Organic Backbone Research Articles

Reproducible Superinsulation Materials: Organosilica-Based Hybrid Aerogels with Flexibility Control.

In this study, we report highly crosslinked hybrid aerogels with an organic backbone based on vinylmethyldimethoxysilane (VMDMS) with tuneable properties. For an improved and highly reproducible synthesis, a prepolymer based on 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane (D4V4) and VMDMS as monomers was prepared and purified. Di-tert-butylperoxide (DTBP) concentrations of 1 mol% initiate the radical polymerization of the mentioned monomers to achieve high yields of polymers. After purification, the obtained viscous polyorganosilane precursor could be reproducibly crosslinked with dimethyldimethoxysilane (DMDMS) or methyltrimethoxysilane (MTMS) to form gels in benzylic alcohol (BzOH), water (H2O) and tetramethylammonium hydroxide (TMAOH). Whereas freeze-drying these silica-based hybrid aerogels led to high thermal conductivity (>20 mW m-1K-1) and very fragile materials, useful aerogels were obtained via solvent exchange and supercritical drying with CO2. The DMDMS-based aerogels exhibit enhanced compressibility (31% at 7 kPa) and low thermal conductivity (16.5 mW m-1K-1) with densities around (0.111 g cm-3). The use of MTMS results in aerogels with lower compressibility (21% at 7 kPa) and higher density (0.124 g cm-3) but excellent insulating properties (14.8 mW m-1K-1).

Increasing catalytic efficiency of cobalt centers in oxygen reduction reaction - Evidence from cobalt with salen ligands polymer complex

Substantial research is performed for cobalt-based catalysts for various applications in catalysis, including oxygen reduction reaction (ORR) catalysis in nonaqueous electrolytes. Cobalt exhibits high catalytic activity due to partially filled d-orbitals, which promote the formation of chemisorption bonds with various molecules. The catalytic activity of metal centers can be influenced both by changing their immediate environment and by varying the reaction conditions. This paper investigates the influence of solvent type, electrolyte concentration, and organic framework conductivity on the efficiency of ORR catalysis in non-aqueous electrolytes as illustrated by poly-CoSal polymer complex. The findings show that the increase in the solvent donor number of and conductivity of the organic backbone leads to highly efficient cobalt catalysts, which can be potentially be applied in oxygen cathodes of Li-O2 batteries. CoSal-based catalysts increase the discharge voltage of Li-O2 cells and can operate in dry atmospheric air.

Single‐Molecule Conductance of Staffanes

We report the first conductance measurements of [n]staffane oligomers in single‐molecule junctions. Our studies reveal two quantum transport characteristics unique to staffanes that emerge from their strained bicyclic structure. First, though staffanes are composed of weakly conjugated C‐C σ‐bonds, staffanes carry a shallower conductance decay value (β = 0.84 ± 0.02 n‐1) than alkane chain analogs (β = 0.96 ± 0.03 n‐1) when measured with the scanning tunneling microscopy break junction (STM‐BJ) technique. Staffanes are more conductive than other σ‐bonded organic backbones in the literature on a per atom basis. Density functional theory calculations suggest staffane backbones are effective conduits for charge transport because their significant bicyclic ring strain destabilizes the HOMO‐2 energy, aligning it more closely with the Fermi energy as oligomer order increases. Second, the monostaffane is significantly lower conducting than expected. DFT calculations suggest that short monostaffanes sterically enforce insulating gauche interelectrode orientations over syn orientations. Meanwhile, [2‐5]staffane wires may accommodate axial mechanical strain by “rod‐bending”. These findings show for the first time how bicyclic ring strain can enhance charge transmission in saturated molecular wires. These studies showcase the STM‐BJ technique as a valuable tool for uncovering the stereoelectronic proclivities of molecules at material interfaces.

Single-Molecule Conductance of Staffanes.

We report the first conductance measurements of [n]staffane (bicyclopentane) oligomers in single-molecule junctions. Our studies reveal two quantum transport characteristics unique to staffanes that emerge from their strained bicyclic structure. First, though staffanes are composed of weakly conjugated C-C σ-bonds, staffanes carry a shallower conductance decay value (β=0.84±0.02 n-1) than alkane chain analogs (β=0.96±0.03 n-1) when measured with the scanning tunneling microscopy break junction (STM-BJ) technique. Staffanes are thus more conductive than other σ-bonded organic backbones reported in the literature on a per atom basis. Density functional theory (DFT) calculations suggest staffane backbones are more effective conduits for charge transport because their significant bicyclic ring strain destabilizes the HOMO-2 energy, aligning it more closely with the Fermi energy of gold electrodes as oligomer order increases. Second, the monostaffane is significantly lower conducting than expected. DFT calculations suggest that short monostaffanes sterically enforce insulating gauche interelectrode orientations over syn orientations; these steric effects are alleviated in longer staffanes. Moreover, we find that [2-5]staffane wires may accommodate axial mechanical strain by "rod-bending". These findings show for the first time how bicyclic ring strain can enhance charge transmission in saturated molecular wires. These studies showcase the STM-BJ technique as a valuable tool for uncovering the stereoelectronic proclivities of molecules at material interfaces.

Biochars from chlorine-rich feedstock are low in polychlorinated dioxins, furans and biphenyls

Chlorinated aromatic hydrocarbons like polychlorinated dibenzo-p-dioxins and -furans (PCDD/F) and polychlorinated biphenyls (PCB) are omnipresent in the environment due to historic production, use, and (unintended) release. Nowadays, their emission and maximum concentration in environmental compartments is strictly regulated. During biochar production, PCDD/F and PCB may be formed and retained on the solid pyrolysis product. Industrial biochars certified, e.g., under the European Biochar Certificate (EBC), exhibit concentrations that were always well below threshold values for soil application and even animal feed. However, this has not been sufficiently tested for chlorine (Cl) rich organic material such as marine biomass or polyvinyl chloride (PVC) contaminated feedstock. Here, we analyzed PCDD/F and PCB contamination in biochars produced at different temperatures from different biomasses with comparatively high Cl contents in the range from 0.2 % to 3.8 % (w/w, seagrass, two types of saltwater macroalgae, tobacco stalks, and PVC contaminated wood). All of the biochars produced showed PCDD/F and PCB contents well below the applicable threshold values given by the EBC (< 20 ng TEQ kg−1 for PCDD/F and < 2×105 ng kg−1 for PCB). The EBC thresholds were undershot by a minimum of factor 1.5 for PCDD/F (mostly factor 20) and by a minimum of factor 90 for PCB. Between 1 and 27 ppb of feedstock Cl were transformed to Cl bound in PCDD/F and PCB in the biochars. No consistent correlation between biomass Cl contents and contents of PCDD/F and PCB were found but higher Cl contents in the feedstock led to a more diverse PCDD/F congener pattern in the biochars. Pyrolysis of PVC-amended wood resulted in consistently higher contamination of PCDD/F and PCB in the biochars compared to pyrolysis of the other biomasses, potentially due to differences in Cl speciation in the feedstocks i.e., Cl in PVC is already covalently bound to an organic carbon backbone. A high contamination in PCDD/F and PCB in biochar was intentionally triggered by separation of pyrogas and biochar in the reactor at < 300 °C to promote condensation of contaminants on the solid product. Between 20 % and 80 % of feedstock Cl was released via the pyrogas, i.e., neutralization of HCl in burnt pyrogas might be necessary when pyrolyzing Cl-rich feedstock in industrial biochar production. Our results indicate that biochars produced from Cl-rich feedstocks with proper biochar production process control are conform with European certification guidelines for PCDD/F and PCB contamination. The results open the opportunity to exploit and valorize so far non-used marine or otherwise Cl enriched biomasses for the production of biochar and carbon sinks.

Polydimethylsiloxane Organic-Inorganic Composite Drug Reservoir with Gliclazide.

A novel organic-inorganic gliclazide-loaded composite bead was developed by an ionic gelation process using acidified CaCl2, chitosan and tetraethylorthosilicate (TEOS) as a crosslinker. The beads were manufactured by crosslinking an inorganic silicone elastomer (-OH terminated polydimethylsiloxane, PDMS) with TEOS at different ratios before grafting onto an organic backbone (Na-alginate) using a 32 factorial experimental design. Gliclazide's encapsulation efficiency (EE%) and drug release over 8 h (% DR 8 h) were set as dependent responses for the optimisation of a pharmaceutical formula (herein referred to as 'G op') by response surface methodology. EE % and %DR 8 h of G op were 93.48% ± 0.19 and 70.29% ± 0.18, respectively. G op exhibited a controlled release of gliclazide that follows the Korsmeyer-Peppas kinetic model (R2 = 0.95) with super case II transport and pH-dependent swelling behaviour. In vitro testing of G op showed 92.17% ± 1.18 cell viability upon testing on C2C12 myoblasts, indicating the compatibility of this novel biomaterial platform with skeletal muscle drug delivery.

Double-inverse-opal structured films of a hydrogel framework and mobile inorganic particles

Double-inverse-opal (DIO) structured assemblies are three-dimensionally ordered porous materials containing core particles inside. In this work, DIO structured films composed of mobile inorganic colloidal particles within an organic polymer gel framework were developed. As the organic backbone, a poly(N-isopropylacrylamide) gel (PNIPAM gel) was employed to enhance the flexibility and processability of the films. A three-dimensional periodic structure of fluorescent-labelled silica core particles in the film was observed with confocal microscopy. Thermally induced volume transitions of the PNIPAM gels were observed, which showed the potential for stimuli-responsive optical materials. By selective etching of the sacrificial shell layers surrounding the core particles, cavities formed around the cores, and they exhibited random Brownian motion inside these pockets in the film. As a new type of organic-inorganic composite material, the proposed DIO structured films possessed unique characteristics originating from the combination of a flexible backbone and mobile cores, applicable to stimuli-responsive photonic devices, reusable catalytic particle assemblies, etc.

Observations regarding the synthesis and redox chemistry of heterobimetallic uranyl complexes containing Group 10 metals

Abstract Literature reports have demonstrated that Schiff-base-type ligands can serve as robust platforms for the synthesis of heterobimetallic complexes containing transition metals and the uranyl dication (UO2 2+). However, efforts have not advanced to include either synthesis of complexes containing second- or third-row transition metals or measurement of the redox properties of the corresponding heterobimetallic complexes, despite the significance of actinide redox in studies of nuclear fuel reprocessing and separations. Here, metalloligands denoted [Ni], [Pd], and [Pt] that contain the corresponding Group 10 metals have been prepared and a synthetic strategy to access species incorporating the uranyl ion (UO2 2+) has been explored, toward the goal of understanding how the secondary metals could tune uranium-centered redox chemistry. The synthesis and redox characterization of the bimetallic complex [Ni,UO2] was achieved, and factors that appear to govern extension of the chosen synthetic strategy to complexes with Pd and Pt are reported here. Infrared and solid-state structural data from X-ray diffraction analysis of the metalloligands [Pd] and [Pt] show that the metal centers in these complexes adopt the expected square planar geometries, while the structure of the bimetallic [Ni,UO2] reveals that the uranyl moiety influences the coordination environment of Ni(II), including inducement of a puckering of the ligand backbone of the complex in which the phenyl rings fold around the nickel-containing core in an umbrella-shaped fashion. Cyclic voltammetric data collected on the heterobimetallic complexes of both Ni(II) and Pd(II) provide evidence for uranium-centered redox cycling, as well as for the accessibility of other reductions that could be associated with Ni(II) or the organic ligand backbone. Taken together, these results highlight the unique redox behaviors that can be observed in multimetallic systems and design concepts that could be useful for accessing tunable multimetallic complexes containing the uranyl dication.

Carbon-dots encapsulated luminescent metal–organic frameworks@surface molecularly imprinted polymer: A facile fluorescent probe for the determination of chloramphenicol

In this study, carbon dots (CDs)-encapsulated luminescent metal–organic frameworks@surface molecularly imprinted polymer (CDs@MOF@SMIP) was facilely prepared and applied as fluorescent probe for specific identification and sensitive detection of chloramphenicol (CAP) in food. Fluorescent CDs, serving as signal tags, were encapsulated within metal–organic backbones (ZIF-8), yielding luminescent MOF materials (CDs@ZIF-8). The synthesized CDs, CDs@ZIF-8 and CDs@ZIF-8@SMIP were investigated by morphological and structural characterizations (UV–Vis, XRD, FT-IR, BET, TEM). The CDs@ZIF-8@SMIP probe was demonstrated to have remarkable selectivity and sensitivity towards CAP. Its fluorescence decreased linearly with CAP concentration from 0.323 μg L-1 (0.001 μM) to 8075.0 μg L-1 (25.0 μM), featuring a low detection limit of 0.08 μg L-1. The CDs@ZIF-8@SMIP-based fluorescence strategy achieved satisfactory recoveries (95.5 % − 101.0 %) in CAP-spiked commercial foods with RSD < 4.4 % (n = 3). These results indicate that this method can effectively detect trace CAP in food matrices and has broad application prospects.

Photoswitchable coordination cages.

Stimuli-responsive behaviour is key to the design of smart materials, surfaces, nano-systems and effector molecules, allowing their application as switchable catalysts, molecular transporters, bioimaging probes or caged drugs. Supramolecular chemistry has embraced the widespread integration of photoswitches because of their precise spatiotemporal addressability and waste-free nature. In the vibrant area of discrete metal-mediated self-assembly, however, photoswitches are still rarely employed. Only recently has it been shown that embedding photoswitches into the organic backbones of coordination cages enables control of their host and material properties and thus unlocks the hitherto unexploited dynamic adaptivity of such systems. Here we discuss four cases where triggering ligand-integrated photoswitches leads to (1) control over disassembly/reassembly, (2) bi-stable switching between defined states, (3) interplay with thermal processes in metastable systems and (4) light-fuelled dissipative self-assembly. We highlight first clues concerning the relationship between fundamental photophysics and dynamic assembly equilibria and propose directions for future development.

Organic iontronic memristors for artificial synapses and bionic neuromorphic computing.

To tackle the current crisis of Moore's law, a sophisticated strategy entails the development of multistable memristors, bionic artificial synapses, logic circuits and brain-inspired neuromorphic computing. In comparison with conventional electronic systems, iontronic memristors offer greater potential for the manifestation of artificial intelligence and brain-machine interaction. Organic iontronic memristive materials (OIMs), which possess an organic backbone and exhibit stoichiometric ionic states, have emerged as pivotal contenders for the realization of high-performance bionic iontronic memristors. In this review, a comprehensive analysis of the progress and prospects of OIMs is presented, encompassing their inherent advantages, diverse types, synthesis methodologies, and wide-ranging applications in memristive devices. Predictably, the field of OIMs, as a rapidly developing research subject, presents an exciting opportunity for the development of highly efficient neuro-iontronic systems in areas such as in-sensor computing devices, artificial synapses, and human perception.

2D Hybrid Perovskites Employing an Organic Cation Paired with a Neutral Molecule.

Two-dimensional (2D) hybrid perovskites harness the chemical and structural versatility of organic compounds. Here, we explore 2D perovskites that incorporate both a first organic component, a primary ammonium cation, and a second neutral organic module. Through the experimental examination of 42 organic pairs with a range of functional groups and organic backbones, we identify five crystallization scenarios that occur upon mixing. Only one leads to the cointercalation of the organic modules with distinct and extended interlayer spacing, which is observed with the aid of X-ray diffraction (XRD) pattern analysis combined with cross-sectional transmission electron microscopy (TEM) and elemental analysis. We present a picture in which complementary pairs, capable of forming intermolecular bonds, cocrystallize with multiple structural arrangements. These arrangements are a function of the ratio of organic content, annealing temperature, and substrate surface characteristics. We highlight how noncovalent bonds, particularly hydrogen and halogen bonding, enable the influence over the organic sublattice in hybrid halide perovskites.

Collective production of hydrogen sulfide gas enables budding yeast lacking MET17 to overcome their metabolic defect.

Assimilation of sulfur is vital to all organisms. In S. cerevisiae, inorganic sulfate is first reduced to sulfide, which is then affixed to an organic carbon backbone by the Met17 enzyme. The resulting homocysteine can then be converted to all other essential organosulfurs such as methionine, cysteine, and glutathione. This pathway has been known for nearly half a century, and met17 mutants have long been classified as organosulfur auxotrophs, which are unable to grow on sulfate as their sole sulfur source. Surprisingly, we found that met17Δ could grow on sulfate, albeit only at sufficiently high cell densities. We show that the accumulation of hydrogen sulfide gas underpins this density-dependent growth of met17Δ on sulfate and that the locus YLL058W (HSU1) enables met17Δ cells to assimilate hydrogen sulfide. Hsu1 protein is induced during sulfur starvation and under exposure to high sulfide concentrations in wild-type cells, and the gene has a pleiotropic role in sulfur assimilation. In a mathematical model, the low efficiency of sulfide assimilation in met17Δ can explain the observed density-dependent growth of met17Δ on sulfate. Thus, having uncovered and explained the paradoxical growth of a commonly used "auxotroph," our findings may impact the design of future studies in yeast genetics, metabolism, and volatile-mediated microbial interactions.

A self-calibration electrochemical sensor for ultrasensitive detection of glutathione based on metal–organic framework-derived Cu nanoparticles/nitrogen-doped porous carbon composites

Glutathione (GSH) is considered to be one of the main factors in maintaining redox homeostasis in living organisms, and alterations in GSH levels are closely associated with many diseases. In this paper, polyvinylpyrrolidone (PVP)-doped copper metal–organic backbone (N-Cu-MOF) was synthesized and N-Cu-MOF was pyrolyzed to produce nano-copper modified nitrogen porous carbon materials (CuNPs@NPC). The CuNPs@NPC modified electrode showed an increased oxidation current due to the presence of CuCl solid-state electrochemistry signal amplification strategy. With the addition of GSH, CuCl was gradually converted to Cu-GSH as a non-electrically active material, which triggered an “extrusion effect” and resulted in a decreased peak current. Meanwhile, the peak current of the internal reference ratio (acetaminophen, APAP), which was added to the electrolyte solution, was almost unchanged. Using the ratio of the peak current variation (ΔICu/IAPAP) as the output signal, the CuNPs@NPC modified electrode achieved an ultra-sensitive detection of GSH in the range of 0.1 nM–10 μM. The detection limit was as low as 0.067 nM. In the detection of human cervical cancer cell lysate, the sensor has high accuracy and selectivity for GSH, which can bring enlightenment for the early diagnosis of clinical diseases.

The cactus bulb-shaped metal-S-C/N nanoparticles supported by highly conductive channels for efficient electrocatalytic hydrogen evolution reaction

Accelerating electron transfer and exposing active sites are key factors that could improve electrocatalytic hydrogen evolution reaction (HER). In this study, Co3S4-Ni3S2-C/N, the cactus bulb-shaped nanoparticles based on metal-organic frameworks (MOFs), were successfully prepared. The catalyst requires only 101 and 227 mV overpotential to reach current densities of 20 and 100 mA cm−2, respectively, in 1 M KOH. The high catalytic activity is attributed to the confinement effect achieved by introducing 2-aminoterephthalic acid as a precursor, allowing the catalyst to have a small particle size and fully exposed metal active sites. Moreover, the catalyst has a highly conductive metal-S-C/N channel that effectively reduces the intrinsic charge transfer resistance of the catalytic electrode, improves its conductivity, and modulates the electron density at the metal active site. Furthermore, compared to other crystal planes, the exposed (111) crystal plane of Co3S4 provides the most octahedral coordination of high spin state Co3+, which is highly catalytically active. This makes it the dominant crystal plane for catalysis. Through spatial confinement effect to limit metal sulfide particle size and introducing an organic backbone to create highly conductive metal-S-C/N channels, our study provides a general approach to developing highly active catalytic materials.

Constructed a bimetallic synergistic organic backbones electrode by the electrochemical deposition for high-performance flexible supercapacitors

A simple and convenient cathodic electrodeposition was developed to prepare a cerium-nickel-bimetallic organic framework (Ce/Ni-MOFs) on carbon cloth and directly used as a supercapacitor electrode material. The two metal ions produced a good synergistic effect and formed a unique folded morphology. The higher capacitance, charge transfer and excellent multiplicative performance of the bimetallic MOFs compared with the monometallic MOFs were found by electrochemical tests, which also demonstrated the scalability of the cathodic electrodeposition method. In addition, the flexible supercapacitor assembled based on Ce/Ni-MOFs and graphene oxide (denoted as Ce/Ni-MOFs//GO) achieved a high voltage of 1.7 V and exhibited high capacitance (298.8 mF cm−2), excellent energy density (120.1 μWh cm−2) and good durability (93 % after 5000 cycles).

Difluoroalkylation of Anilines via Photoinduced Methods.

The development of sustainable and mild protocols for the fluoroalkylation of organic backbones is of current interest in chemical organic synthesis. Herein, we present operationally simple and practical transition-metal-free methods for the preparation of difluoroalkyl anilines. First, a visible-light organophotocatalytic system working via oxidative quenching is described, providing access to a wide range of difluoroalkyl anilines under mild conditions. In addition, the formation of an unprecedented electron donor-acceptor (EDA) complex between anilines and ethyl difluoroiodoacetate is reported and exploited as an alternative, efficient, and straightforward strategy to prepare difluoroalkyl derivatives.

Porphyrin-based metal-organic frameworks enhanced electrochemiluminescence (ECL) by overcoming aggregation-caused quenching: A new ECL emitter for the detection of trenbolone

The development of new electrochemiluminescence (ECL) luminophores has become a hot research topic in the field of ECL. Metal-organic frameworks (MOFs) are widely used in ECL sensors due to their excellent ECL performance, high porosity, and abundant surface functional groups. In the work, we developed a cerium-based organic backbone as an ECL luminophor using 5,10,15,20-tetrakis(4-carboxyphenyl)-porphyrin (TCPP) as organic ligand for the detection of trenbolone (TRE). Importantly, the Ce-MOFs can effectively prevent the self-aggregation and self-quenching of TCPP, so that the ECL signal is amplified. To further improve the conductivity and antigen loading capacity of the Ce-MOFs, platinum nanosheets (Pt NPs) were modified at its surface (Pt NPs@MOFs). The Au-ZnO with good biocompatibility is used as the substrate material to load that antibody through the Au-NH2. Based on the above strategy, we constructed a competitive immunosensor to achieve a highly sensitive detection of TRE. Under suitable circumstances, it was discovered that the ECL sensor had a linear relationship with the logarithm of the TRE concentration, with a limit of detection (LOD) of 3.61 fg/mL (S/N = 3). This work provides direction for the application of organic luminescent porphyrins and their derivatives in ECL sensors.

Autoionization from the plasmon resonance in isolated 1-cyanonaphthalene.

Polycyclic aromatic hydrocarbons have widely been conjectured to be ubiquitous in space, as supported by the recent discovery of two isomers of cyanonaphthalene, indene, and 2-cyanoindene in the Taurus molecular cloud-1 using radioastronomy. Here, the photoionization dynamics of 1-cyanonaphthalene (1-CNN) are investigated using synchrotron radiation over the hν = 9.0-19.5eV range, revealing that prompt autoionization from the plasmon resonance dominates the photophysics for hν = 11.5-16.0eV. Minimal photo-induced dissociation, whether originating from an excited state impulsive bond rupture or through internal conversion followed by a statistical bond cleavage process, occurs over the microsecond timescale (as limited by the experimental setup). The direct photoionization cross section and photoelectron angular distributions are simulated using an ezDyson model combining Dyson orbitals with Coulomb wave photoejection. When considering these data in conjunction with recent radiative cooling measurements on 1-CNN+, which showed that cations formed with up to 5eV of internal energy efficiently stabilize through recurrent fluorescence, we conclude that the organic backbone of 1-CNN is resilient to photodestruction by VUV and soft XUV radiation. These dynamics may prove to be a common feature for the survival of small polycyclic aromatic hydrocarbons in space, provided that the cations have a suitable electronic structure to support recurrent fluorescence.

Fractal characteristics for coal chemical structure: Principle, methodology and implication

Despite coal chemical structure's importance as the organic backbone for hydrocarbon production, the fractal characteristics for coal chemical structure remains unexplored. Therefore, this paper proposed a novel method to calculate the fractal dimension Df for coal chemical structure. The principle and methodology of the proposed method were deduced and summarized in detail. This method was applied to calculate the fractal dimension Df for the coal chemical structure from lignite to anthracite. The research results indicate that the fractal dimension Df for coal chemical structure decreases first and then increases with coalification. The turning point of the variation trend of fractal dimension Df and coalification corresponds to the second coalification jump (maximum vitrinite reflectance Ro, max = 1.30 %). This study has achieved the micro characterization on coal chemical structure at molecular scale, which has potential application value on the functional properties analysis and molecular synthesis design of coal-based material research fields.