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The development of highly efficient and ultrastable electrocatalysts for hydrogen generation from water/real seawater faces huge challenges. Herein, porous carbon-supported amorphous RuPt nanoclusters (Ru5.67Pt/PC) achieve mass activities of 42.28/10.93 A mgPt−1 and ultralong cycling stability in alkaline water/seawater because of the unique cluster structure and atomic Ru–Pt dual sites. [ABSTRACT FROM AUTHOR]

Engineering effective bifunctional electrocatalysts that outperform the benchmark Pt/C for direct methanol proton exchange membrane fuel cells is desired and challenging. Here, we designed H-PtCu/PtL OH catalysts with a sub-nanometer Pt(111) shell layer featuring Cu- and Co-vacancies, which exhibited high activity in acidic oxygen reduction and methanol oxidation reactions. [ABSTRACT FROM AUTHOR]

1 at% Ce3+-doped Gd3Ga2Al3O12 (GGAG) single crystals were grown by an optical floating zone (OFZ) method and a traveling solvent floating zone (TSFZ) method. To reveal their structure and chemical composition homogeneity, X-ray diffraction (XRD) and high-resolution inductively coupled plasma atomic emission spectrometry (ICP-AES) were conducted on the as-grown Ce:GGAG crystals at 4 different positions along the growth direction. Compared with the Ce:GGAG crystals grown by the OFZ method (Ce:GGAG-OFZ), the Ce:GGAG crystals grown by the TSFZ method (Ce:GGAG-TSFZ) presented better Ce3+ distribution homogeneity which varied from 0.21 to 0.29 at%. However, the segregation coefficient of Ce3+ in Ce:GGAG-OFZ was found to be higher than that in Ce:GGAG-TSFZ, revealing a different solidification rate between them. The comparison study shows that the photoluminescence (PL) intensity of Ce:GGAG-TSFZ is about twice higher than that of Ce:GGAG-OFZ and the maximum light yield (LY) of 35 340 photons per MeV also occurs in the former. Trap depths were measured to be 0.70 eV and 0.98 eV by TL glow curves. The LY value of Ce:GGAG-TSFZ along the growth direction fluctuated to a lesser extent with respect to that of Ce:GGAG-OFZ; the latter decreases gradually along the growth direction. It is concluded that the TSFZ method helps to improve the homogeneity of crystal composition when growing crystals with multiple compositions or incongruent compounds. [ABSTRACT FROM AUTHOR]

Metallene is receiving continuous attention because of its unique properties in electrocatalysis. Herein, we report a new class of three-dimensional (3D) Cr-doped Pd metallene nanoribbon (PdCr MNR) assembly. The 3D PdCr MNR was about 4 or 5 atomic layers thick with high-density low-coordinated Pd sites and abundant defects. The 3D PdCr MNR/C exhibited significantly enhanced oxygen reduction reaction and formic acid oxidation reaction compared with the commercial Pt/C and Pd/C and long-term durability. This work introduces a new member in the class of the metallene family, and this novel material is a promising bifunctional electrocatalyst for practical direct methanol/formic acid fuel cell devices. [ABSTRACT FROM AUTHOR]

Protein–ligand interactions are crucial in many biochemical processes and biomedical applications, yet accurately calculating the binding free energy of the interactions still remains challenging. In this work, we systematically investigate the performance of a generic force field GFN-FF and some semi-empirical quantum mechanical (SQM) methods (GFNn, n = 0, 1, 2) in terms of the accuracy of the calculated binding free energy. It is found that the performance of the GFN-FF method is quite good in a neutral-ligand system since the Pearson correlation coefficient (rp) is 0.70 and the mean absolute error (MAE) is 5.49 kcal mol−1. However, it may fail in a charged-ligand system (the MAE is 18.98 kcal mol−1). Moreover, we also propose a cluster model (i.e., truncating the protein at a given cutoff) along with the SQM method in the GFN family. Importantly, the GFN2-xTB shows the best performance among the SQM methods (the MAE is 4.91 kcal mol−1 and 10.25 kcal mol−1 in the neutral-ligand and charged-ligand systems, respectively), much better than GFN-FF in the charged-ligand system. Notably, the computing cost of the GFN2-xTB in the appropriate cluster model is even lower than that of the GFN-FF (in the entire complex). The present study sheds some light on the potential power of the GFN family in the efficient calculation of the binding free energy in bio-systems. [ABSTRACT FROM AUTHOR]

Histone deacetylase 6 (HDAC6) can deacetylate many substrates, including α-tubulin, cortactin, and HSP90α. This makes HDAC6 an interesting, emerging target. In this study, we selected 52 benzohydroxamate-based compounds and conducted 3D-QSAR studies using CoMFA and CoMSIA models. The results showed that CoMFA (n = 9; q2 = 0.556; r2 = 0.998) and CoMSIA (n = 9; q2 = 0.656; r2 = 0.996) have robust stability and predictability. The contour maps of the steric field, hydrophobic field, and hydrogen-bond donor field revealed the modified regions of these compounds. Subsequently, molecular docking was used to explore the docking mode of compounds and receptors. Based on these results, we designed 11 new benzohydroxamate-based compounds and predicted their activity and ADME/T properties. The results indicated that these compounds have strong pharmaceutical properties, and MD simulation analysis confirmed that Asp742 and His610 in the active site played a key role in this. Overall, these results serve as an important reference for the discovery and design of new HDAC6 inhibitors. [ABSTRACT FROM AUTHOR]

Pt is the most active anode electrocatalyst for the oxidation of methanol in direct methanol fuel cells (DMFCs); however, its weak resistance to CO or CO-like species poisoning has been a matter of great concern. Therefore, the development of a highly durable anode Pt-based electrocatalyst is indispensable for large-scale application of DMFCs. Here, we demonstrate that a CO-free pathway, 6-electron full electrooxidation of methanol, is realized in highly dispersed Cu-doped PtBi alloy-phase nanocrystals by combining nuclear magnetic resonance (NMR) spectroscopy and in situ Fourier transform infrared (FTIR) spectroscopy analysis. A mass activity (MA) of 5.25 A mgPt−1 and durability for 30 hours without current decay are obtained for the PtBiCu nanoalloys. The abundant surface defects, downshift of the Pt d-band center and the dual active site of "Pt–Bi" and "Pt–Cu" endow the PtBiCu nanoalloys with faster methanol oxidation kinetics, thus enhancing activity and durability. This work provides a new strategy to synthesize alloy-phase PtBiCu nanocrystals by crystal phase transition as a highly efficient and durable anode electrocatalyst for DMFCs. [ABSTRACT FROM AUTHOR]

A silver-mediated phosphorylation/cyclization of N-allylbenzamides with phosphine oxides for the synthesis of phosphoryl-substituted dihydroisoquinolones was developed. This protocol features broad substrate scope, experimental simplicity, high efficiency, step-economy, and facile scalability. [ABSTRACT FROM AUTHOR]

Ascorbic acid plays a crucial role in biochemical processes as a scavenger for preventing oxidative damage. Herein, a sensitive and selective fluorescent biosensor for the detection of ascorbic acid was proposed based on green-emission fluorescent silicon nanoparticles (SiNPs) and bovine serum albumin (BSA) templated-MnO2 nanosheets. Green-emission fluorescent SiNPs have been synthesized by a facile one-pot reduction reaction at room temperature by using DAMO and 3-hydroxytyramine hydrochloride as the silicon source and the reactants, respectively. The fluorescence of the SiNPs could be effectively quenched by MnO2 nanosheets. When ascorbic acid is introduced, the MnO2 nanosheets are reduced to Mn2+ ions by ascorbic acid, resulting in the fluorescence recovery of SiNPs. This sensing system exhibits a good linear range for ascorbic acid detection from 1 to 400 μM with a detection limit of 0.102 μM. Meanwhile, the detection system also exhibits high selectivity against other possible co-existing species. The present sensor was successfully applied for the detection of ascorbic acid in a commercially available vitamin C supplement, suggesting this sensing system holds great potential in food safety and disease diagnosis. [ABSTRACT FROM AUTHOR]

The first aromatic quaternary ammonium-group-containing [FeFe]H2ase models have been prepared by a simple and convenient two-step method in high yields. Thus, on the basis of preparation of the N-pyridylazadiphosphine-bridged diiron complex (μ-PDT)Fe2(CO)4[μ-3-(Ph2P)2NC5H4N] (A) by CO substitution of parent complex (μ-PDT)Fe2(CO)6 with N-pyridylazadiphosphine 3-(Ph2P)2NC5H4N in refluxing xylene, further quaternization of the pyridyl N atom in complex A with electrophile 1,3-propanesultone, 1,3,2-dioxathiolane-2,2-dioxide, or 4-bromobutyric acid in refluxing MeCN afforded the pyridyl quaternary ammonium-group-containing models (μ-PDT)Fe2(CO)4[μ-3-(Ph2P)2NC5H4NR] (1, R = (CH2)3SO3; 2, R = (CH2)2OSO3) and (μ-PDT)Fe2(CO)4[μ-3-(Ph2P)2NC5H4N(CH2)3CO2H]Br (3). Similarly, the N-pyridylmethylazadiphosphine-bridged diiron complex (μ-PDT)Fe2(CO)4[μ-3-(Ph2P)2NCH2C5H4N] (B) could be prepared by CO substitution of parent complex (μ-PDT)Fe2(CO)6 with N-pyridylmethylazadiphosphine 3-(Ph2P)2NCH2C5H4N in refluxing xylene, while further quaternization of the pyridylmethyl N atom in complex B with 1,3-propanesultone and 3-bromo-1-propanol in MeCN at reflux resulted in formation of the pyridylmethyl quaternary ammonium-group-containing models (μ-PDT)Fe2(CO)4[μ-3-(Ph2P)2NCH2C5H4N(CH2)3SO3] (4) and (μ-PDT)Fe2(CO)4[μ-3-(Ph2P)2NCH2C5H4N(CH2)3OH]Br (5), respectively. All new complexes A, B, and 1–5 were characterized by elemental analysis and various spectroscopies, while the molecular structures of complexes A, B, 2 and 5 were further confirmed by X-ray crystallography. The electrochemical study on hydrophilic models 1 and 3 in MeCN and the MeCN/H2O mixed solvent indicated that the reduction potentials were shifted to less-negative potentials as the water content increased; such an observation implies that both 1 and 3 are easily reduced in the mixed MeCN/H2O solvent than in MeCN. In addition, the electrocatalytic study demonstrated that both 1 and 3 can serve as electrocatalysts for H2 production from acetic acid with higher icat/ip and TONs in MeCN/H2O than in MeCN. [ABSTRACT FROM AUTHOR]

The difference in the micro-dynamics mechanism between aromatic nylon and aliphatic nylon during water absorption was studied to explore the reason for the significantly smaller decline of barrier performance of poly(m-xylene adipamide) (MXD6) film than that of polyamide 6 (PA6) film under high humidity. Attenuated total reflection (ATR) FTIR, combined with scaling moving-window 2D correlation spectroscopy (scaling-MW2D) and generalized 2D correlation analysis, was used. The scaling-MW2D confirmed that the water absorption of MXD6 comprises two processes, designated process I (2.0–12.0 min) and process II (12.0–27.0 min). According to the sequential order of the functional groups’ movement obtained from the generalized 2D correlation analysis, processes I and II undergo three and two steps, respectively. Process I is the process of water plasticizing MXD6, which primarily consists of hydrophilic groups forming hydrogen bonds with water molecules and the hydration of hydrophobic groups. Process II is the strong crystallization of MXD6 induced by water molecules, entailing the generation of the double hydrogen bond and the rearrangement of hydrophilic groups into the crystal lattice. However, for PA6, the results confirmed that its water absorption only had a single process with two steps, which was actually the plasticization of PA6 macromolecular chains by water molecules. Therefore, the reason for the barrier performance decline of the MXD6 film being significantly smaller than that of the PA6 film is that water molecules induced a large amount of new crystalline regions in the MXD6 matrix during plasticization. [ABSTRACT FROM AUTHOR]

As [FeFe]-hydrogenase models, the first thiodithiolate (TDT) ligand-containing μ-hydride complexes [(μ-TDT)Fe2(CO)4(PMe3)2(μ-H)]+Y− (2–7, Y = Cl, ClO4, PF6, BF4, CF3CO2, CF3SO3) have been prepared by protonation reactions of (μ-TDT)Fe2(CO)4(PMe3)2 (1) with the corresponding HY acids. While the protonation reactions are monitored by in situ1H and 31P{1H} NMR spectroscopy to show the isomer type and stability of 2–7, the structures of the isolated 2–7 are characterized by elemental analysis, spectroscopy and for some of them by X-ray crystallography. Although the H/D exchange of μ-hydride complex 7 (Y = CF3SO3) with D2 or D2O has been proved not to occur under the studied conditions, the H/D exchange of 7 with DCl gives the μ-deuterium complex [(μ-TDT)Fe2(CO)4(PMe3)2(μ-D)]+[CF3SO3]− (8) in a nearly quantitative yield. To our knowledge, 8 is the first crystallographically characterized μ-deuterium-containing butterfly [2Fe2S] complex produced by H/D exchange reaction. [ABSTRACT FROM AUTHOR]

A mitochondria-targetable fluorescence probe, methyl(4-hydroxyphenyl)amino-substituted pyronin (1), was exploited, which could highly selectively sense peroxynitrite (ONOO−) within seconds. [ABSTRACT FROM AUTHOR]

A new efficient and highly enantioselective direct asymmetric hydro-genation of α-keto acids employing the Ir/SpiroPAP catalyst under mild reaction conditions has been developed. This method might be feasible for the preparation of a series of chiral α-hydroxy acids on a large scale. [ABSTRACT FROM AUTHOR]

A but-3-yn-2-one-based 7-diethylaminocoumarin dye was exploited as a fluorescent probe to specifically detect Cys over Hcy/GSH in pure PBS buffer. The probe itself is nonfluorescent due to the donor-excited photoinduced electron transfer (d-PET) process. The Cys-induced Michael addition–rearrangement cascade reaction leads to an amino-substituted product 3a with strong fluorescence due to inhibiting C=C isomerization induced fluorescence quenching by a produced intramolecular N–H…O hydrogen bond. The Hcy (or GSH)-induced Michael addition reaction leads to a thiol-substituted product 2b (or 4), which lacks any intramolecular hydrogen-bonding interaction, and thus displays very poor fluorescence due to the efficient C=C isomerization induced fluorescence quenching. Even in the presence of Hcy (or GSH), the probe could also detect Cys with the obvious fluorescence enhancement. Assisted by using a laser scanning confocal microscope, we demonstrated that the probe could selectively image Cys in the human renal cell carcinoma 786-0 cells. [ABSTRACT FROM AUTHOR]

A rhodamine-inspired fluorescence dye (2) bearing 7-diethylaminocoumarin fluorophore was designed as a platform for the construction of an NIR and ratiometric fluorescent probe. The ring-open form of 2 shows NIR absorption and emission; however, its ring-closed form displays the visible absorption and emission because an intact 7-diethylaminocoumarin fluorophore was involved in the structure, providing the basis for an NIR and ratiometric fluorescent platform based on the spirocyclization-induced fluorescence switching mechanism. With the platform, we developed a novel NIR and ratiometric fluorescent probe R1, a thiolactone of 2, for sensing Hg2+, an environmentally and biologically concerned species. R1 displays an emission peak with the maximum at 480 nm, which is the typical emission of 7-diethylaminocoumarin moiety; however, upon addition of Hg2+ ions, the emission intensity at 480 nm gradually decreased with the simultaneous appearance of a new NIR emission band centred at 695 nm. Thus, the Hg2+-promoted ratiometric fluorescence response can be realized. The high selectivity towards Hg2+ over various cations and the high stability in a wide pH range of 1–12 indicate its potential for applications in biological systems. The subsequent cell imaging experiment revealed that R1 is cell permeable, and could be employed for ratiometric fluorescence imaging of Hg2+ in living cells. [ABSTRACT FROM AUTHOR]

A novel strategy for the determination of oxalate anions was successfully established using a copper ion and pyrocatechol violet (PV) ensemble. The sensor ensemble can discriminate oxalate over other common anions including F−, Cl−, I−, Br−, HPO42−, PO43−, AcO−, CO32−, SO42−, ClO4−, P2O74−, S2−(deposited by Ag), CN−(shielded by Fe3) and can detect oxalate at low microgram levels in quasi-physiological aqueous solutions. The detection of the oxalate anion gives rise to a rapid observable visual color change from blue to yellow. [ABSTRACT FROM AUTHOR]

A fluorescent turn-on probe for H2S was exploited based on a H2S-induced substitution–cyclization cascade reaction towards the bis-electrophilic centers of a new H2S trap group 2-(iodomethyl)benzoate. [ABSTRACT FROM AUTHOR]

A coumarin-hemicyanine dye 1 was reported for ratiometric fluorescent detection of SO2 derivatives HSO3- and SO32- based on a novel addition-rearrangement cascade reaction. [ABSTRACT FROM AUTHOR]

A coumarin−hemicyanine dye 1 was reported for ratiometric fluorescent detection of SO2 derivatives HSO3− and SO32− based on a novel addition-rearrangement cascade reaction. [ABSTRACT FROM AUTHOR]

A new ratiometric fluorescent cyanide probe was developed based on the nucleophilic attack of CN−toward the indolium group of a hybrid coumarin–hemicyanine dye, by which high selectivity as well as large emission shift could be achieved. [ABSTRACT FROM AUTHOR]

High-selectivity, uniform three-dimensional (3D) flower-like bismuth telluride (Bi2Te3) nanocrystals consisting of few-quintuple-layer nanoplatelets with a thickness down to 4.5 nm were synthesized for the first time by a facile, one-pot polyol method with acetic acid as the structure-director. Micrometre-sized 2D films and honeycomb-like spheres can be obtained using the uniform 3D Bi2Te3nanocrystals as building blocks. [ABSTRACT FROM AUTHOR]

A coumarin-based thiol probe featuring the 1,4-addition reaction of thiols to nitroolefin was reported. The molecular probe exhibited higher selectivity toward biothiols (Cys, Hcy and GSH) than other amino acids. [ABSTRACT FROM AUTHOR]

A Pt nanoparticle netlike-assembly (Pt-NNA) synthesized through a facile hydrothermal method, with high specific surface area and large overall size, exhibits much higher durability and 2.9 times higher mass activity for oxygen reduction reaction than commercial Pt black catalyst. [ABSTRACT FROM AUTHOR]

Novel anisotropic hybrid particles with various morphologies have been synthesized by radiation miniemulsion polymerization for the first time. [ABSTRACT FROM AUTHOR]

The first aromatic quaternary ammonium-group-containing [FeFe]H2ase models have been prepared by a simple and convenient two-step method in high yields. Thus, on the basis of preparation of the N-pyridylazadiphosphine-bridged diiron complex (μ-PDT)Fe2(CO)4[μ-3-(Ph2P)2NC5H4N] (A) by CO substitution of parent complex (μ-PDT)Fe2(CO)6 with N-pyridylazadiphosphine 3-(Ph2P)2NC5H4N in refluxing xylene, further quaternization of the pyridyl N atom in complex A with electrophile 1,3-propanesultone, 1,3,2-dioxathiolane-2,2-dioxide, or 4-bromobutyric acid in refluxing MeCN afforded the pyridyl quaternary ammonium-group-containing models (μ-PDT)Fe2(CO)4[μ-3-(Ph2P)2NC5H4NR] (1, R = (CH2)3SO3; 2, R = (CH2)2OSO3) and (μ-PDT)Fe2(CO)4[μ-3-(Ph2P)2NC5H4N(CH2)3CO2H]Br (3). Similarly, the N-pyridylmethylazadiphosphine-bridged diiron complex (μ-PDT)Fe2(CO)4[μ-3-(Ph2P)2NCH2C5H4N] (B) could be prepared by CO substitution of parent complex (μ-PDT)Fe2(CO)6 with N-pyridylmethylazadiphosphine 3-(Ph2P)2NCH2C5H4N in refluxing xylene, while further quaternization of the pyridylmethyl N atom in complex B with 1,3-propanesultone and 3-bromo-1-propanol in MeCN at reflux resulted in formation of the pyridylmethyl quaternary ammonium-group-containing models (μ-PDT)Fe2(CO)4[μ-3-(Ph2P)2NCH2C5H4N(CH2)3SO3] (4) and (μ-PDT)Fe2(CO)4[μ-3-(Ph2P)2NCH2C5H4N(CH2)3OH]Br (5), respectively. All new complexes A, B, and 1-5 were characterized by elemental analysis and various spectroscopies, while the molecular structures of complexes A, B, 2 and 5 were further confirmed by X-ray crystallography. The electrochemical study on hydrophilic models 1 and 3 in MeCN and the MeCN/H2O mixed solvent indicated that the reduction potentials were shifted to less-negative potentials as the water content increased; such an observation implies that both 1 and 3 are easily reduced in the mixed MeCN/H2O solvent than in MeCN. In addition, the electrocatalytic study demonstrated that both 1 and 3 can serve as electrocatalysts for H2 production from acetic acid with higher icat/ip and TONs in MeCN/H2O than in MeCN.

As [FeFe]-hydrogenase models, the first thiodithiolate (TDT) ligand-containing μ-hydride complexes [(μ-TDT)Fe2(CO)4(PMe3)2(μ-H)](+)Y(-) (2-7, Y = Cl, ClO4, PF6, BF4, CF3CO2, CF3SO3) have been prepared by protonation reactions of (μ-TDT)Fe2(CO)4(PMe3)2 (1) with the corresponding HY acids. While the protonation reactions are monitored by in situ(1)H and (31)P{(1)H} NMR spectroscopy to show the isomer type and stability of 2-7, the structures of the isolated 2-7 are characterized by elemental analysis, spectroscopy and for some of them by X-ray crystallography. Although the H/D exchange of μ-hydride complex 7 (Y = CF3SO3) with D2 or D2O has been proved not to occur under the studied conditions, the H/D exchange of 7 with DCl gives the μ-deuterium complex [(μ-TDT)Fe2(CO)4(PMe3)2(μ-D)](+)[CF3SO3](-) (8) in a nearly quantitative yield. To our knowledge, 8 is the first crystallographically characterized μ-deuterium-containing butterfly [2Fe2S] complex produced by H/D exchange reaction.

A new efficient and highly enantioselective direct asymmetric hydrogenation of α-keto acids employing the Ir/SpiroPAP catalyst under mild reaction conditions has been developed. This method might be feasible for the preparation of a series of chiral α-hydroxy acids on a large scale.

Composition-tunable PdPt bimetallic nanoalloys with sub-2.0 nm islands have been successfully synthesized through a facile aqueous solution approach. Among them, the Pd50Pt50 nanoalloys exhibit considerably higher catalytic activity and durability for methanol oxidation reaction than commercial Pt black.

A fluorescent turn-on probe for H2S was exploited based on a H2S-induced substitution-cyclization cascade reaction towards the bis-electrophilic centers of a new H2S trap group 2-(iodomethyl)benzoate.

A rhodamine-inspired fluorescence dye (2) bearing 7-diethylaminocoumarin fluorophore was designed as a platform for the construction of an NIR and ratiometric fluorescent probe. The ring-open form of 2 shows NIR absorption and emission; however, its ring-closed form displays the visible absorption and emission because an intact 7-diethylaminocoumarin fluorophore was involved in the structure, providing the basis for an NIR and ratiometric fluorescent platform based on the spirocyclization-induced fluorescence switching mechanism. With the platform, we developed a novel NIR and ratiometric fluorescent probe R1, a thiolactone of 2, for sensing Hg2+, an environmentally and biologically concerned species. R1 displays an emission peak with the maximum at 480 nm, which is the typical emission of 7-diethylaminocoumarin moiety; however, upon addition of Hg2+ ions, the emission intensity at 480 nm gradually decreased with the simultaneous appearance of a new NIR emission band centred at 695 nm. Thus, the Hg2+-promoted ratiometric fluorescence response can be realized. The high selectivity towards Hg2+ over various cations and the high stability in a wide pH range of 1–12 indicate its potential for applications in biological systems. The subsequent cell imaging experiment revealed that R1 is cell permeable, and could be employed for ratiometric fluorescence imaging of Hg2+ in living cells.

A coumarin-hemicyanine dye was reported for ratiometric fluorescent detection of SO2 derivatives HSO3(-) and SO3(2-) based on a novel addition-rearrangement cascade reaction.

A fluorescence turn-on probe for bisulfite has been developed by taking advantage of the specific reaction of bisulfite and aldehyde in combination with the hydrogen bond inhibited C=N isomerization mechanism. The practical value of this selective and sensitive fluorescent probe was confirmed by its application to detection of bisulfite in granulated sugar.

Platinum(II) anticancer drugs are among the most effective and often used chemotherapeutic drugs. In recent years, there has been increasing interest in exploiting inert platinum(IV) scaffolds as a prodrug strategy to mitigate the limitations of platinum(II) anticancer complexes. In this prodrug strategy, the axial ligands are released concomitantly upon intracellular reduction to the active platinum(II) congener, offering the possibility of conjugating bioactive co-drugs which may synergistically enhance cytotoxicity on cancer cells. Existing techniques of tethering bioactive molecules to the axial positions of platinum(IV) prodrugs suffer from limited scope, poor yields and low reliability. This report explores the applications of current chemoselective ligation chemistries to platinum(IV) anticancer complexes with the aim of addressing the aforementioned limitations. Here, we describe the synthesis of a platinum(IV) complex bearing an aromatic aldehyde functionality and explored the scope of imine ligation with various hydrazide and aminooxy functionalized substrates. As a proof of concept, we tethered a six sequence long peptide mimetic (AMVSEF) of the anti-inflammatory protein, ANXA1.

A new ratiometric fluorescent cyanide probe was developed based on the nucleophilic attack of CN(-) toward the indolium group of a hybrid coumarin-hemicyanine dye, by which high selectivity as well as large emission shift could be achieved., (This journal is © The Royal Society of Chemistry 2011)