Infinite Polymer Research Articles

Sensor array and color-coded test paper tongue based on multivariate cross-responsive AIEgen functionalized bimetallic lanthanide infinite coordination polymers: Toward smart identification and systematic analysis of antibiotics

Building and improving the monitoring technology system for newly emerging contaminants with a positive attitude is the first step to enhance governance capacity, which is in good accordance with the requirements of worldwide sustainable development strategy nowadays. With the urgent needs of smart identification and simultaneous detection of multiple antibiotics co-existing in the aquatic system in mind, we intentionally synthesized the aggregation-induced emission luminogen (AIEgen) functionalized bimetallic lanthanide infinite coordination polymers (TPE-TS@Tb/Eu-AMP ICPs) series. The intrinsic physical and chemical properties of target antibiotics (flumequine, four kinds of tetracyclines, and sulfadiazine) triggered the complex chemical recognition reactions of TPE-TS@Tb/Eu-AMP ICPs series to give birth to multivariate cross-responses. Based on these theoretical-oriented sensing elements and rationally selected smart statistical tools, the “lab-on-TPE-TS@Tb/Eu-AMP ICPs” antibiotic sensor array is established with superior analytical performance. Moreover, the unique optical dominance of TPE-TS@Tb/Eu-AMP ICPs series on solid substrate enabled the subsequent exploitation of test paper tongue (TPT) with simultaneously altered RGB values as elements. Being further coded by the excitation modulation on commercial dark box UV-lamp, even promoted analytical behaviors of the TPT can be realized for the first time. With the aid of the smartphone, robust pattern recognition and accurate systematic analysis of antibiotics in the actual environmental samples were achieved by our sensor array and color-coded TPT, which may provide important scientific supports and technical reserves for the antibiotic control actions in future.

Nonempirical Prediction of the Length-Dependent Ionization Potential in Molecular Chains.

The ionization potential of molecular chains is well-known to be a tunable nanoscale property that exhibits clear quantum confinement effects. State-of-the-art methods can accurately predict the ionization potential in the small molecule limit and in the solid-state limit, but for intermediate, nanosized systems prediction of the evolution of the electronic structure between the two limits is more difficult. Recently, optimal tuning of range-separated hybrid functionals has emerged as a highly accurate method for predicting ionization potentials. This was first achieved for molecules using the ionization potential theorem (IPT) and more recently extended to solid-state systems, based on an ansatz that generalizes the IPT to the removal of charge from a localized Wannier function. Here, we study one-dimensional molecular chains of increasing size, from the monomer limit to the infinite polymer limit using this approach. By comparing our results with other localization-based methods and where available with experiment, we demonstrate that Wannier-localization-based optimal tuning is highly accurate in predicting ionization potentials for any chain length, including the nanoscale regime.

1D heteronuclear coordination polymers of hexacyanocobaltate(III) with 2-hydroxymethylpyridine

Three new hexacyanocobaltate(III) complexes, {[M2(hmpy)4Co(µ-CN)4(CN)2]∙2H2O}n (M = Cu(II) (1), Zn(II) (2) and Cd(II) (3)) were synthesized with 2-hydroxymethylpyridine (hmpy) ligand, and characterized by vibration (FT-IR and Raman) spectral, single crystal X-ray diffraction (SC-XRD) and powder X-ray diffraction (PXRD), thermal and elemental analyses techniques. The crystallographic analyses revealed that cyanide complexes 1–3 are infinite one-dimensional coordination polymers. Each M ion is coordinated by two nitrogen and two oxygen atoms from the hmpy ligands and two nitrogen atoms from the cyanide ligands, displaying a distorted octahedral coordination geometry. Similarly, each Co(III) ion is coordinated by six carbon atoms from cyanide ligands to form a distorted octahedral coordination geometry. These complexes form 3D supramolecular networks through OH···O hydrogen bonds and CH···N interactions. Additionally, structural analyses such as metal salts, pH values of the compounds obtained under different conditions were evaluated. A synthesis-structural analyses relation was made from these data.

Lanthanide coordination polymers@CuO nanoparticles: Enhanced self-cascade nanoenzyme activity and ratiometric fluorescence assay of glutathione

Tandem enzyme can catalyze some cascade reactions with high efficiency, and some few tandem enzyme-like mimics have been discovered recently. Further improving the catalytic efficiency of tandem nanoenzymes with facile method may undoubtedly promote and broaden their applications in various fields. In this work, cupric oxide nanoparticles (CuO NPs) with dual-functional enzyme mimics were synthesized using the rapid deposition method in advance, which simultaneously combined with lanthanide infinite coordination polymers (Ln ICPs) during the self-assemble of Tb3+, guanine-5′-triphosphate (GTP) and auxiliary ligand terephthalic acid (TA). Excitingly, the obtained Tb-GTP/TA@CuO ICPs, not only displayed obviously enhanced tandem catalytic activity compared with pure CuO NPs, but also provided a versatile ratiometric platform for ultrahigh selective and sensitive detection of glutathione (GSH) under single-wavelength excitation. A good linear relationship between the ratio signal and the GSH concentration was spanning from 0.001 to 20 μM with an impressive detection limit of 0.50 nM. This study opens a new and universal avenue for preparing integrated multifunctional probes by coupling of nanoenzyme catalytic activity with superior luminescent Ln ICPs through facile method.

Four-component of double-layer infinite coordination polymer nanocomposites for large tumor trimodal therapy via multi high-efficiency synergies

Multimodal /components tumors synergistic therapy is a crucial approach for enhancing comprehensive efficacy. Our research has identified lots of high efficiency synergies among four suitable components, revealing combinations with remarkably low combination index (CI) values (10-3-10-8). These combinations hold promise for large tumor powerful electrothermal-thermodynamic-multi-chemo trimodal therapy. To implement this approach, we developed four-component of double-layer infinite coordination polymer (ICP) nanocomposites, in which hypoxia-activated AQ4N and thermodynamic agent AIPH coordinated with Cu(Ⅱ) to form initial layer of positively charged ICPs-l NPs, chemotherapeutic agents gossypol-hyaluronic acid (G-HA) and CA4 coordinated with Fe(Ⅲ) to form out layer of negatively charged ICPs-2 NPs, then double-layer infinite coordination polymer nanocomposites (ICPs-1@ICPs-2 CNPs) were fabricated by electrostatic adsorption using ICPs-l NPs and ICPs-2 NPs. Cell experiments have extensively optimized the coordination combinations of the four components and the composition of the two layers. A programmable three-stage therapeutic procedure, assisted by a micro-electrothermal needle (MEN), was developed. Under this procedure the resulting nanocomposites demonstrate the powerful trimodal comprehensive therapeutic outcomes for large tumors using lower components dosage, achieving a tumor inhibition rate nearly reaching 100 % and no recurrence for 60 days. This study offers remarkable potential for tumor multimodal /components synergistic therapy in future.

Structure of native four-repeat satellite III sequence with non-canonical base interactions.

Tandem-repetitive DNA (where two or more DNA bases are repeated numerous times) can adopt non-canonical secondary structures. Many of these structures are implicated in important biological processes. Human Satellite III (HSat3) is enriched for tandem repeats of the sequence ATGGA and is located in pericentromeric heterochromatin in many human chromosomes. Here, we investigate the secondary structure of the four-repeat HSat3 sequence 5'-ATGGAATGGA ATGGA ATGGA-3' using X-ray crystallography, NMR, and biophysical methods. Circular dichroism spectroscopy, thermal stability, native PAGE, and analytical ultracentrifugation indicate that this sequence folds into a monomolecular hairpin with non-canonical base pairing and B-DNA characteristics at concentrations below 0.9 mM. NMR studies at 0.05-0.5 mM indicate that the hairpin is likely folded-over into a compact structure with high dynamics. Crystallographic studies at 2.5 mM reveal an antiparallel self-complementary duplex with the same base pairing as in the hairpin, extended into an infinite polymer. The non-canonical base pairing includes a G-G intercalation sandwiched by sheared A-G base pairs, leading to a cross-strand four guanine stack, so called guanine zipper. The guanine zippers are spaced throughout the structure by A-T/T-A base pairs. Our findings lend further insight into recurring structural motifs associated with the HSat3 and their potential biological functions.

Hyaluronic acid-decorated curcumin-based coordination nanomedicine for enhancing the infected diabetic wound healing

Persistent over-oxidation, inflammation and bacterial infection are the primary reasons for impaired wound repairing in diabetic patients. Therefore, crucial strategies to promote diabetic wound repairing involve suppressing the inflammatory response, inhibiting bacterial growth and decreasing reactive oxygen species (ROS) within the wound. In this work, we develop a multifunctional nanomedicine (HA@Cur/Cu) designed to facilitate the repairing process of diabetic wound. The findings demonstrated that the synthesized infinite coordination polymers (ICPs) was effective in enhancing the bioavailability of curcumin and improving the controlled drug release at the site of inflammation. Furthermore, in vitro and in vivo evaluation validate the capacity of HA@Cur/Cu to inhibit bacterial growth and remove excess ROS and inflammatory mediators, thereby significantly promoting the healing of diabetic wound in mice. These compelling findings strongly demonstrate the enormous promise of this multifunctional nanomedicine for the treatment of diabetic wound.

Intravenous injectable metformin-Cu(II)-EGCG coordination polymer nanoparticles for electrothermally enhanced dual-drug synergistic tumor therapy.

Intravenous injectable metformin-Cu(II)-EGCG infinite coordination polymer nanoparticles (metformin-Cu(II)-EGCG ICP NPs) have been synthesized, and an efficient strategy for synergistic tumor therapy by utilizing these nanoparticles in conjunction with micro-electrothermal needles (MENs) was proposed. These nanoparticles display exceptional uniformity with a diameter of 117.5 ± 53.3 nm, exhibit an extraordinary drug loading capacity of 90% and allow for precise control over the drug ratio within the range of 1 : 1 to 1 : 20 while maintaining excellent thermal stability. Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and X-ray diffraction were employed to determine their chemical structure and coordination state. The combination index (CI) value of the metformin-Cu(II)-EGCG ICP NPs was calculated to be 0.19, surpassing that of the two individual drugs and metformin mixed with EGCG (0.98). Importantly, upon intravenous injection, metformin in nanoparticles demonstrated exceptional stability in the bloodstream, while both drugs were rapidly released within the acidic tumor microenvironment. Animal experiments showcased an impressive tumor inhibition rate of 100% within a mere 20-day time frame after the synergistic therapy with a lower dosage (5.0 mg kg-1 of nanoparticles), coupled with a minimal tumor recurrence rate of only 18.75% over a 60-day observation period. These findings indicate the promising prospects of these nanoparticles in tumor treatment.

Self-Calibrating Lanthanide Infinite Coordination Polymer Constructs Fluorescent Probes: A Sensitive Approach for Early Diagnosis of Hepatocellular Carcinoma and Environmental Analysis.

The development of a self-calibrating ratio fluorescence probe without the need for additional substrates is a major advancement in biosensing. In this study, at room temperature, a self-calibrating infinite coordination polymer (SSA-Tb-ATP ICPs) has been proposed by self-assembling adenosine triphosphate (ATP) with 5-sulfosalicylic acid (SSA) and Tb3+. Due to the antenna effect, SSA-Tb-ATP ICPs exhibited strong green fluorescence emission of Tb3+ (at 547 nm) and blue fluorescence emission of SSA (at 407 nm). This material offers several advantages over existing detection methods, including simplicity of synthesis and exceptional sensitivity. Our self-calibrating SSA-Tb-ATP ICPs demonstrated excellent performance in detecting alkaline phosphatase (ALP) and phosphate (Pi) in both serum and environmental samples with detection limits of 0.076 U/L and 0.025 μM, respectively. Moreover, we successfully employed the SSA-Tb-ATP ICPs to perform cellular imaging of ALP in both hepatocellular carcinoma cells (HepG2) and normal liver cells (LO2), representing a significant advancement in ALP detection and imaging. The simplicity of the synthesis and high sensitivity make this probe a promising tool for early diagnosis of hepatocellular carcinoma in clinical settings and environment analysis.

An intelligent “chemical tongue” for high-order monitoring ATP-related physiological phosphates and ATP hydrolysis through diverse transduction principles

For discriminating diverse analytes and monitoring a specific chemical reaction, the emerging multi-channel “chemical nose/tongue” is challenging multi-material “chemical nose/tongue”. The former contributes greatly to integrating different transduction principles from a single sensing material, avoiding the need for complex design, high cost, and tedious operation involved with the latter. Therefore, this high-order sensing puts a particular emphasis on the effects of encapsulation. Herein, the plasmonic gold nanoparticles (Au NPs) are encapsulated as a core into the fluorescent guanine monophosphate-Tb3+ infinite coordination polymer nanoparticles (GMP-Tb ICPs) to obtain a core-shell nanocomposite named Au NPs@GMP-Tb ICPs. Hence, a dual-channel “chemical tongue” based on Au NPs@GMP-Tb ICPs is present to realize high-order sensing of adenosine triphosphate (ATP)-related physiological phosphates and the monitoring of ATP hydrolysis. Considering the affinity of Tb3+ towards P–O bonds, four inorganic phosphates and three nucleotide phosphates with different phosphate group numbers and steric hindrance effect directly regulate two stimulus responses (fluorescence intensity and UV–vis absorbance) of Au NPs@GMP-Tb ICPs. Robust statistical methods, such as linear discriminant analysis and hierarchical cluster analysis, are used to recognize each phosphate by the developed sensor array either in the aqueous solution or in complex media such as serum, together with efficiently monitored ATP hydrolysis at different intervals. These findings and blind test clarify that the designed “chemical tongue” guarantees interference resistance and strengthens analytical capacity, together with offering valuable insight into “lab-on-a-nanoparticle” development for monitoring specific chemical reactions.

Predicting the mass spectrum of polymerizing linoleates using weighted random graph modeling

Biopolymers and biopolymer networks that form via autoxidation, like in drying of oil paint or fat degradation in food components, contain a large variety of monomeric building blocks. While the monomer variety complicates the modeling itself, obtaining experimental validation of infinite polymer networks is inherently difficult as well. A new model is developed, where an automated reaction network generation (ARNG) procedure is used to automatically generate the monomer components, structures and masses, and their reactions. This methodology is combined with random graph (RG) modeling to predict global polymer properties: distributions of numbers of monomer units and molar masses, gel point and gel fraction. This computational framework is applied to two model systems for linseed oil paint binder: the polymerization of ethyl linoleate (EL) and methyl linoleate (ML). A novel method was constructed to deal with the variability of monomer masses that complicates inferring molar mass from monomer number distribution. By modeling the polymer as a weighted random graph where the nodes contain information about the monomer masses in the system, the total weight of the finite connected components is computed. The predicted mass spectrum of finite connected components is used for validation with experimental data. A size exclusion chromatography (SEC) trace of ML is employed, which after calibration using the proposed framework, proves consistency between model and SEC data. The model provides a practical approach to both characterize complex biopolymers as polymers in terms of molar mass distribution and gel point, while preserving the information down to the level of monomeric units.

Chemodynamic therapy agent optimized mesoporous TiO2 nanoparticles for Glutathione-Enhanced and Hypoxia-Tolerant synergistic Chemo-Sonodynamic therapy

Sonodynamic therapy (SDT) can generate reactive oxygen species to kill cancer cells by activating sonosensitizers under ultrasound (US) irradiation. Nevertheless, its application is greatly limited by low quantum yield of sonosensitizers, high levels of endogenous glutathione (GSH) and tumor hypoxia. Herein, a GSH-activated sonosensitizers with synergistic therapy effect (chemodynamic therapy (CDT) and SDT) are developed by depositing Fe(III)-artemisinin infinite coordination polymers (Fe(III)-ART CPs) in pores of mesoporous TiO2 nanoparticles (NPs). The formed Fe(III)-ART-TiO2 NPs have high sono-induced electron-hole separation efficiency because the deposited Fe(III)-ART CPs can provide isolated intermediate bands to capture sono-induced electrons in TiO2 NPs. Meanwhile, Fe3+ in Fe(III)-ART-TiO2 NPs are reduced to Fe2+ by GSH with oxygen-deficient sites generated to further capture sono-induced electrons in TiO2 NPs. Based on this, the reaction efficiency between water molecules and sono-induced holes is high enough to generate numerous hydroxyl radicals (•OH) without oxygen participated for overcoming tumor hypoxia. Additionally, through consuming GSH, the generated Fe2+ can catalyze ART to produce C-centered free radicals for CDT. Owing to these characteristics, Fe(III)-ART-TiO2 NPs show significant tumor suppression ability and good biocompatibility in vivo. The strategy of using CDT agent to modify sonosensitizers offers new options to improve SDT effect without introducing harmful substances.

Doxorubicin-Fe(III)-Gossypol Infinite Coordination Polymer@PDA:CuO2 Composite Nanoparticles for Cost-Effective Programmed Photothermal-Chemodynamic-Coordinated Dual Drug Chemotherapy Trimodal Synergistic Tumor Therapy.

To achieve the maximum therapeutic effects and minimize adverse effects of trimodal synergistic tumor therapies, a cost-effective programmed photothermal (PTT)-chemodynamic (CDT)-coordinated dual drug chemotherapy (CT) trimodal synergistic therapy strategy in chronological order is proposed. According to the status or volumes of the tumors, the intensity and time of each therapeutic modality are optimized, and three modalities are combined programmatically and work in chronological order. The optimal synergistic therapy begins with high-intensity PTT for 10 min to ablate larger tumors, followed by medium-intensity CDT for several hours to eliminate medium-sized tumors, and then low-intensity coordinated dual drugs CT lasts over 48 h to clear smaller residual tumors. Composite nanoparticles, made of Fe-coordinated polydopamine mixed with copper peroxide as the cores and their surface dotted with lots of doxorubicin-Fe(III)-gossypol infinite coordination polymers (ICPs), have been developed to implement the strategy. These composite nanoparticles show excellent synergistic effects with the minimum dose of therapeutic agents and result in nearly 100% tumor inhibition for mice bearing PC-3 tumors and no observed recurrence within 60 days of treatment. The ratios of the different therapeutic agents in the composite nanoparticles can be adjusted to accommodate different types of tumors with this cost-effective programmed trimodal therapy strategy.

Anthracene‐Porphyrin Nanoribbons

Abstractπ‐Conjugated nanoribbons attract interest because of their unusual electronic structures and charge‐transport behavior. Here, we report the synthesis of a series of fully edge‐fused porphyrin‐anthracene oligomeric ribbons (dimer and trimer), together with a computational study of the corresponding infinite polymer. The porphyrin dimer and trimer were synthesized in high yield, via oxidative cyclodehydrogenation of singly linked precursors, using 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ) and trifluoromethanesulfonic acid (TfOH). The crystal structure of the dimer shows that the central π‐system is flat, with a slight S‐shaped wave distortion at each porphyrin terminal. The extended π‐conjugation causes a dramatic red‐shift in the absorption spectra: the absorption maxima of the fused dimer and trimer appear at 1188 nm and 1642 nm, respectively (for the nickel complexes dissolved in toluene). The coordinated metal in the dimer was changed from Ni to Mg, using p‐tolylmagnesium bromide, providing access to free‐base and Zn complexes. These results open a versatile avenue to longer π‐conjugated nanoribbons with integrated metalloporphyrin units.

Anthracene-Porphyrin Nanoribbons.

π-Conjugated nanoribbons attract interest because of their unusual electronic structures and charge-transport behavior. Here, we report the synthesis of a series of fully edge-fused porphyrin-anthracene oligomeric ribbons (dimer and trimer), together with a computational study of the corresponding infinite polymer. The porphyrin dimer and trimer were synthesized in high yield, via oxidative cyclodehydrogenation of singly linked precursors, using 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and trifluoromethanesulfonic acid (TfOH). The crystal structure of the dimer shows that the central π-system is flat, with a slight S-shaped wave distortion at each porphyrin terminal. The extended π-conjugation causes a dramatic red-shift in the absorption spectra: the absorption maxima of the fused dimer and trimer appear at 1188 nm and 1642 nm, respectively (for the nickel complexes dissolved in toluene). The coordinated metal in the dimer was changed from Ni to Mg, using p-tolylmagnesium bromide, providing access to free-base and Zn complexes. These results open a versatile avenue to longer π-conjugated nanoribbons with integrated metalloporphyrin units.

Isomorphous and Isostructural Coordination Polymers Besides Metal‐Organic Frameworks (MOFs) of bis(4‐Nitrophenyl)‐phosphoric Acid in Conjunction with Some N‐donor Compounds

AbstractVarious coordination complexes, in the form of infinite coordination polymers and metal‐organic frameworks (MOFs) of an organophosphorous acid, bis(4‐nitrophenyl)phosphoric acid (BNPP), in the presence of some N‐donor compounds like 4,4′‐bipyridine (bpy), 1,2‐bis(4‐pyridyl)ethene (bpyee), 1,2‐bis(4‐pyridyl)ethane (bpyea) and 1,3‐bis(4‐pyridyl)propane (bpypa) along with metal ions, Co+2, Cd+2, Cu+2, and Ni+2, have been reported. Using the single crystal X‐ray diffraction method, the obtained structures are classified into isomorphous, isostructural coordination polymers, and metal‐organic framework structures. Except for the structures, formed by bpy with Ni(II) and Cu(II), bpypa with Cu(II) and bpyee with Co(II) and Ni(II), all of the complexes crystallize with both BNPP and N‐donor ligands forming coordinate bonds with the metal ions, yielding dumbbell‐shaped moieties in the lattices. A noteworthy feature in the structures obtained with bpyee, is that BNPP molecules do not form coordination bonds with metal ions Co(II) and Ni(II), while N‐donor ligands (bpyee) are only connected to the metal ions. Furthermore, in these complexes, the BNPP molecules occupy the same positions in the crystal lattice as those of coordinated BNPP moieties, but by hydrogen bonds, thus, establishing a high correlation of isostructurality in three‐dimensional packing between structures having coordinated and uncoordinated BNPP molecules, and highlighting the significance of hydrogen bonds in comparison with coordinated bonds. All of the complexes described, herein, are stabilized by different types of intermolecular interactions, specifically through a large number of C−H⋅⋅⋅O hydrogen bonds. Hirshfeld analysis further demonstrates surface properties and establishes accountability of various intermolecular interactions towards the stabilization of the complexes, emphasising, in particular, the importance of the C−H⋅⋅⋅O hydrogen bonds

Self-healing and shape-adaptive nanocomposite hydrogels with anti-inflammatory, antioxidant, antibacterial activities and hemostasis for real-time visual regeneration of diabetic wounds

Diabetic severe wounds are difficult to heal and regenerate, and are extremely challenging to manage in clinical practice with common wound dressings. There is a need to develop multifunctional dressings that meet the requirements for efficient treatment of diabetic wounds. Therefore, the nanocomposite hydrogel with oxidized chondroitin sulfate (OCS), carboxymethyl chitosan (CMC), and phenol red-modified ε-poly-l-lysine (EPL-PR) as the backbones, encapsulated with chondroitin sulfate-modified selenium nanoparticles (CS@SeNPs) and infinite coordination polymer nanomedicine (ICPs) composed of procyanidins, berberine hydrochloride and Fe(III), was designed and fabricated. The prepared nanocomposite hydrogel system allows for rapid in situ gelation and complete coverage of irregular wounds. In vivo and in vitro investigations demonstrate that the nanocomposite hydrogel shows excellent tissue adhesion, antibacterial activities, biocompatibility and free radical scavenging properties. The rapid hemostasis of the nanocomposite hydrogel is confirmed through hemorrhage models of liver and caudal amputation. All the advantages enable the nanocomposite hydrogel to effectively induce skin tissue remodeling, promote vascular and hair follicle regeneration, remove free radicals from wounds, and accelerate wound healing. The nanocomposite hydrogel can also successfully monitor the pH range of 5–10, thus enabling real-time visual monitoring of the wound healing phase, facilitating wound management in clinical settings. This multifunctional wound dressing opens up ideas for the treatment and management of diabetic full-thickness wounds.

Fluorescent Probes Based on Metal and Aggregation-induced Luminescent Organic Molecule Complexes for Bioimaging and Sensing Applications

Metal-Organic Coordination polymer (MOCPs) is an emerging class of inorganic-organic porous hybrid materials with infinite coordination polymers (CPs) or metal-organic backbones (MOFs) formed by the interaction between metal ions and organic ligands and ligand functional groups. The molecular structure of the organic ligands composing MOCPs is rich in variation, while inorganic metal ions generally have good photoelectromagnetic properties. Therefore, MOCPs have diverse structural variations, adjustable pore size, high stability and controllable synthesis, and have received wide attention in gas storage, multiphase catalysis, chemical sensing and biological applications. Fluorescence properties are one of the most widely used techniques for bioimaging and sensing detection. However, conventional luminescent groups are usually affected by aggregation-induced quenching (ACQ) effects. Aggregation-induced luminescence molecules (AIEs) based on metal-organic coordination polymers combine the advantages of organic AIEs and transition metal centers to improve photophysical properties and therapeutic effects.

A luminescent sensor based on in-situ formed copper nanocluster-loading terbium coordination polymer with multicolor response for identification of antibiotics

Identification of multiple antibiotics is of great interest owing to the requirement of food safety and pollution control in environment. Herein, a multicolor luminescent sensor (GT-GC) was designed based on an infinite coordination polymer (GT) formed by guanosine monophosphate (GMP) and lanthanoid ions Tb3+ as host matrix, and in-situ formed copper nanoclusters (CuNCs, GC) formed by glutathione and Cu2+ as guest species. TEM and SEM images showed that CuNCs further aggregated under the host-guest interaction. As a result, the as-prepared GT-GC not only emit characteristic luminescence of Tb3+ at 490, 544, 586 and 620 nm, but also emit the luminescence of CuNCs at 631 nm due to AIE effect. In addition, including the intrinsic luminescence of antibiotics in GT-GC at about 439 nm, the GT-GC exhibits 6-channel luminescence originated from three luminescence centers of Tb3+, CuNCs and antibiotics. In this work, 26 antibiotics were well identified based on the luminescence responses of the GT-GC and consequent linear discrimination analysis (LDA). The unknown antibiotics in real samples were also successfully identified. Due to the multi-color variation of GT-GC upon the addition of antibiotics, the visual on-site rapid detection of antibiotics was realized by a smartphone installed color recognition program.

Helical Organic and Inorganic Polymers.

Despite being a staple of synthetic plastics and biomolecules, helical polymers are scarcely studied with Gaussian-basis-set ab initio electron-correlated methods on an equal footing with molecules. This article introduces an ab initio second-order many-body Green's function [MBGF(2)] method with nondiagonal, frequency-dependent Dyson self-energy for infinite helical polymers using screw-axis-symmetry-adapted Gaussian-spherical-harmonics basis functions. Together with the Gaussian-basis-set density-functional theory for energies, analytical atomic forces, translational-period force, and helical-angle force, it can compute correlated energy, quasiparticle energy bands, structures, and vibrational frequencies of an infinite helical polymer, which smoothly converge at the corresponding oligomer results. These methods can handle incommensurable structures, which have an infinite translational period and are hard to characterize by any other method, just as efficiently as commensurable structures. We apply them to polyethylene (2/1 helix), polyacetylene (Peierls' system) and polytetrafluoroethylene (13/6 helix) to establish the quantitative accuracy of MBGF(2)/cc-pVDZ in simulating their (angle-resolved) ultraviolet photoelectron spectra and of B3LYP/cc-pVDZ or 6-31G** in reproducing their structures, infrared and Raman band positions, phonon dispersions, and (coherent and incoherent) inelastic neutron scattering spectra. We then predict the same properties for infinitely catenated chains of nitrogen or oxygen and discuss their possible metastable existence under ambient conditions. They include planar zigzag polyazene (N2)x (Peierls' system), 11/3-helical isotactic polyazane (NH)x, 9/4-helical isotactic polyfluoroazane (NF)x, and 7/2-helical polyoxane (O)x as potential high-energy-density materials.