-structured ligands. [ABSTRACT FROM AUTHOR]

Platinum(II) complexes bearing N‐heterocyclic carbenes based guanosine and caffeine have been synthesized by unassisted C−H oxidative addition, leading to the corresponding trans‐hydride complexes. Platinum guanosine derivatives bearing triflate as counterion or bromide instead of hydride as co‐ligand were also synthesized to facilitate correlation between structure and activity. The hydride compounds show high antiproliferative activity against all cell lines (TC‐71, MV‐4‐11, U‐937 and A‐172). Methyl Guanosine complex 3, bearing a hydride ligand, is up to 30 times more active than compound 4, with a bromide in the same position. Changing the counterion has no significant effect in antiproliferative activity. Increasing bulkiness at N7, with an isopropyl group (compound 6), allows to maintain the antiproliferative activity while decreasing toxicity for non‐cancer cells. Compound 6 leads to an increase in endoplasmic reticulum and autophagy markers on TC71 and MV‐4‐11 cancer cells, induces reductive stress and increases glutathione levels in cancer cells but not in non‐cancer cell line HEK‐293. [ABSTRACT FROM AUTHOR]

Precise combination therapy, involving multiple chemotherapeutics with pharmacologically synergistic antitumor effects, is a promising approach to address the challenge of monotherapy with insufficient activity towards their targets of interest. We employed Pt←pyridine coordination-driven assembly to construct a stoichiometric coordination complex of camptothecin and organoplatinum (II) (Pt-CPT). The Pt-CPT complex exhibited a remarkable synergistic effect toward several tumor cell lines, which is equal to the optimal synergistic effect of (PEt 3) 2 Pt(OTf) 2 (Pt) and CPT mixture at various ratios. An amphiphilic polymer with H 2 O 2 -responsiveness and glutathione (GSH)-depleting ability (PO) was used to encapsulate Pt-CPT complex to enable the nanomedicine (Pt-CPT@PO) with prolonged blood circulation and elevated tumor accumulation. The Pt-CPT@PO nanomedicine exhibited remarkable synergistic antitumor efficacy and antimetastatic effect on a mice orthotopic breast tumor model. This work demonstrated the potential of stoichiometric coordination-driven assembly of organic therapeutics with metal-based drugs in developing advanced nanomedicine with optimal synergistic antitumor activity. In this study, for the first time, we employed Pt←pyridine coordination-driven assembly to construct a stoichiometric coordination complex of camptothecin and organoplatinum (II) (Pt-CPT), with an optimal synergistic effect at various ratios. Then it was encapsulated into an amphiphilic polymer with H 2 O 2 -responsiveness and glutathione (GSH)-depleting ability (PO) to enable the nanomedicine (Pt-CPT@PO) with prolonged blood circulation and elevated tumor accumulation. The Pt-CPT@PO nanomedicine exhibited remarkable synergistic antitumor efficacy and antimetastatic effect on a mice orthotopic breast tumor model. [Display omitted] [ABSTRACT FROM AUTHOR]

This article is a systematic overview of the literature published predominantly between 2020 and 2023 focusing on the preparation methods, reactions, and structural characteristics of organoplatinum compounds featuring two or more platinum–carbon bonds. Additionally, examples illustrating their potential applications are highlighted. Special emphasis is placed on discussing the most effective synthetic approaches. The formation reactions of organic platinum compounds with multiple Pt–C bonds are explored, alongside insights into their catalytic and biological activities. [ABSTRACT FROM AUTHOR]

ObjectiveWomen with persistent, recurrent, and/or metastatic cervical cancer have a poor prognosis. Even with the availability of cisplatin plus paclitaxel and bevacizumab, median overall survival (OS) is only 17.0 months, with median post-progression survival of approximately seven months. We studied the therapeutic vaccine, Axalimogene filolisbac (ADXS-HPV), in women who had progressed following at least one prior line of therapy (Gynecologic Oncology Group protocol 265/NCT01266460).MethodsVolunteers ≥18 years with advanced cervical cancer and GOG performance status score of 0 or 1 were eligible for participation in this 2-stage, phase II trial. In stage 1, women received up to three doses of ADXS-HPV (1 × 109 colony-forming units in 250 mL IV over 15 min every 28 days) and were monitored for tumor progression. In stage 2, women were treated until progression, intolerable adverse events (AEs), or voluntary withdrawal of consent. Co-primary endpoints were safety and proportion of volunteers surviving ≥12 months. An estimated, combined (stages 1 + 2) 12-month OS of 35% was calculated from historical GOG cohorts to declare ADXS-HPV sufficiently active in this platinum-pre-treated population. Secondary endpoints were OS and progression-free survival (PFS).ResultsAmong 50 evaluable volunteers, the 12-month OS was 38% (n = 19). Median OS was 6.1 months (95% CI: 4.3-12.1) and median PFS was 2.8 months (95% CI: 2.6-3.0). The most common treatment-related AEs were fatigue, chills, fever, nausea, and anemia. The majority of AEs were grade 1 or 2 and resolved spontaneously or with appropriate treatment.ConclusionAt the dose and schedule studied, ADXS-HPV immunotherapy was tolerable and met the protocol-specified benchmark for activity required to warrant further investigation in volunteers with cervical carcinoma.

When the 5-fluorouracil, leucovorin, and oxaliplatin (FOLFOX) chemotherapy regimen is used to treat colorectal cancer (CRC), chemotherapy-induced peripheral neuropathy (CIPN) caused by oxaliplatin can substantially affect quality of life (QOL) in the CRC patients. This study compared emotional distress and QOL during FOLFOX in CRC patients with and without CIPN symptoms.This cross-sectional, descriptive, and comparative study recruited 68 CRC patients receiving FOLFOX at a local teaching hospital and at a medical center in southern Taiwan. Self-reported structured questionnaires (oxaliplatin-associated neuropathy questionnaire, profile of mood states short form, and the European Organization for Research and Treatment of Cancer Quality of Life Questionnaire, Core 30, version 3.0) were used for 1-time data collection. The Chi-square test, Fisher exact test, and Mann-Whitney U test were used to analyze data, and a P-value

BACKGROUND/AIM:We have previously developed a novel bone-targeting platinum compound, 3Pt, and showed that it has strong inhibitory activity against osteosarcoma cells and orthotopic cell-line xenograft mouse models. In the present report, we compared the efficacy of 3Pt to cisplatinum (CDDP) in a CDDP-resistant relapsed osteosarcoma patient-derived orthotopic xenograft (PDOX) mouse model. PATIENTS AND METHODS:The tumor of a patient with osteosarcoma of the distal femur was treated with CDDP-based chemotherapy followed by surgery. The surgical specimen was used to establish a PDOX model. An osteosarcoma cell line was also established from the original patient tumor. Osteosarcoma cell viability was assessed with the WST-8 assay and the IC50 values were calculated. The PDOX models were randomized into three groups: untreated control, CDDP-treated group, and 3Pt-treated group. Tumor size and body weight were measured twice a week. RESULTS:3Pt had a strong concentration-dependent cytocidal effect in vitro. The IC50 value of 3Pt was significantly lower than that of CDDP. On day 14 of the treatment, 3Pt caused a significantly greater tumor growth inhibition compared to the untreated control and CDDP-treated mice. CONCLUSION:3Pt is a promising clinical candidate for the treatment of recalcitrant osteosarcoma.

Context/objectivesThis is the first study to determine the minimal clinically important difference (MCID) of the European Organisation of Research and Treatment of Cancer Quality of Life Questionnaire-CIPN twenty-item scale (EORTC QLQ-CIPN20), a validated instrument designed to elicit cancer patients' experience of symptoms and functional limitations related to chemotherapy-induced peripheral neuropathy.MethodsCancer patients receiving neurotoxic chemotherapy completed EORTC QLQ-CIPN20 and the Functional Assessment of Cancer Therapy/Gynecologic Oncology Group-Neurotoxicity [FACT/GOG-NTX] at baseline, second cycle of chemotherapy (T2, n = 287), and 12 months after chemotherapy (T3, n = 191). Anchor-based approach used the validated FACT/GOG-NTX neurotoxicity (Ntx) subscale to identify optimal MCID cutoff for deterioration. Distribution-based approach used one-third standard deviation (SD), half SD, and one standard error of measurement of the total EORTC QLQ-CIPN20 score.ResultsThere was a moderate correlation between the change scores of the Ntx subscale and sensory and motor subscales of QLQ-CIPN20 (T2: r = - 0.722, p

A series of new platinum square planar complexes [Pt(NCN)L]+/0 with the pincer N^C^N cyclometallated ligand (NC(H)N = 1,3-bis(1-phenyl-1H-phenanthro[9,10-d]imidazol-2-yl)benzene) containing the following L: Cl−, acetonitrile, pyridine, dimethylaminopyridine, 2,6-dimethylphenylisocyanide, has been synthesized. Application of bridging acetate ion as L ligand allowed obtaining a binuclear [Pt(NCN)]2OOCCH3 complex. The bulky and rigid structure of N^C^N-ligand provokes instability of its pincer coordination that makes possible transformation of the molecular architecture to give a heteronuclear complex with the Pt-Ag-Pt coordination core. The composition and structure of the obtained compounds were characterized in solution and in the solid state using ESI mass-spectrometry, NMR spectroscopy, elemental analysis, and single-crystal XRD crystallography. The complexes luminesce in solid state, solution, and in polymeric matrix demonstrating moderate to bright emission at ca. 550 nm with quantum yields up to 22% and lifetime of excited state up to 22 µs. TD DFT computational approach together with analysis of the photophysical properties in different media reveals the predominant ligand-centered 3IL nature of the radiative excited state localized at the N^C^N-ligand. The ancillary ligand L demonstrates a minor influence on the energy of emission but affects dramatically emission efficiency and lifetime. The chloride complex displays dual (fluorescence and phosphorescent) luminescence due to labile coordination of an N-coordinated functionality that produces a dangling aromatic fragment, which gives emission from a singlet excited state. [ABSTRACT FROM AUTHOR]

A novel flexible humidity sensor incorporating gold nanoparticles (Au NPs) and a trifunctional organosilica compound has been developed through the integration of sol–gel processing, free radical polymerization, and self-assembly techniques. The trifunctional organosilica was initially synthesized by modifying (3-mercaptopropyl)trimethoxysilane (thiol-MPTMS) with 3-(trimethoxysilyl)propyl methacrylate (vinyl-TMSPMA). Subsequently, a hydrophilic polyelectrolyte, [3(methacryloylamino)propyl]trimethyl ammonium chloride (MAPTAC), was grafted onto the MPTMS-TMSPMA gel. The Au NPs were assembled onto the thiol groups present in the MPTMS-TMSPMA-MAPTAC gel network. The compositional and microstructural properties of the Au NPs/MPTMS-TMSPMA-MAPTAC composite film were investigated utilizing Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The presence of thiol groups and mesoporous silica skeletons ensured the stability of the humidity-sensing film on the substrate under highly humid conditions, while the hydrophilic groups functioned as humidity-sensitive sites. This innovative humidity sensor demonstrated high sensitivity, acceptable linearity, minimal hysteresis, and rapid response time across a broad range of working humidity levels. Based on the complex impedance spectra analysis, hydronium ions (H3O+) were determined to govern the conductance process of the flexible humidity sensor. [ABSTRACT FROM AUTHOR]

Anthracene-based ligand L1 comprising an imine functionality and a tellurium (Te) donor moiety has been prepared. This ligand L1 has been characterized using 1H, 13C and 125Te NMR spectroscopic techniques. The novel palladium(II) complex 1 and ruthenium(II) complex 2 have been synthesized by reacting organotellurium ligand L1 and Na2PdCl4/[Ru p(cymene)Cl2]2, respectively. The Pd(II) complex 1 and Ru(II) complex 2 were characterized with high resolution mass spectrometry (HR-MS) and 125Te NMR spectra. The molecular structures of complexes 1 and 2 were authenticated with single crystal X-ray diffraction. Both the complexes are thermally stable, robust, and air and moisture insensitive. Palladium complex 1 exhibits nearly square planar geometry. The molecular structure of complex 2 has a pseudo-octahedral half sandwich piano-stool geometry around ruthenium. The catalytic activity of complex 1 has been explored for O-arylation of phenol, whereas the catalytic activity of complex 2 was explored for aldehyde to amide conversion. A variety of structurally different chloroarenes have been coupled with phenol employing 1 as a catalyst. A wide range of aldehydes containing different functional groups (viz. H, –Me, –NO2, F, OMe, Cl and Br at the para position) were readily converted into their corresponding amide by employing Ru(II) complex 2 as a catalyst in a reaction time of 12 hours. [ABSTRACT FROM AUTHOR]

Organoindium compounds of redox active 1,2‐benzenedithiolate and 2‐amidobenzenethiolate ligands were synthesized and tested for reactivity against mild oxidants. The reaction of Me3In and (NCN)InMe2 [NCN=2,6‐bis(dimethylaminomethy)phenyl] with 3,4‐toluenedithiol (H2tdt) at room temperature afforded [MeIn(tdt)(py)]2 (1) and (NCN)In(tdt) (2), respectively. A similar reaction of Me3In with 2‐aminobenzenethiol (H2abt) in toluene under reflux afforded [MeIn(abt)(py)]2 (3). The reaction of (NCN)InCl2 with one equivalent of Li2(abt) or two equivalents of Li(Habt) afforded the compounds [(NCN)In(abt)]⋅LiCl(thf)2 (4⋅LiCl(thf)2) and (NCN)In(Habt)2 (5), respectively. The X‐ray crystal structures of 1 and 3 are similar and show dimeric structures via μ‐S‐(tdt) and μ‐N‐(abt) ligands, respectively. Compounds 2 and 4 possess similar monomeric structures and tridentate NCN pincer ligands. DFT computational studies have been used to rationalize the observed solid‐state structures and discern the potential reactivity of compounds 1–4 against oxidants. The reaction of 1 and 2 with excess iodine resulted in loss of the 3,4‐toluenedithiolate ligand and the formation of the oligomeric disulfide [tdt]n, while 3 and 4 showed no reactivity under similar conditions. This contrasts the reactivity of previously reported organoindium o‐amidophenolate complexes which undergo oxidative addition of iodine to afford ligand‐centered radical species. [ABSTRACT FROM AUTHOR]

Cis-[MoVIO2(CH3-hptb)(MeOH)] (1) has been synthesized by the reaction of [MoVIO2(acac)2] and deferasirox [ICL670: 4-[3,5-bis(2-hydroxyphenyl)-1H-1,2,4-triazol-1-yl]benzoic acid, H3hptb, I] in 1:1 molar ratio in MeOH. Complex 1 has been characterized successfully by several spectral techniques, viz. FT-IR, UV–Vis, 1H and 13C NMR, elemental (CHN) and thermogravimetric analysis. The esterification of the carboxylic group of ligand was observed during the complexation process with molybdenum. The analogous heterogeneous complex [MoVIO2(hptb)(MeOH)]@APTMS-TiO2 (2) has been synthesized by immobilizing I on amine-functionalized TiO2, {[H2hptb]@APTMS-TiO2 (II)} and then reacting it with [MoVIO2(acac)2] in MeOH. Characterization of the immobilized complex was achieved through FT-IR, DRS, P-XRD, TEM, thermogravimetric analysis and MP-AES. Both the complexes have been utilized in synthesizing organobromine compounds through oxidative bromination of styrene in the presence of KBr, oxidant (30% aq. H2O2) and 70% aq. HClO4 at room temperature. With the formation of 2-bromo-1-phenylethane-1-ol and 1-phenylethane-1,2-diol under the optimized reaction conditions, 72 and 100% conversion of styrene was achieved in the presence of catalysts 1 and 2, respectively. The oxidative bromination of thymol with catalyst 2 provides 2-bromothymol (52%) and 2,4-dibromothymol (48%) with 100% conversion. Dioxidomolybdenum(VI) complex of ICL670 immobilized on amine-functionalized titania has been synthesized and used as a functional model of haloperoxidases for the oxidative bromination of thymol and styrene. [ABSTRACT FROM AUTHOR]

PurposeMAVERICC compared the efficacy and safety of modified leucovorin/5-fluorouracil/oxaliplatin plus bevacizumab (mFOLFOX6-BV) with leucovorin/5-fluorouracil/irinotecan plus bevacizumab (FOLFIRI-BV) in patients with previously untreated metastatic colorectal cancer (mCRC).Patients and Methods: MAVERICC was a global, randomized, open-label, phase II study. Primary objectives were to assess associations between (i) excision repair cross-complementing 1 (ERCC1) expression with progression-free survival (PFS), and (ii) plasma VEGF A (VEGF-A) with PFS in patients with previously untreated mCRC receiving mFOLFOX6-BV or FOLFIRI-BV. Before randomization, patients were stratified by tumoral ERCC1/β-actin mRNA expression level and region.ResultsOf 376 enrolled patients, 188 each received mFOLFOX6-BV and FOLFIRI-BV. PFS and overall survival (OS) were comparable between FOLFIRI-BV and mFOLFOX6-BV, with numerically higher PFS [HR = 0.79; 95% CI (confidence interval): 0.61-1.01; P = 0.06] and OS (HR = 0.76; 95% CI: 0.56-1.04; P = 0.09) observed for FOLFIRI-BV. In the high ERCC1 subgroup, PFS and OS were comparable between treatment groups (PFS, HR = 0.84; 95% CI: 0.56-1.26; P = 0.40; OS, HR = 0.80; 95% CI: 0.51-1.26; P = 0.33). Across treatment groups, high plasma VEGF-A levels (>5.1 pg/mL) were observed with shorter PFS (HR = 1.19; 95% CI: 0.93-1.53; P = 0.17) and significantly shorter OS (HR = 1.64; 95% CI: 1.20-2.24; P < 0.01) versus low levels (≤5.1 pg/mL). Safety findings for FOLFIRI-BV or mFOLFOX6-BV were comparable with those reported previously.ConclusionsFirst-line FOLFIRI-BV and mFOLFOX6-BV had comparable PFS and OS, similar to results in patients with high baseline tumor ERCC1 levels. There were no new safety signals with these bevacizumab-containing regimens.

Spin crossover (SCO) complexes have been extensively explored as bistable materials and recently used as molecular modules for the development of new multifunctional molecular magnetic materials. Herein, we present the synthesis, crystal structure, magnetic, and electrical properties of a mononuclear cobalt complex constructed by a halogen‐functionalized terpyridine derivative and organosulfonate. A complete and gradual spin transition with the T1/2=200 K was observed for the Co2+ ions through both the magnetic measurement and dynamic crystallographic experiments. Interestingly, considerable room temperature proton conductivity of 6.9×10−5 S cm−1 under 98% relative humidity was evidenced because of the presence of sulfonate‐assisted hydrogen‐bonded proton hopping pathways. The forgoing results not only provide an unprecedented proton‐conducting cobalt(II) SCO complex but also a promising way for the design and construction of bifunctional SCO molecular conductors via the incorporation of SCO transition and proton conduction. [ABSTRACT FROM AUTHOR]

Simple Summary: Colorectal cancer is the third most common cancer worldwide. The treatment of the advanced stages is based on poly-chemotherapies, including oxaliplatin. However, the development of resistance to chemotherapy is observed in 50% of cases, leading to treatment failures. A better understanding of the resistance mechanisms is therefore crucial to improve treatment efficiency and patient survival. In our previous work, showed that ROS production and the p38 MAPK pathway were strongly involved in resistance to oxaliplatin. In this study, we tested several chemotherapies and observed that only gemcitabine efficiently treated oxaliplatin-resistant cancer cells. Indeed, gemcitabine was able to induce apoptosis by inhibiting both the Akt and p38 MAPK pathways. Taken together, our results show that gemcitabine could be an interesting therapeutic option for patients with oxaliplatin-resistant tumors. Resistance to treatments is one of the leading causes of cancer therapy failure. Oxaliplatin is a standard chemotherapy used to treat metastatic colorectal cancer. However, its efficacy is greatly reduced by the development of resistances. In a previous study, we deciphered the mechanisms leading to oxaliplatin resistance and highlighted the roles played by ROS production and the p38 MAPK pathway in this phenomenon. In this report, we studied the effects of different chemotherapy molecules on our oxaliplatin-resistant cells to identify alternative treatments. Among all the studied molecules, gemcitabine was the only one to present a major cytotoxic effect on oxaliplatin-resistant cancer cells both in vivo and in vitro. However, the combination of oxaliplatin and gemcitabine did not present any major interest. Indeed, the study of combination efficiency using Chou and Talalay's method showed no synergy between oxaliplatin and gemcitabine. Using PamGene technology to decipher gemcitabine's effects on oxaliplatin-resistant cells, we were able to show that gemcitabine counteracts chemoresistance by strongly inhibiting the Akt and src/p38 MAPK pathways, leading to apoptosis induction and cell death. In view of these results, gemcitabine could be an interesting alternative therapy for patients with colorectal cancer not responding to oxaliplatin-based protocols such as FOLFOX. [ABSTRACT FROM AUTHOR]

The mixed‐ligand fluorophore‐labelled copper(II) complex aqua[2,4‐dioxo‐3‐azatricyclo[7.3.1.05,13]trideca‐1(12),5,7,9(13),10‐pentaen‐3‐olato‐κ2O2,O3](1,10‐phenanthroline‐κ2N,N′)copper(II) nitrate, [Cu(C12H6NO3)(C12H8N2)(H2O)]NO3·CH3OH or [Cu(L)(phen)(H2O)]NO3·CH3OH (where phen is 1,10‐phenanthroline and HL is N‐hydroxynaphthalene‐1,8‐dicarboximide), (1), was synthesized and structurally characterized. The structure of (1) was confirmed by single‐crystal X‐ray structure determination. The complex crystallized in the triclinic space group P. The geometry around the copper centre is distorted square pyramidal, with the apical position occupied by a water molecule. The complex is highly fluorescent in organic and aqueous solutions. It has good anticancer activity, with an IC50 value of 17 µM, which is almost five times greater than cisplatin (IC50 = 82 µM) under identical experimental conditions. [ABSTRACT FROM AUTHOR]

Two new copper(II) complexes [Cu(Boc–glycine)(2,2–bipyridyl) 2 ]NO 3 1 and [Cu(Boc–glycine)(1,10–phenanthroline) 2 ]NO 3 2 were prepared, and thoroughly characterized by multiple spectroscopic methods and SC X–ray diffraction studies. pBR322 plasmid DNA cleavage studies showed that the complexes induced single–strand cleavage of DNA at a low concentration of 20 µM and 15 µM which mediated via an oxidative mechanism. SOD memetic activity of the complexes was investigated by using NBT assay which confirmed the superoxide ion scavenging ability of 1. The cytotoxicity activity of complexes was evaluated against MCF–7, PC–3, and HCT–116 cancer cells and the complexes displayed exceptionally good cytotoxic response. [Display omitted] Two new copper(II) complexes [Cu(Boc–glycine)(2,2–bipyridyl) 2 ]NO 3 1 and [Cu(Boc–glycine)(1,10–phenanthroline) 2 ]NO 3 2 were prepared, and thoroughly characterized by multiple spectroscopic methods. The SC X–ray diffraction studies revealed that the complexes crystallized in triclinic (P 1 ¯) system with distorted square pyramidal and octahedral geometry in 1 and 2 , respectively. To predict the anticancer potential of the drug candidates 1 and 2 , binding studies with the ct–DNA were performed by using various complimentary biophysical methods. The drug candidates 1 and 2 interact strongly with DNA exhibiting 'hypochromic' effect in the absorbance bands at 300 nm implicating non–covalent intercalation binding mode that could be induced by the presence of strong recognition domain ligand (phen) which is known to 'wedge–in' in-between the bases of DNA helix. The intrinsic binding constant, K b values were quantified by employing Wolfe–Shimer equation, and were found to be 0.10(±0.14) × 105 M−1 and 1.53 × 106(±0.1) M−1, respectively, showing higher binding propensity of 2 as compared to 1. pBR322 plasmid DNA cleavage studies of the complexes 1 and 2 showed that the complexes induced single–strand cleavage of DNA at a low concentration of 20 µM and 15 µM which mediated via an oxidative mechanism. The cytotoxicity activity of complexes was evaluated against MCF–7, PC–3, and HCT–116 cancer cells and the complexes displayed exceptionally good cytotoxicity against the tested cell lines (1 , HCT–116:IC 50 = 0.6 ± 0.02 μM and 2 , MCF–7:IC 50 = 1.91 ± 0.1 μM). [ABSTRACT FROM AUTHOR]

BackgroundAdding modified FOLFOX6 (folinic acid, fluorouracil, and oxaliplatin) after chemoradiotherapy and lengthening the chemoradiotherapy-to-surgery interval is associated with an increase in the proportion of rectal cancer patients with a pathological complete response.ObjectiveThe purpose of this study was to analyze disease-free and overall survival.DesignThis was a nonrandomized phase II trial.SettingsThe study was conducted at multiple institutions.PatientsFour sequential study groups with stage II or III rectal cancer were included.InterventionAll of the patients received 50 Gy of radiation with concurrent continuous infusion of fluorouracil for 5 weeks. Patients in each group received 0, 2, 4, or 6 cycles of modified FOLFOX6 after chemoradiation and before total mesorectal excision. Patients were recommended to receive adjuvant chemotherapy after surgery to complete a total of 8 cycles of modified FOLFOX6.Main outcome measuresThe trial was powered to detect differences in pathological complete response, which was reported previously. Disease-free and overall survival are the main outcomes for the current study.ResultsOf 259 patients, 211 had a complete follow-up. Median follow-up was 59 months (range, 9-125 mo). The mean number of total chemotherapy cycles differed among the 4 groups (p = 0.002), because one third of patients in the group assigned to no preoperative FOLFOX did not receive any adjuvant chemotherapy. Disease-free survival was significantly associated with study group, ypTNM stage, and pathological complete response (p = 0.004,

Purpose: Matrix metalloproteinase-9 (MMP9) is implicated in protumorigenic processes. Andecaliximab (GS-5745, a monoclonal antibody targeting MMP9) was evaluated as monotherapy and in combination with mFOLFOX6.Patients and Methods: Three dosages of andecaliximab monotherapy [200, 600, and 1800 mg i.v. every 2 weeks (q2w)] were investigated in patients with advanced solid tumors (n = 13 in a 3+3 design). After determining a recommended dose, patients with advanced HER2-negative gastric/gastroesophageal junction (GEJ) adenocarcinoma (n = 40) received 800 mg andecaliximab + mFOLFOX6 q2w. Pharmacokinetics, pharmacodynamics, safety, and efficacy were assessed.Results: Andecaliximab monotherapy demonstrated no dose-limiting toxicity (DLT) in any cohort, displaying target-mediated drug disposition at the lowest dose (200 mg) and linear pharmacokinetics at higher doses. Based on target engagement, recommended doses for further study are 800 mg q2w or 1,200 mg q3w. Maximal andecaliximab target binding, defined as undetectable andecaliximab-free MMP9 in plasma, was observed in the gastric/GEJ adenocarcinoma cohort. We observed no unusual toxicity, although there were four deaths on study not attributed to andecaliximab treatment. In first-line patients (n = 36), median progression-free survival (PFS) was 9.9 months [95% confidence interval (CI), 5-13.9 months], and the overall response rate (ORR) was 50%. Among all patients (n = 40), median PFS was 7.8 (90% CI, 5.5-13.9) months, and ORR was 48%, with a median duration of response of 8.4 months.Conclusions: Andecaliximab monotherapy achieved target engagement without DLT. Andecaliximab + mFOLFOX6 showed encouraging clinical activity without additional toxicity in patients with HER2-negative gastric/GEJ adenocarcinoma. A phase III study evaluating mFOLFOX6 ± andecaliximab in this setting is ongoing. Clin Cancer Res; 24(16); 3829-37. ©2018 AACR.

Purpose Treatment of oropharyngeal squamous cell carcinoma (OPSCC) is evolving toward risk-based modification of therapeutic intensity, which requires patient-specific estimates of overall survival (OS) and progression-free survival (PFS). Methods To develop and validate nomograms for OS and PFS, we used a derivation cohort of 493 patients with OPSCC with known p16 tumor status (surrogate of human papillomavirus) and cigarette smoking history (pack-years) randomly assigned to clinical trials using platinum-based chemoradiotherapy (NRG Oncology Radiation Therapy Oncology Group [RTOG] 0129 and 0522). Nomograms were created from Cox models and internally validated by use of bootstrap and cross-validation. Model discrimination was measured by calibration plots and the concordance index. Nomograms were externally validated in a cohort of 153 patients with OPSCC randomly assigned to a third trial, NRG Oncology RTOG 9003. Results Both models included age, Zubrod performance status, pack-years, education, p16 status, and T and N stage; the OS model also included anemia and age × pack-years interaction; and the PFS model also included marital status, weight loss, and p16 × Zubrod interaction. Predictions correlated well with observed 2-year and 5-year outcomes. The uncorrected concordance index was 0.76 (95% CI, 0.72 to 0.80) for OS and 0.70 (95% CI, 0.66 to 0.74) for PFS, and bias-corrected indices were similar. In the validation set, OS and PFS models were well calibrated, and OS and PFS were significantly different across tertiles of nomogram scores (log-rank P = .003;< .001). Conclusion The validated nomograms provided useful prediction of OS and PFS for patients with OPSCC treated with primary radiation-based therapy.

The attractive challenge in green chemistry is exploring novel heterogeneous catalyst system for catalyst-controlled product selectivity for oxidation of olefins. Hence, we proposed efficient and green catalytic methods for the selective synthesis of aldehydes and ketones, the selectivity of the reaction is exclusively dependent on the metals from the catalyst. A series of novel glycosyl pyridyl triazole-platinum (GPT-Pt) complex have been successfully synthesized and fully characterized for the first time. The GPT-Pt catalysts have been applied in the selective oxidative cleavage of alkenes to yield the corresponding aldehydes in the presence of H2O2 as an oxidant in water. With GPT-Pd as the catalyst, the oxidation reaction give the ketones as the main products. Moreover, the catalysts were recovered and reused six times without significant yield decrease. Novel glycosyl pyridyl triazole-platinum (GPT-Pt) complex have been successfully synthesized.The selective synthesis of aldehydes or ketones is exclusively dependent on the metals from the catalyst. Moreover, the catalysts can be separated and reused at least six times with superior activity. [ABSTRACT FROM AUTHOR]