Control of Molecular Weight and Polydispersity of Hyperbranched Polymers Using a Reactive B(3) Core: A Single-Step Route to Orthogonally Functionalizable Hyperbranched Polymers

Molecular weight and polydispersity are two structural features of hyperbranched polymers that are difficult to control because of the statistical nature of the step-growth polycondensation of AB(2) type monomers; the statistical growth also causes the polydispersity index to increase with percent conversion (or molecular weight). We demonstrate that using controlled amounts of a specifically designed B(3) core, containing B-type functionality that are more reactive than those present in the AB(2) monomer, both the molecular weight and the polydispersity can be readily controlled; the PDI was shown to improve with increasing mole-fraction of the B(3) core while the polymer molecular weight showed an expected decrease. Incorporation of a ``clickable'' propargyl group in the B(3) core unit permitted the generation of a core-functionalizable hyperbranched polymer. Importantly, this clickable core, in combination with a recently developed AB(2) monomer, wherein the B-type groups are allyl ethers and A is an hydroxyl group, led to the generation of a hyperbranched polymer carrying orthogonally functionalizable core and peripheral groups, via a single-step melt polycondensation. Selective functionalization of the core and periphery using two different types of chromophores was achieved, and the occurrence of fluorescence resonance energy transfer (FRET) between the donor and acceptor chromophores was demonstrated.

Control of Molecular Weight and Polydispersity of Hyperbranched Polymers Using a Reactive B(3) Core: A Single-Step Route to Orthogonally Functionalizable Hyperbranched Polymers

Molecular weight and polydispersity are two structural features of hyperbranched polymers that are difficult to control because of the statistical nature of the step-growth polycondensation of AB(2) type monomers; the statistical growth also causes the polydispersity index to increase with percent conversion (or molecular weight). We demonstrate that using controlled amounts of a specifically designed B(3) core, containing B-type functionality that are more reactive than those present in the AB(2) monomer, both the molecular weight and the polydispersity can be readily controlled; the PDI was shown to improve with increasing mole-fraction of the B(3) core while the polymer molecular weight showed an expected decrease. Incorporation of a ``clickable'' propargyl group in the B(3) core unit permitted the generation of a core-functionalizable hyperbranched polymer. Importantly, this clickable core, in combination with a recently developed AB(2) monomer, wherein the B-type groups are allyl ethers and A is an hydroxyl group, led to the generation of a hyperbranched polymer carrying orthogonally functionalizable core and peripheral groups, via a single-step melt polycondensation. Selective functionalization of the core and periphery using two different types of chromophores was achieved, and the occurrence of fluorescence resonance energy transfer (FRET) between the donor and acceptor chromophores was demonstrated.

Nanosphere Templated Metallic Grating Assisted Enhanced Fluorescence

In this paper, enhanced fluorescence from a silver film coated nanosphere templated grating is presented. Initially, numerical simulation was performed to determine the plasmon resonance wavelength by varying the thickness of the silver film on top of a monolayer of 400 nm nanospheres. The simulation results are verified experimentally and tested for enhancing fluorescence from fluorescein isothiocyanate whose excitation wavelength closely matches with the plasmon resonance wavelength of the substrate with 100 nm silver film over nanosphere. The 12 times enhancement in the intensity is attributed to the local field enhancement in addition to the excitation of surface plasmon polaritons along the surface.

Fluorescence Enhancement Using Silver Nanotriangle Arrays

We describe the fabrication of silver nanotriangle array using angle resolved nanosphere lithography and utilizing the same for enhancing fluorescence. The well established nanosphere lithography is modified by changing the angle of deposition between the nanosphere mask and the beam of silver being deposited resulting in nanotriangles of varying surface area and density. The 470 nm plasmon resonance wavelength of the substrate was determined using minimum reflectivity method which closely matches with excitation wavelength of the fluorophore. Ten times enhancement in fluorescence emission intensity is obtained from fluorescein isothiocyanate coated on top of silver nanotriangle array separated by a spacer layer of poly vinyl alcohol as compared to glass. The enhanced fluorescence emission is attributed to the increase in local field enhancement.

Tetraethylammonium Tetraselenotungstate: A Versatile Selenium Transfer Reagent in Organic Synthesis

Organoselenium compounds have attracted intense research owing to their unique biological properties as well as pharmaceutical significance. Progress has been made in developing reagents for incorporation of selenium in an efficient and controlled manner. Herein, we present a review on the recently developed selenium reagent, tetraethylammonium tetraselenotungstate, Et4N](2)WSe4 as a versatile selenium transfer reagent in organic synthesis. Tetraselenotungstate has been successfully used for the synthesis of a number of functionalized diselenides, sugar- and nucleoside-derived diselenides, seleno-cystines, selenohomocystines, selenoamides, selenoureas and sugar- and nucleoside-based cyclic-selenide derivatives. Additionally, this reagent has been employed for the ring opening of aziridines to synthesize a variety of beta-aminodiselenides. A new selena-aza-Payne type rearrangement of aziridinemethanoltosylates mediated by tetraselenotungstate for the synthesis of allyl amines is also discussed.

Computational tools for mechanistic discrimination in the reductive and metathesis coupling reactions mediated by titanium(IV) isopropoxide

A theoretical study has been carried out at the B3LYP/LANL2DZ level to compare the reactivity of phenyl isocyanate and phenyl isothiocyanate towards titanium(IV) alkoxides. Isocyanates are shown to favour both mono insertion and double insertion reactions. Double insertion in a head-to-tail fashion is shown to be more exothermic than double insertion in a head-to-head fashion. The head-to-head double insertion leads to the metathesis product, a carbodiimide, after the extrusion of carbon dioxide. In the case of phenyl isothiocyanate, calculations favour the formation of only mono insertion products. Formation of a double insertion product is highly unfavourable. Further, these studies indicate that the reverse reaction involving the metathesis of N,N-'-diphenyl carbodiimide with carbon dioxide is likely to proceed more efficiently than the metathesis reaction with carbon disulphide. This is in excellent agreement with experimental results as metathesis with carbon disulphide fails to occur. In a second study, multilayer MM/QM calculations are carried out on intermediates generated from reduction of titanium(IV) alkoxides to investigate the effect of alkoxy bridging on the reactivity of multinuclear Ti species. Bimolecular coupling of imines initiated by Ti(III) species leads to a mixture of diastereomers and not diastereoselective coupling of the imine. However if the reaction is carried out by a trimeric biradical species, diastereoselective coupling of the imine is predicted. The presence of alkoxy bridges greatly favours the formation of the d,l (+/-) isomer, whereas the intermediate without alkoxy bridges favours the more stable meso isomer. As a bridged trimeric species, stabilized by bridging alkoxy groups, correctly explains the diastereoselective reaction, it is the most likely intermediate in the reaction.

Biotin-conjugated tumour-targeting photocytotoxic iron(III) complexes

Iron(III) complexes FeL(B)] (1-4) of a tetradentate phenolate-based ligand (H3L) and biotin-conjugated dipyridophenazine bases (B), viz. 7-aminodipyrido 3,2-a: 2',3'-c]-phenazine (dppza in 1), (N-dipyrido3,2-a: 2',3'-c]-phenazino) amidobiotin (dppzNB in 2), dipyrido 3,2-a: 2',3'-c]-phenazine-11-carboxylic acid (dppzc in 3) and 2-((2-biotinamido) ethyl) amidodipyrido 3,2-a: 2',3'-c]-phenazine (dppzCB in 4) are prepared, characterized and their interaction with streptavidin and DNA and their photocytotoxicity and cellular uptake in various cells studied. The high-spin iron(III) complexes display Fe(III)/Fe(II) redox couple near -0.7V versus saturated calomel electrode in dimethyl sulfoxide-0.1M tetrabutylammonium perchlorate. The complexes show non-specific interaction with DNA as determined from the binding studies. Complexes with appended biotin moiety show similar binding to streptavidin as that of free biotin, suggesting biotin conjugation to dppz does not cause any loss in its binding affinity to streptavidin. The photocytotoxicity of the complexes is tested in HepG2, HeLa and HEK293 cell lines. Complex 2 shows higher photocytotoxicity in HepG2 cells than in HeLa or HEK293, forming reactive oxygen species. This effect is attributed to the presence of overexpressed sodium-dependent multi-vitamin transporters in HepG2 cells. Microscopic studies in HepG2 cells show internalization of the biotin complexes 2 and 4 essentially occurring by receptor-mediated endocytosis, which is similar to that of native biotin and biotin fluorescein isothiocyanate conjugate.

Enantiospecific total synthesis of indole alkaloids (+)-eburnamonine, (-)-aspidospermidine and (-)-quebrachamine

An enantiospecific total synthesis of indole alkaloids eburnamonine, aspidospermidine and quebrachamine is described from lactic acid. Synthesis of all three alkaloids is accomplished from a single chiral building block. Johnson-Claisen rearrangement of a chiral allyl alcohol is the main feature for the installation of the required quaternary centre.

Single-step synthesis of internally functionalizable hyperbranched polyethers

Radical catalyzed thiol-ene reaction has become a useful alternative to the Huisgen-type azide-yne click reaction as it helps expand the variability in reaction conditions as well as the range of clickable entities. In this study, the direct generation of a hyperbranched polyether (HBPE) having decyl units at the periphery and a pendant allyl group on every repeat unit of the polymer backbone is described; the allyl groups serve as a reactive handle for postpolymerization modifications and permits the generation of a variety of internally functionalized HBPEs. In this design, the AB(2) monomer carries two decylbenzyl ether units (B-functionality), an aliphatic OH (A-functionality) and a pendant allyl group within the spacer segment; polymerization of the monomer readily occurs at 150 degrees C via melt transetherification process by continuous removal of 1-decanol under reduced pressure. The resulting HBPE has a hydrophobic periphery due to the presence of numerous decyl chains, while the allyl groups that remain unaffected during the melt polymerization provides an opportunity to install a variety of functional groups within the interior; thiol-ene click reaction with two different thiols, namely 3-mercaptopropionic acid and mercaptosuccinic acid, generated interesting amphiphilic structures. Preliminary field emission scanning electron microscope (FESEM) and Atomic Force Microscopy (AFM) imaging studies reveal the formation of fairly uniform spherical aggregates in water with sizes ranging from 200 to 400 nm; this suggests that these amphiphilic HBPs is able to reconfigure to generate jellyfish-like conformations that subsequently aggregate in an alkaline medium. The internal allyl functional groups were also used to generate intramolecularly core-crosslinked HBPEs, by the use of dithiol crosslinkers; gel permeation chromatography traces provided clear evidence for reduction in the size after crosslinking. In summary, we have developed a simple route to prepare core-clickable HBPEs and have demonstrated the quantitative reaction of the allyl groups present within the interior of the polymers; such HB polymeric systems that carry numerous functional groups within the core could have interesting applications in analyte sequestration and possibly sensing, especially from organic media. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4125-4135

Insertion Reactions of Six-Membered Cyclopalladated N,N `,N `'-Triarylguanidine, Pd{kappa(2)(C,N)-C6H3Me-3(NHC(NHAr)(=NAr))-2)(mu-Br)](2) (Ar=2-MeC6H4) with PhCC C-C(O)OR (R = Me and Et): A Gateway to Second Orthopalladation through Novel Rearrangements

The reaction of Pd{kappa(2)(C,N)-C6H3Me-3-(NHC(NHAr)(=NAr))-2}(mu-Br)](2) (Ar = 2-MeC6H4; 1) with 4 equiv of PhC C-C(O)OMe in CH2Cl2 afforded Pd{kappa(2)(C,N)-C(Ph)=C(C(O)OMe)C(Ph)=C(C(O)-OMe)C6H3Me-3(N=C(NH Ar)(2))-2}Br] (Ar = 2-MeC6H4; 2) in 70% yield, and the aforementioned reaction carried out with 10 equiv of PhC C-C(O)OR (R = Me, and Et) afforded an admixture of two regioisomers of Pd{kappa(3)(N,C,O)-O=C(OR)-C5Ph3(C(O)OR)C(C(O)OR)C6H3Me-3(N=C(NHAr)( 2))- 2}Br] (Ar = 2-MeC6H4; R = Me (3a/3b), Et (4a/4b)) in 80 and 87% yields, respectively. In one attempt, the minor regioisomer, 4b, was isolated from the mixture in 6% yield by fractional crystallization. Palladacycles 3a/3b and 4a/4b, upon stirring in CH2Cl2/MeCN (1/1, v/v) mixture at ambient condition for S days, afforded Pd{eta(3)-allyl,(KN)-N-1)-C-5(C(O)OR)(2)Ph3C-(C(O)OR)C6H3Me-3(N=C(NH Ar)(2))(-2)}Br] (Ar = 2-MeC6H4; R = Me (5a/5b), Et (6a/6b)) in 94 and 93% yields, respectively. Palladacycles 3a/3b and 4a/4b, upon reaction with AgOTf in CH2CH2/Me2C(O) (1/1, v/v) mixture at ambient temperature for 15 min, afforded Pd{kappa(3)(N,C,O)-O=C(OR)C5Ph3(C(O)OR)C(C(O)OR)C6H3Me-3(N=C(NHAr)(2 ))-2}(OTf)] (Ar = 2-MeC6H4; R = Me (7a/7b), Et (8a/8b)) in 79 and 77% yields, respectively. Palladacycles 7a/7b and 8a/ 8b, upon reflux in PhC1 separately for 6 h, or palladacycles 5a/5b and 6a/6b, upon treatment with AgOTf in CH2Cl2/Me2C(O) (7/3, v/v) mixture for 15 min, afforded Pd{(eta(2)-Ph)C5Ph2(C(O)OR)kappa(2)(C,N)-C(C(O)OR)C6H3Me-3(N=C(NHAr) (2))-2}(OTf)] (Ar = 2-MeC6H4; R = Me (9a/9h), Et (10a/10b)) in >= 87% yields. Palladacycles 9a/9b, upon stirring in MeCN in the presence of excess NaOAc followed by crystallization of the reaction mixture in the same solvent, afforded Pd{kappa(3)(N,C,C)-(C6H4)C5Ph2(C(O)OMe)(2)C(C(O)OMe)(2)C6H3Me-3(N=C( NHAr)(2))-2}(NCMe)] (Ar = 2-MeC6H4; 11a/11b) in 82% yield. The new palladacycles were characterized by analytical, IR, and NMR (H-1 and C-13) spectroscopic techniques, and the molecular structures of 2, 3a, 4a, 4b, 5a, 6a, 7a, 9a, 10a, and 11a-d(3) were determined by single crystal X-ray diffraction. The frameworks in the aforementioned palladacycles, except that present in 2, are unprecedented. Plausible pathways for the formation of new palladacycles and the influence of the guanidine unit in 1, substituents in alkynes, reaction conditions, and electrophilicity of the bromide and the triflate upon the frameworks of the insertion products have been discussed.

Periodically Clickable Polyesters: Study of Intrachain Self-Segregation Induced Folding, Crystallization, and Mesophase Formation

A series of polyesters based on 2-propargyl-1,3-propanediol or 2,2-dipropargyl-1,3-propanediol or 2-allyl-2-propargyl-1,3-propanediol and 1,20-eicosanedioic acid were prepared by solution polycondensation using the corresponding diacid chloride; these polyesters were quantitatively ``clicked'' with a fluoroalkyl, azide, namely CF3(CF2)(7)CH2CH2N3, to yield polyesters carrying long-chain alkylene segments in the backbone and either one or two perfluoroalkyl segments located at periodic intervals along the polymer chain. The immiscibility of the alkylene and fluoroalkyl segments causes the polymer chains to fold in a zigzag fashion to facilitate the segregation of these segments; the folded chains further organize in the solid state to form a lamellar structure with alternating domains of alkyl (HC) and fluoroalkyl (FC) segments. Evidence for the self-segregation is provided by DSC, SAXS, WAXS, and TEM studies; in two of the samples, the DSC thermograms showed two distinct endotherms associated with the melting of the individual domains, while the WAXS patterns confirm the existence of two separate peaks corresponding to the interchain distances within the crystalline lattices of the HC and FC domains. SAXS data, on the other hand, reveal the formation of an extended lamellar morphology with an interlamellar spacing that matches reasonably well with those estimated from TEM studies. Interestingly, a smectic-type liquid crystalline phase is observed at temperatures between the two melting transitions. These systems present a unique opportunity to develop interesting nanostructured polymeric materials with precise control over both the domain size and morphology; importantly, the domain sizes are far smaller than those typically observed in traditional block copolymers.

A Thiol- ene Clickable Hyperbranched Polyester via a Simple Single- Step Melt Trans- Esterification Process

Self-condensation of AB(2) type monomers (containing one A-type and two B-type functional groups) generates hyperbranched (HB) polymers that carry numerous B-type end-groups at their molecular periphery; thus, development of synthetic methods that directly provide quantitatively transformable peripheral B groups would be of immense value as this would provide easy access to multiply functionalized HB systems. A readily accessible AB(2) monomer, namely diallyl, 5-(4-hydroxybutoxy)isophthalate was synthesized, which on polymerization under standard melt-transesterfication conditions yielded a peripherally clickable HB polyester in a single step; the allyl groups were quantitatively reacted with a variety of thiols using the facile photoinitiated thiol-ene reaction to generate a wide range of derivatives, with varying solubility and thermal properties. Furthermore, it is shown that the peripheral allyl double bonds can also be readily epoxidized using meta-chloroperoxybenzoic acid to yield interesting HB systems, which could potentially serve as a multifunctional cross-linking agent in epoxy formulations. (c) 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40248.

Total synthesis of the indole alkaloids henrycinol A and B

The total synthesis of new indole alkaloids henrycinol A and B were accomplished starting from L-tryptophan methyl ester. The key step is a stereochemically flexible Pictet-Spengler reaction governed by the presence or absence of an N-allyl group in the tryptophan precursor. The natural products henrycinol A and B were synthesized in good overall yield in eight and nine steps, respectively. (C) 2014 Elsevier Ltd. All rights reserved.

2-(Phenylazo)pyridineplatinum(II) Catecholates Showing Photocytotoxicity, Nuclear Uptake, and Glutathione-Triggered Ligand Release

Platinum(II) complexes Pt(pap)(an-cat)] (1) and Pt(pap)(py-cat)] (2) with 2-(phenylazo)pyridine (pap), 4-2-(anthracen-9-ylmethylene)amino]ethyl]benzene-1,2-diol (H(2)an-cat), and 4-2-(pyren-1-ylmethylene)amino]ethyl]benzene-1,2-diol (H2py-cat) were prepared, and their photoinduced cytotoxicity was studied. The complexes were found to release catecholate ligand in the presence of excess glutathione (GSH), resulting in cellular toxicity in the cancer cells. The catecholate complex Pt(pap)(cat)] (3) was prepared and used as a control. Complex 3, which is structurally characterized by X-ray crystallography, has platinum(II) in a distorted square-planar geometry. The complexes are redox-active, showing responses near 0.6 and 1.0 V versus SCE in N,N-dimethylformamide/0.1 M tetrabutylammonium perchlorate corresponding to a two-step catechol oxidation process and at -0.3 and -1.3 V for reduction of the pap ligand. Complex 1 showed remarkable light-induced cytotoxicity in HaCaT (human skin keratinocytes) and MCF-7 (human breast cancer) cells, giving IC50 value of similar to 5 mu M in visible light of 400-700 nm and >40 mu M in the dark. The 2',7'-dichlorofluorescein diacetate (DCFDA) assay showed the generation of reactive oxygen species (ROS), which seems to trigger apoptosis, as is evident from the annexin V-fluorescein isothiocyanate (FITC)/propidium iodide (PI) assay. The fluorescence microscopic images showed significant nuclear localization of the complexes and free ligands. A mechanistic study revealed possible reduction of the coordinated azo bond of pap by cellular GSH, releasing the catecholate ligand and resulting in remarkable photochemotherapeutic action of the complexes.

Catalytic Enantioselective 1,4-lodofunctionalizations of Conjugated Dienes

The first catalytic enantioselective 1,4-iodofunctionalizations of conjugated dienes have been developed. Starting from beta,gamma,delta,epsilon-unsaturated oximes and 4-Ns hydrazones, these N-iodosuccinimide-mediated reactions are catalyzed by newly modified tertiary aminothiourea derivatives and furnish Delta(2)-isoxazoline and Delta(2)-pyrazoline derivatives, respectively, containing an (E)-allyl iodide group at the quaternary stereogenic center generally in high yield and with excellent enantioselectivity (up to 98.5:1.5 er).