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The ligand combination of semirigid 2,6-bis(imidazole-1-yl)pyridine (2,6-bip) and rigid benzenecarboxylate allow the isolation of three new zinc coordination polymers. Hydrothermal synthesis between Zn(NO3)2·6H2O, 2,6-bip, and terephthalic acid under basic condition affords [Zn(1,4-bdc)(2,6-bip)·2H2O]n (1) (1,4-bdc =1,4-benzenedicarboxylate), which shows an undulating 2D (4,4)-network with 2-fold interpenetration. Contrastingly, solvothermal synthesis with identical starting materials in DMF, yields [Zn(1,4-bdc)(2,6-bip)·DMF]n (2), which exhibits noninterpenetrating 2D (4,4)-network. Thus 1 and 2 are pseudo-supramolecular isomeric pair, illustrating the strong effect of guest solvents in controlling the entanglement. A similar hydrothermal reaction to 1 but using 1,3,5-benzenetricarboxylic acid instead yields [Zn2(μ−OH)(1,3,5-btc)(2,6-bip)·H2O]n (3) (btc = benzenetricarboxylate), which exhibits a (3,4,6)-connected 3D framework with an unprecedented {5.6.7}2{52.6.7.82}2{54.62.73.84.92} topology. Compound 1 and 2 show reversible solvent incorporation properties. A pseudo-supramolecular isomeric pair, namely, {Zn(1,4-bdc)(2,6-bip)·2H2O}n (1) and {Zn(1,4-bdc)(2,6-bip)·DMF}n (2) [bdc = benzenedicarboxylate; bip = bis(imidazole-1-yl)pyridine], was synthesized under hydro- and solvothermal conditions, respectively. 1 exhibits an undulating 2D (4,4)-network with 2-fold interpenetration, whereas 2 shows a similar 2D network without entanglement. [Zn2(μ−OH)(1,3,5-btc)(2,6-bip)·H2O]n (3) (btc = benzenetricarboxylate) exhibits a (3,4,6)-connected 3D framework with an unprecedented {5.6.7}2{52.6.7.82}2{54.62.73.84.92} topology. [ABSTRACT FROM AUTHOR]

Gold nanoparticles (AuNPs) have been studied as a potential solid-state matrix for laser desorption/ionization mass spectrometry (LDI-MS) but the efficiency in ionization remains low. In this report, AuNPs are capped by a self-assembled monolayer of cysteamine and modified with α-cyano-4-hydroxycinnanic acid (CHCA) for effective MALDI measurements. CHCA-terminated AuNPs offer marked improvement on peptide ionization compared with citrate-capped or cysteamine-capped AuNPs. The coating also effectively suppresses formation of Au cluster ions and analyte fragment ions, leading to cleaner mass spectra. Addition of glycerol and citric acid to the peptide/AuNPs sample further improves the performance of these AuNPs for LDI-MS analysis. Glycerol appears to enhance the dispersion of AuNPs in sample spots, increasing the sample ionization and shot-to-shot reproducibility, while citric acid serves as an external proton donor, providing high production of protonated analyte ions and reducing fragmentation of peptides on the nanoparticle-based surface. Optimal ratios of citric acid, glycerol, and AuNPs in sample solution have been systematically studied. A more than 10-fold increase for desorption ionization of peptides can be achieved by combining 5% glycerol and 20 mM citric acid with the CHCA-terminated AuNPs. The applicability of the CHCA-AuNPs for LDI-MS analysis of protein digests has also been demonstrated. This work shows the potential of AuNPs for SALDI-MS analysis, and the improvement with chemical functionalization, controlled dispersion, and use of an effective proton donor. [ABSTRACT FROM AUTHOR]

Localized surface plasmon resonance (LSPR) represents a sensitive and versatile method for detection of biomolecules in a label-free fashion, but identification of bound analytes can be challenging with LSPR alone, especially for samples in a complex medium. We report the fabrication of an optically active, plasmonic film of gold nanoparticles by using a self-assembly and calcination process, which offers orthogonal measurements enabling multifaceted characterization on the same surface with LSPR and surface-assisted laser desorption/ionization mass spectrometry. This proof-of-concept study involves plasmonic characterization of the fabricated nanofilm, real-time monitoring of vesicle-surface interactions toward formation of fluid lipid bilayer, and mass spectrometric analysis of peptides and cytochrome c digest. This multifunction-enabling surface material can yield complementary analytical information, providing new tools for comprehensive analysis of biomolecular samples.

Optical sensors capable of colorimetric visualization and/or fluorescence detection have shown tremendous potential for field technicians and emergency responders, owing to the portability and low cost of such devices. Polydiacetylene (PDA)-enhanced nanofibers are particularly promising due to high surface area, facile functionalization, simple construction, and the versatility to empower either colorimetric or fluorescence signaling. We demonstrate here a dual-mode optical sensing with electrospun nanofibers embedded with various PDAs. The solvent-dependent fluorescent transition of nanofibers generated a pattern that successfully distinguished four common organic solvents. The colorimetric and fluorescent sensing of biotin-avidin interactions by embedding biotinylated-PCDA monomers into silica-reinforced nanofiber mats were realized for detection of biomolecules. Finally, a PDA-based nanofiber sensor array consisting of three monomers has been fabricated for the determination and identification of organic amine vapors using colorimetry and principal component analysis (PCA). The combination of PCA and the strategy of probing analytes in two different concentration ranges (ppm and ppth) led to successful analysis of all eight amines.

Vibronic characteristics and spin-density distributions in the core bacteriochlorin macrocycle were revealed by spectroscopic and theoretical studies of 16 isotopologues. The vibrational modes in copper bacteriochlorin isotopologues were examined via resonance Raman and Fourier-transform infrared spectroscopy. The resonance Raman spectra exhibit an exceptional sparcity of vibronically active modes of the core macrocycle, in contrast with the rich spectra of the natural bacteriochlorophylls. The Q y -excitation resonance Raman spectrum is dominated by a single mode at 727 cm -1 , which calculations suggest is due to a symmetrical accordion-like deformation of the five-atom C m (C a NC a ) pyrrole C m portion of the ring core. This deformation also dominates the vibronic features in the absorption and fluorescence spectra. The spin-density distributions in the π-cation radical of the zinc bacteriochlorin isotopologues were studied by electron paramagnetic resonance spectroscopy. The spectra indicate a significant electron/spin density (ρ ∼ 0.1) on each meso-carbon atom. This observation contradicts the predictions of early calculations that have been assumed to be correct for nearly four decades. Collectively, these findings have implications for how the structural features that characterize natural bacteriochlorophylls might influence energy- and electron-transfer processes in photosynthesis and alter the thinking on the design of synthetic, bacteriochlorin-based arrays for solar-energy conversion.

Synthetic bacteriochlorins containing site-specific isotopic substitution enable spectroscopic interrogation to delineate physicochemical features relevant to bacteriochlorophylls in photosynthesis but have been little explored. A de novo synthesis has been employed to prepare bacteriochlorins wherein each macrocycle contains a pair of (13)C or (15)N atoms yet lacks substituents other than a geminal dimethyl group in each pyrroline ring. Preparation of a dihydrodipyrrin–acetal with single-isotopic substitution gives rise to a bacteriochlorin that contains two isotopic substitutions symmetrically disposed by a 180° rotation about the normal to the plane of the macrocycle. Eight such isotopically substituted bacteriochlorins were prepared from commercially available reactants (bacteriochlorin sites): ((13)C)paraformaldehyde (1, 11); ((13)C)formamide (4, 14); triethyl ((13)C)orthoformate (5, 15); K(13)CN (6, 16); (13)CH3NO2 (9, 19); N,N-dimethyl((13)C)formamide (10, 20); ((15)N)pyrrole (21, 23); CH3(15)NO2 (22, 24). Some loss of (15)N upon TiCl3-mediated McMurry-type ring closure of a nitro((15)N)hexanone is attributed to a parallel sequence of three reactions (Nef, exchange with natural-abundance NH4OAc buffer, and Paal–Knorr ring closure) leading to the dihydrodipyrrin–acetal. Zinc and copper chelates of each bacteriochlorin also were prepared. Together, the 24 bacteriochlorin isotopologues should provide valuable benchmarks for understanding ground- and excited-state molecular physics of the macrocycles related to photosynthetic function of bacteriochlorophylls.

The effect of the rigid bulky pentiptycene scaffolds on the photoluminescence, redox properties, and oxygen sensing behavior of unichromophoric Pt-acetylides is reported. When the pentiptycene groups are near the Pt(PBu3)2 center, the Pt-acetylides display both blue fluorescence and green phosphorescence with long phosphorescence lifetimes (90-202 μs) in THF. Their phosphorescence intensity is highly sensitive to molecular oxygen, and the emission color depends on the concentration of not only oxygen but also the complexes, which allows a feasible determination of oxygen in the range of 1-5% air volume. The dynamic quenching rate constants decrease linearly with increasing the number of pentiptycene groups, revealing the steric shielding effect of the peripheral rings of pentiptycene. A dependence of oxidation potential on the number of pentiptycene groups also revealed the steric shielding effect on the electron transfer between the complexes and the electrode. In a PMMA matrix, the dual emissive properties are diminished due to increased phosphorescence and decreased fluorescence intensity, and the phosphorescence lifetimes are significantly increased (up to ∼700 μs), leading to an "on-off" optical response to oxygen concentration. Both the dual emissive properties and long-lived triplet excitons are attributed to diminished spin-orbit couplings caused by twisting and steric shielding of the π-conjugated backbone around the Pt center.

We present a highly sensitive metal enhanced fluorescence (MEF) method based on a novel silver nanostructure fabricated with Cy5-functionalized silver nanoparticles (AgNPs) and AgNO(3). The analytical performance has been demonstrated by microarray detection of streptavidin (SA) and human IgE. The fluorescence intensity can be enhanced substantially with the combined use of AgNPs and fluorescence enhanced solution (FES). Aptamers have been used for the preparation of Tag-C, which demonstrate IgE detection from 0.5 ng/mL to 16 ng/mL, and the limit of detection is determined to be 0.25 ng/mL. SEM images show nanogaps exist in the aggregated silver nanoparticles and the nanogaps allow for the trap of fluorophores in the nanostructures that emit brighter light upon excitation. The silver nanostructures formed by Tags and FES proved to be an excellent platform for MEF of fluorophores whose excitation and emission occurred between 436 nm and 1000 nm. Finite-difference time-domain (FDTD) simulation has been carried out to confirm the enhanced electromagnetic field inside silver nanostructures, leading to strong overlap/resonance coupling and eventual fluorescence enhancement.

Access to metallobacteriochlorins is essential for investigation of a wide variety of fundamental photochemical processes, yet relatively few synthetic metallobacteriochlorins have been prepared. Members of a set of synthetic bacteriochlorins bearing 0-4 carbonyl groups (1, 2, or 4 carboethoxy substituents, or an annulated imide moiety) were examined under two conditions: (i) standard conditions for zincation of porphyrins [Zn(OAc)(2)·2H(2)O in N,N-dimethylformamide (DMF) at 60-80 °C], and (ii) treatment in tetrahydrofuran (THF) with a strong base [e.g., NaH or lithium diisopropylamide (LDA)] followed by a metal reagent MX(n). Zincation of bacteriochlorins that bear 2-4 carbonyl groups proceeded under the former method whereas those with 0-2 carbonyl groups proceeded with NaH or LDA/THF followed by Zn(OTf)(2). The scope of metalation (via NaH or LDA in THF) is as follows: (a) for bacteriochlorins that bear two electron-releasing aryl groups, M = Cu, Zn, Pd, and InCl (but not Mg, Al, Ni, Sn, or Au); (b) for bacteriochlorins that bear two carboethoxy groups, M = Ni, Cu, Zn, Pd, Cd, InCl, and Sn (but not Mg, Al, or Au); and (c) a bacteriochlorin with four carboethoxy groups was metalated with Mg (other metals were not examined). Altogether, 15 metallobacteriochlorins were isolated and characterized. Single-crystal X-ray analysis of 8,8,18,18-tetramethylbacteriochlorin reveals the core geometry provided by the four nitrogen atoms is rectangular; the difference in length of the two sides is ∼0.08 Å. Electronic characteristics of (metal-free) bacteriochlorins were probed through electrochemical measurements along with density functional theory calculation of the energies of the frontier molecular orbitals. The photophysical properties (fluorescence yields, triplet yields, singlet and triplet excited-state lifetimes) of the zinc bacteriochlorins are generally similar to those of the metal-free analogues, and to those of the native chromophores bacteriochlorophyll a and bacteriopheophytin a. The availability of diverse metallobacteriochlorins should prove useful in a variety of fundamental photochemical studies and applications.

Two compounds, namely, [TTPH(2)](Cl)(2) x 4 H(2)O (1) and [TTPH(2)](Br)(2) x 4 H(2)O (2), (TTP = 4'-p-tolyl-2,2':6',2''-terpyridine) were synthesized from purely aqueous media and characterized by physical techniques. In the solid-state structures of these compounds, interesting supramolecular assemblies are observed. In 1, an unusual staircase-like architecture of the tape of edge-shared planar water hexamer is of importance, where the chloride ions are at the two edges of the tape. In 2, the polymeric nature of the water-bromide assembly is of interest, where discrete open-cube water octamers are doubly bridged by bromide ions. Semiempirical and DFT calculations confirm that the nature of the anion indeed affects the topology of the water-halide assemblies. We conclude that the protonated [TTPH(2)](2+) species can act as appropriate receptors for halide ions, which in turn act as a matrix for the formation of polymeric 1D water-halide assemblies.

The achiral 2,6-bis(imidazol-1-yl)pyridine (L) was used as the ditopic organic tecton for the formation of coordination polymers with Zn(II) ions. Hydrothermal reaction between L and ZnX2 (X=Br, Cl) afforded spontaneous resolved double helical motifs in ZnLCl2.0.5H2O (1) and ZnLBr2.0.25H2O (2). In the homochiral crystals of 1a and 2a, the helices are of M-helicity, whereas, in 1b and 2b, they are of P-helicity. In contrast, solvothermal reaction between L and ZnCl2 in dried DMF afforded achiral ZnLCl2 (3a), which exhibits a zigzag polymeric motif. An achiral polymorph 3b which contains 21 helical chains was obtained in wet DMF. The formation of different 1D motifs was related to the conformations of L. All these compounds were characterized by infrared spectroscopy, elemental analyses, and single-crystal X-ray diffraction. As revealed by thermal gravimetric analysis and powder X-ray diffraction study, the homochiral motif in 1 was stable even upon removal of guest water molecules. Contrastingly, structural transformation from 3a or 3b to 1 is possible upon hydration.

The synthesis and structural characterization of several new silver complexes of L (L = a bidendate ligand of pyrazole and N-heterocyclic carbene) are described. The result shows that the choice of counterions, N-substitutions of L, and reaction conditions are crucial which lead to a variety of structural motifs, including novel metallomacrocycles [Ag2(mu-L)2]2+ with or without Ag...Ag close contact, a mononuclear [AgL2]+ complex, and a [LAg(NO3)]n coordination polymer. In particular, the nonbonding Ag...Ag distance and the overall geometry of the metallomacrocycles are controllable with different N-substitutions and counterions. All these complexes have been determined by X-ray diffraction. The solid-state aggregates are retained in solution as supported by the electrospray mass spectroscopic studies.