3D Cyclophane for the Selective Conversion of Epoxide to Cyclic Carbonate.

A novel three-dimensional (3D) cyclophane molecule 1 was synthesized and fully characterized. Cyclophane 1, which can form a N heterocyclic carbene, was tested for conversion of certain epoxides (3-6) [scheme 2] to cyclic carbonates in the presence of CO2. Propylene oxide (3) was found to have more reactivity with cyclophane 1 compared to the other epoxides. The theoretical calculations based on N,N'-disubstituted imidazol(in)ium-2-carboxylates derived from N,N' disubstituted imidazole as the source of N-heterocyclic carbene show lower activation energy in the case of the reactivity of epoxides 5 and 6 as compared to 3 and 4. However, cyclophane 1, which possesses a 3D geometry, can form the open intermediate with CO2 and propylene oxide more feasibly than the other three epoxides, which have larger sizes as compared to propylene oxide. Hence, the reaction of propylene oxide, CO2, and cyclophane 1 can follow the mechanistic path 1, whereas the epoxides 4-6 can follow a different mechanistic path 2. Cyclophane 1 is the first example of a cyclophane to act as an organocatalyst for the conversion of CO2 and epoxide to cyclic carbonate via the N heterocyclic carbene pathway.

Rapid reconstruction of highly undersampled, non-Cartesian real-time cine k-space data using a perceptual complex neural network (PCNN).

Highly accelerated real-time cine MRI using compressed sensing (CS) is a promising approach to achieve high spatio-temporal resolution and clinically acceptable image quality in patients with arrhythmia and/or dyspnea. However, its lengthy image reconstruction time may hinder its clinical translation. The purpose of this study was to develop a neural network for reconstruction of non-Cartesian real-time cine MRI k-space data faster (<1 min per slice with 80 frames) than graphics processing unit (GPU)-accelerated CS reconstruction, without significant loss in image quality or accuracy in left ventricular (LV) functional parameters. We introduce a perceptual complex neural network (PCNN) that trains on complex-valued MRI signal and incorporates a perceptual loss term to suppress incoherent image details. This PCNN was trained and tested with multi-slice, multi-phase, cine images from 40 patients (20 for training, 20 for testing), where the zero-filled images were used as input and the corresponding CS reconstructed images were used as practical ground truth. The resulting images were compared using quantitative metrics (structural similarity index (SSIM) and normalized root mean square error (NRMSE)) and visual scores (conspicuity, temporal fidelity, artifacts, and noise scores), individually graded on a five-point scale (1, worst; 3, acceptable; 5, best), and LV ejection fraction (LVEF). The mean processing time per slice with 80 frames for PCNN was 23.7 ± 1.9 s for pre-processing (Step 1, same as CS) and 0.822 ± 0.004 s for dealiasing (Step 2, 166 times faster than CS). Our PCNN produced higher data fidelity metrics (SSIM = 0.88 ± 0.02, NRMSE = 0.014 ± 0.004) compared with CS. While all the visual scores were significantly different (P < 0.05), the median scores were all 4.0 or higher for both CS and PCNN. LVEFs measured from CS and PCNN were strongly correlated (R2 = 0.92) and in good agreement (mean difference = -1.4% [2.3% of mean]; limit of agreement = 10.6% [17.6% of mean]). The proposed PCNN is capable of rapid reconstruction (25 s per slice with 80 frames) of non-Cartesian real-time cine MRI k-space data, without significant loss in image quality or accuracy in LV functional parameters.

Bridging the Gap Between Computational Photography and Visual Recognition.

What is the current state-of-the-art for image restoration and enhancement applied to degraded images acquired under less than ideal circumstances? Can the application of such algorithms as a pre-processing step improve image interpretability for manual analysis or automatic visual recognition to classify scene content? While there have been important advances in the area of computational photography to restore or enhance the visual quality of an image, the capabilities of such techniques have not always translated in a useful way to visual recognition tasks. Consequently, there is a pressing need for the development of algorithms that are designed for the joint problem of improving visual appearance and recognition, which will be an enabling factor for the deployment of visual recognition tools in many real-world scenarios. To address this, we introduce the UG 2 dataset as a large-scale benchmark composed of video imagery captured under challenging conditions, and two enhancement tasks designed to test algorithmic impact on visual quality and automatic object recognition. Furthermore, we propose a set of metrics to evaluate the joint improvement of such tasks as well as individual algorithmic advances, including a novel psychophysics-based evaluation regime for human assessment and a realistic set of quantitative measures for object recognition performance. We introduce six new algorithms for image restoration or enhancement, which were created as part of the IARPA sponsored UG 2 Challenge workshop held at CVPR 2018. Under the proposed evaluation regime, we present an in-depth analysis of these algorithms and a host of deep learning-based and classic baseline approaches. From the observed results, it is evident that we are in the early days of building a bridge between computational photography and visual recognition, leaving many opportunities for innovation in this area.

A tri-metallic palladium complex with breast cancer stem cell potency.

A multi-nuclear, triangular-shaped palladium(ii) complex is shown to equipotently kill bulk cancer cells and cancer stem cells (CSCs) in the micromolar range. The palladium(ii) complex evokes CSC apoptosis by entering CSC nuclei and damaging genomic DNA.

Green Synthesis of Novel Polyesterurethane Materials from Epoxides and Carbon Dioxide by New Set of One-Dimensional Coordination Polymer Catalyst.

Two novel polyesterurethane materials, PEU1 and PEU2, were synthesized via nontoxic and isocyanate-free route by simple conversion of two epoxides 1,2-epoxy-3-phenoxy propane (2) and styrene epoxide (3) utilizing CO2. Epoxides 2 and 3 were converted to the respective cyclic carbonates 4 and 5 by a new set of cobalt-based catalyst 1a in the presence of 10 bar of CO2 and 80 °C temperature without using cocatalyst tetrabutylammonium bromide (TBAB). The mechanistic pathway of the catalysis reaction for the cycloaddition of epoxides with CO2 to generate the cyclic carbonates was investigated by several spectroscopic techniques and utilizing analogous zinc-based 1D coordination polymer 1b, which does not act as an efficient catalyst in the absence of TBAB. Cyclic carbonates 4 and 5 were converted to the respective polyesterurethanes PEU1 and PEU2 sequentially by first synthesizing the ring-opened diols 6 and 7 reacting with ethylenediamine and subsequently annealing the respective diols 6 and 7 at 120 °C in the presence of terepthalyl chloride and triethylamine. The polyesterurethanes PEU1 and PEU2 were characterized by multinuclear NMR and FTIR. PEU1 was also characterized by MALDI-TOF mass spectrometry. The thermal studies of PEU1 and PEU2 showed the stability up to 200-270 °C. The number-average and weight-average molecular weights were determined for PEU1 and PEU2 by GPC analysis. The weight-average molecular weight for PEU1 was found to be 5948 with a polydispersity of 1.1, and PEU2 showed the weight-average molecular weight as 4224 with a polydispersity of 1.06.

New Set of Multicomponent Crystals as Efficient Heterogeneous Catalysts for the Synthesis of Cyclic Carbonates.

Three new multicomponent crystals 1a-1c of Zn(II), Mn(II), and Co(II), respectively, were synthesized by the reaction of 2,6-bis(hydroxymethyl)pyridine, the respective metal salts, and sodium benzoate in a 1:1:2 ratio. One component of these multicomponent crystals 1a-1c is the dicationic 2,6-bis(hydroxymethyl)pyridine metal complex and the other component is the dianionic tetrabenzoate complex of the same metal. The complexes were fully characterized by single-crystal X-ray structure determination. The X-ray structure of these compounds 1a-1c reveals the formation of 1D supramolecular chain parallel to the crystallographic b axis via H-bonding interactions between the dicationic and dianionic parts of the respective compound. The Mn(II) (1b) and Co(II) (1c) complexes show antiferromagnetic coupling between the two associated metal centers via the H-bonding interaction pathway. All the three compounds 1a-1c were tested as heterogeneous catalytic systems for the successful conversion of epoxides to cyclic carbonates in solvent-free condition under approximately 10 bar of pressure of CO2 and temperature ranging between 60 and 80 °C along with tetrabutyl ammonium bromide acting as a cocatalyst. All the three compounds 1a-1c were found to have turnover number more than 1000 for the respective epoxides except for the conversion of cyclohexene oxide to cyclohexene carbonate.

A Triangular Platinum(II) Multinuclear Complex with Cytotoxicity Towards Breast Cancer Stem Cells.

The preparation of multinuclear metal complexes offers a route to novel anticancer agents and delivery systems. The potency of a novel triangular multinuclear complex containing three platinum atoms, Pt-3, towards breast cancer stem cells (CSCs) is reported. The trinuclear platinum(II) complex, Pt-3 exhibits selective toxicity towards breast CSCs over bulk breast cancer cells and non-tumorigenic breast cells. Remarkably, Pt-3 inhibits the formation, size, and viability of mammospheres to a better extent than salinomycin, an established CSC-potent agent, and cisplatin and carboplatin, clinically used platinum drugs. Mechanism of action studies show that Pt-3 effectively enters breast CSCs, penetrates the nucleus, induces genomic DNA damage, and prompts caspase-dependent apoptosis. To the best of our knowledge, Pt-3 is the first multinuclear platinum complex to selectively kill breast CSCs over other breast cell types.

Synthesis, characterization, and cytotoxic properties of mono- and di-nuclear cobalt(ii)-polypyridyl complexes.

We report the synthesis and characterisation of mono- and di-nuclear cobalt(ii) complexes (1-3) containing L1, a polypyridyl ligand with pyrazole moieties. DNA binding studies suggest that the mono-nuclear complex, 1, binds to DNA via the grooves prior to inducing oxidative DNA cleavage whereas the larger di-nuclear complexes, 2 and 3, bind to DNA via the grooves and through intercalation prior to inducing oxidative DNA cleavage. The cobalt(ii) complexes display micromolar potency towards U2OS (bone osteosarcoma), HepG2 (liver hepatocellular carcinoma), and GM05757 (normal human fibroblast) cells, comparable to clinically used platinum agents, cisplatin and carboplatin. The cellular mechanism of action studies show that the most effective cobalt(ii) complex, 2, enters U2OS cells, penetrates the nucleus, induces genomic DNA damage, and triggers caspase-dependent apoptosis in a p53-independent manner. This study highlights the potential of di-nuclear cobalt(ii) complexes as artificial oxidative metallonucleases and tangible cancer cell-potent agents.

Assembly of palladium(II) and platinum(II) metallo-rectangles with a guanosine-substituted terpyridine and study of their interactions with quadruplex DNA.

Two novel [2+2] metallo-assemblies based on a guanosine-substituted terpyridine ligand (1) coordinated to palladium(II) (2 a) and platinum(II) (2 b) are reported. These supramolecular assemblies have been fully characterized by NMR spectroscopy, ESI mass spectrometry and elemental analyses. The palladium(II) complex (2 a) has also been characterized by single crystal X-ray diffraction studies confirming that the system is a [2+2] metallo-rectangle in the solid state. The stabilities of these [2+2] assemblies in solution have been confirmed by DOSY studies as well as by variable temperature (1)H NMR spectroscopy. The ability of these dinuclear complexes to interact with quadruplex and duplex DNA was investigated by fluorescent intercalator displacement (FID) assays, fluorescence resonance energy transfer (FRET) melting studies, and electrospray mass spectrometry (ESI-MS). These studies have shown that both these assemblies interact selectively with quadruplex DNA (human telomeric DNA and the G-rich promoter region of c-myc oncogene) over duplex DNA, and are able to induce dimerization of parallel G-quadruplex structures.

Synthesis of a self-assembled copper(II) metallo-rectangle with a guanosine-substituted terpyridine.

The synthesis of a terpyridine-guanosine ligand and its reaction with copper(II) to yield a new [2 + 2] metallo-rectangle is reported. The metallo-rectangle was characterized by single crystal X-ray diffraction and the structure showed significant intramolecular π-π stacking interactions between the two terpyridine moieties of the molecule. This prompted us to investigate the magnetic properties of the new di-copper(II) assembly which displayed ferromagnetic interactions in the solid state.

Self-assembly of a Pd(II) neutral molecular rectangle via a new organometallic Pd(II)(2) molecular clip and oxygen donor linker.

Two components self-assembly of a Pd(4) neutral molecular rectangle driven by Pd-O bond coordination has been achieved and this pi-electron rich rectangle shows fluorescence quenching in presence of nitroaromatics, which are the chemical signatures of many explosives.

Self-assembled Pd(II) metallocycles using an ambidentate donor and the study of square-triangle equilibria.

The self-assembly reaction of a cis-blocked 90 degrees square planar metal acceptor with a symmetrical linear flexible linker is expected to yield a [4 + 4] self-assembled square, a [3 + 3] assembled triangle, or a mixture of these. However, if the ligand is a nonsymmetrical ambidentate, it is expected to form a complex mixture comprising several linkage isomeric squares and triangles as a result of different connectivities of the ambidentate linker. We report instead that the reaction of a 90 degrees acceptor cis-(dppf)Pd(OTf)(2) [where dppf = 1,1'-bis(diphenylphosphino)ferrocene] with an equimolar amount of the ambidentate unsymmetrical ligand Na-isonicotinate unexpectedly yields a mixture of symmetrical triangles and squares in the solution. An analogous reaction using cis-(tmen)Pd(NO(3))(2) instead of cis-(dppf)Pd(OTf)(2) also produced a mixture of symmetrical triangles and squares in the solution. In both cases the square was isolated as the sole product in the solid state, which was characterized by a single crystal structure analysis. The equilibrium between the triangle and the square in the solution is governed by the enthalpic and entropic contributions. The former parameter favors the formation of the square due to less strain in the structure whereas the latter one favors the formation of triangles due to the formation of more triangles from the same number of starting linkers. The effects of temperature and concentration on the equilibria have been studied by NMR techniques. This represents the first report on the study of square-triangle equilibria obtained using a nonsymmetric ambidentate linker. Detail NMR spectroscopy along with the ESI-mass spectrometry unambiguously identified the components in the mixture while the X-ray structure analysis determined the solid-state structure.

Design, synthesis, and characterizations of a series of Pt(4) macrocycles and fluorescent sensing of Fe3+/Cu2+/Ni2+ through metal coordination.

A Pt(II)(2) organometallic "clip" (1a) containing ethynyl functionality is synthesized. Multinuclear NMR and electrospray ionization mass spectrometry characterized this "clip", and the molecular structure was determined in an X-ray single-crystal diffraction study. A series of discrete molecular rectangles (2a-d) have been synthesized from this "clip" in combination with dipyridyl-based linear linkers (L(1-4)) by a metal-ligand coordination driven self-assembly approach [where L(1) = 4,4'-bipyridine, L(2) = trans-1,2-bis(4-pyridyl)ethylene, L(3) = N-(4-pyridyl)isonicotinamide, and L(4) = N,N'-bis(4-pyridylidene)ethylenediamine]. Rectangle 2d was designed using the imine-based ligand L(4) to make it a system composed of a fluorophore-receptor-fluorophore combination. The imine N(4) pocket is the receptor site, while the anthracene-based "clip" is the fluorophore. Complex 2d is fluorescent in nature and showed fluorescence quenching in solution upon the binding of hard transition metal ions (Fe(3+), Cu(2+), Ni(2+), and Mn(2+)) into the N(4) pocket. The nonresponsive nature of the fluorescence intensity upon the addition of soft metal ions (Zn(2+) and Cd(2+)) having d(10) configuration makes it a suitable sensor for transition metal ions. The fluorescence intensity of the Ni(2+) bound complex was regained when the metal was removed by a stronger chelating 2,2'-dipyridyl ligand.

Coordination driven self-assembly of four new molecular boats using a flexible imidazole-containing donor linker.

Using a metal-ligand coordination bonding approach, the self-assembly of four new metallamacrocycles from Pd(ii)-based 90 degrees acceptors and a diimidazole donor ligand 1,3-bis(imidazole-1-ylmethyl)-2,4,6-trimethylbenzene (L) has been achieved. The assemblies are characterized fully by NMR and electrospray ionization-mass spectroscopic (ESI-MS) analysis and in two cases the X-ray single-crystal structure analysis established the gross structures. The selective formation of a diimidazole-based linker (L) containing macrocycle [(en)Pd(micro-L)2Pd(en)]4+ from a 1 : 1 : 1 mixture of cis-Pd(en)(NO3)2, and 1,2-bis(4-pyridyl)ethane is also established. Measuring the binding constants established the stronger Pd- binding force compared to traditional Pd-N(pyridyl linker) interaction, which reveals the possibility of using imidazole donor ligands as potential linkers or even better ligands compared to the widely used pyridyl donor ligands in the construction of metal-based large supramolecular assemblies.

Self-assembly of a heterometallic molecular triangle using an ambidentate ligand and self-selection for a single linkage isomer.

Self-assembly and self-selection of a single linkage isomer of a mixed-metal molecular triangle with ferrocene functionality have been achieved using an ambidentate ligand, and the product was characterized by multinuclear NMR spectroscopy and X-ray single crystal structure determination.

Self-assembly of metal-organic hybrid nanoscopic rectangles.

The combination of an amide containing a linear ligand (L1) and an organometallic molecular "clip" (clip-1) leads to the self-assembly of a Pt4 nanoscopic framework representing the first example of a Pt-based molecular rectangle (rectangle-1) incorporating amide functionality. A complementary approach was also followed to prepare a Pd(II)-based molecular rectangle (rectangle-2) by reaction of a donor organic rigid clip (clip-2) and trans-(PEt3)2Pd(OTf)2 as the linear metal acceptor (L2). The Pd(II)-rectangle was characterised by multinuclear NMR and ESI-mass spectroscopy.

Self-assembly of molecular nanoball: design, synthesis, and characterization.

The design and self-assembly of two new flexible supramolecular nanoballs are described. These assemblies incorporate two flexible tritopic amide and ester building blocks and were prepared in excellent yields (96-97%) via coordination driven self-assembly. The first resulted from the reaction of 4 equiv of a new tritopic ester ligand N,N',N' '-tris(4-pyridylmethyl) trimesic ester and 3 equiv of C4 symmetric Pd(NO3)2. The second analogous structure was obtained by the self-assembly of a flexible N,N',N' '-tris(3-pyridylmethyl) trimesic amide and Pd(NO3)2. The assemblies were characterized with multinuclear NMR spectroscopy, electrospray ionization mass spectroscopy, elemental analysis, and TGA. Mass spectrometry along with NMR data and TEM view confirms the existence of the two assemblies. MM2 force field simulations of the cages showed a ball shape with the diameter of the inner cavity of about 2.1 and 1.8 nm for 2a and 2b, respectively, which were also corroborated by TEM analysis.