Linker Molecules Research Articles

Local current analysis on defective zigzag graphene nanoribbons devices for biosensor material applications.

In this contribution, we aim at investigating the mechanism of biosensing in graphene-based materials from first principles. Inspired by recent experiments, we construct an atomistic model composed of a pyrene molecule serving as a linker fragment, which is used in experiment to attach certain aptamers, and a defective zigzag graphene nanoribbons (ZGNRs). Density functional theory including dispersive interaction is employed to study the energetics of the linker absorption on the defective ZGNRs. Combining non-equilibrium Green's function and the Landauer formalism, the total current-bias voltage dependence through the device is evaluated. Modifying the distance between the linker molecule and the nanojunction plane reveals a quantitative change in the total current-bias voltage dependence, which correlates to the experimental measurements. In order to illuminate the geometric origin of these variation observed in the considered systems, the local currents through the device are investigated using the method originally introduced by Evers and co-workers. In our new implementation, the numerical efficiency is improved by applying sparse matrix storage and spectral filtering techniques, without compromising the resolution of the local currents. Local current density maps qualitatively demonstrate the local variation of the interference between the linker molecule and the nanojunction plane.

Synchronization of Nanoparticle Sensitization and Radiosensitizing Chemotherapy through Cell Cycle Arrest Achieving Ultralow X-ray Dose Delivery to Pancreatic Tumors.

Pancreatic cancer is among the leading causes of cancer-related death and remains a formidable therapeutic challenge. To date, surgical resection and chemotherapy have been the standards of care. Methotrexate (MTX), which is recognized as a refractory drug for pancreatic cells, was conjugated to the surface of LiYF4:Ce3+ nanoparticles (NP-MTX) through a photocleavable linker molecule. When LiYF4:Ce3+ NPs are stimulated by X-rays, they emit light, which induces the photocleavage of the photolabile linker molecule to release MTX. MTX can target pancreatic tumors, which overexpress folic acid (FA) receptors and are internalized into the cell through receptor-mediated endocytosis. The synergistic effect of the NP-MTX treatment initiated by X-ray irradiation occurs due to the combination of nanoparticle sensitization and the radiosensitizing chemotherapy of the photocleaved MTX molecule. This dual sensitization effect mediated by NP-MTX enabled 40% dose enhancement, which corresponded with an increase in the generation of cytotoxic cellular reactive oxygen species (ROS) and enhanced S phase arrest within the cell cycle. The delivery of an ultralow radiation dose of 0.1 Gy resulted in the photocleavage of MTX from NP-MTX, and this strategy demonstrated in vivo efficacy against AsPC-1 and PANC-1 xenografted pancreatic tumors.

Simple fluorescence optosensing probe for spermine based on ciprofloxacin-Tb3+ complexation.

We developed a facile detection method of spermine based on the fluorescence (FL) quenching of the ciprofloxacin-Tb3+ complex, which shows astrong green emission. Ciprofloxacin (CP) makes efficient bondings to Tb3+ ion as a linker molecule through carboxylic and ketone groups to form a kind of lanthanide coordination polymer. The addition of spermine that competes with Tb3+ ions for the interaction with CP due to its positive charge brings about weakened coordination linkage of CP and Tb3+. The probe exhibited high sensitivity, selectivity, and good linearity in the range of 2–180 μM with a low limit of detection of 0.17 μM. Moreover, we applied this method on the paper strip test (PST), along with the integration of a smartphone and Arduino-based device. The practical reliability of the developed probe was evaluated on human serum samples with acceptable analytical results.

TiO₂-Chitosan Hybrid Materials for Drug Delivery Applications: Conjugation Reaction with a Model Drug and Evaluation of the Functional Properties.

The combination of TiO₂ and chitosan is known to allow the achievement of implantable devices which combines the mechanical properties of TiO₂, with the presence of chitosan, which ensures antibacterial properties combined with an in-situ drug-delivery of biomolecules physisorbed and/or covalently linked to chitosan. In this study, 5-aminofluorescein (5-AF), a derivative of fluorescein containing a primary amino group, has been used as model molecule to simulate a drug. This dye is characterized by low cost and low toxicity, and due to its high molar absorptivity it can easily be detected by means of absorption and emission spectroscopies. The combination of 5-AF and maleic anhydride (MA) with TiO₂-chitosan materials has generated a range of novel hybrid materials tailored to applications in localized stimuli-responsive drug delivery systems. Maleic anhydride has been used as pH sensitive spacer for the covalent functionalization of the TiO₂-chitosan hybrid with MA as linker molecule. This functionalization allowed to obtain a pH-sensitive hybrid material. The efficiency of the functionalization has been verified by means of different physico-chemical characterization techniques. The behaviour of the functionalized materials is related to different parameters, among which the ratio between physisorbed/coordinated and chemisorbed 5-AF and the matrix degradation. Moreover, delivery tests in simulated body solutions at different pH have been performed showing a pH-sensitive drug delivery behaviour and indicating that the release of 5-AF is favoured at basic pH.

金属有機構造体を用いた分子ふるい作用によるパラキシレン分離

Metal-organic frameworks (MOFs) consisting of organic linker such as terephthalic acid or fumaric acid and cation such as Al3+ or Zr4+ were prepared by the hydro- and solvo-thermal methods. MOFs were characterized by XRD, N2 adsorption-desorption isotherm and FE-SEM. The prepared MOFs were mostly crystalline and phase-pure. MOFs were used as the column packing for chromatographic separation of p-xylene from a xylene mixture. With MOFs prepared with large linker molecules, xylenes diffused into the micropores and eluted fundamentally according to kinetic molecular size. With MOFs of low crystallinity or very small micropores, xylenes passed through spaces between MOF particles and separation of p-xylene was not possible. With MOFs consisting of fumaric acid and Zr4+ (MOF-801), o- and m-xylenes eluted quickly and p-xylene eluted later, because o- and m-xylenes passed through spaces between MOF particles, whereas p-xylene diffused into the micropores of MOF-801. Temperature dependence of separation with MOF-801 revealed that at temperatures lower than 140 °C, xylenes could not diffuse into the micropores. At 170 °C, the smallest p-xylene diffused into the micropores and thus p-xylene could be separated from o- and m-xylenes by the molecular-sieving mechanism. MOF-801 was robust against repeated exposure to xylenes and heat treatment at high temperature for elution of adsorbed xylene.

NH2 linker for femtomolar label-free detection with reduced graphene oxide screen-printed electrodes

Surface modification with linker molecules is necessary for the effective immobilization of bioreceptors and for improving the performance of biosensors. In this work, we present a novel functionalization technique to attach amine (NH2) linker on graphene-based sensor surfaces. This is achieved by reacting the commercially available reduced graphene oxide (rGO) screen-printed electrodes (SPEs) with ammonia solution at room temperature. The NH2 linkers are attached predominantly on the edge and defect sites of rGO SPE through chemisorption as shown by XPS, Raman and FTIR analysis. The functionalized SPEs are further characterized using morphological and electrochemical techniques. The validation of the linker is done by using the functionalized SPEs for the detection of Aβ1-40 and Aβ1-42 biomarkers. A limit of detection (LOD) of 9.51 fM is achieved over a linear dynamic range of 10 fM-10 pM for Aβ1-40. Similarly, LOD of 8.65 fM is achieved over a linear dynamic range of 10 fM-50 pM for Aβ1-42. This excellent sensitivity is attributed to the functionalization of rGO surface with NH2 linker, which provides a large number of binding sites for bioreceptors. High specificity for the target biomarkers over interfering Aβ and ApoE ε4 species is also demonstrated. The biosensor is further validated for the analysis of spiked human plasma. The proposed technique provides a promising approach for improving the detection sensitivity of graphene biosensors for application in biofluids based minimally invasive and cost- and time-efficient disease diagnosis.

The Modulating Effect of Ethanol on the Morphology of a Zr-Based Metal–Organic Framework at Room Temperature in a Cosolvent System

We report that ethanol, used together with water, plays a crucial role in tuning the structures of a zirconium-based metal–organic framework and the 12-connected MOF-801, as well as the possible mechanisms of this modulating effect. By employing a cosolvent system of ethanol and water at just under room temperature without the presence of a monotopic carboxylic acid as the modulator, MOF-801 in various morphologies of different sizes could be synthesized. A linear correlation between the ethanol/water ratio and the crystal sizes is also demonstrated. The growth mechanism is mainly explained by ethanol’s bonding with the metal ion clusters and the Marangoni flow effect. Ethanol competes with the linker molecules in coordinating with the Zr metal clusters, a role similar to that of the modulators. The Marangoni flow effect, which dominates at a certain solvent ratio, further promotes the 1D alignment of the MOF-801 crystals.

Mechanism of Heterogenization of Dirhodium Catalysts: Insights from DFT Calculations.

Dirhodium(II) complexes such as [Rh2(TFA)4] bound to a functionalized mesoporous SBA-15 carrier material have proven to be valuable candidates for heterogeneous catalysis in the field of pharmaceutical synthesis. However, the mechanistic steps of immobilization by linker molecules containing carboxyl or amine functionalities remain the subject of discussion. Here we present a theoretical study of possible mechanistic binding pathways for the [Rh2(TFA)4] complex through model representations of synthetically investigated linkers, namely n-butylamine and n-butyric acid. Experimentally proposed intermediates of the immobilization process are investigated and analyzed by density functional theory calculations to gain insights into structural properties and the influence of solvation. An evaluation of the thermodynamic data for all identified intermediates allowed distinguishing between two possible reaction pathways that are characterized by a first axial complexation of either n-butyric acid or n-butylamine. In agreement with results from NMR spectroscopy, singly or doubly n-butylamine-fixated complexes were found to present possible immobilization products. Initial binding through a carboxy-functionalized linker is proposed as the most favorable reaction pathway for the formation of the mixed linker pattern [Rh2(TFA)3]·(n-butylamine)·(n-butyrate). The linkers n-butyric acid and n-butyrate, respectively, are found to exhibit an unaltered binding affinity to the dirhodium complex despite their protonation states, indicating invariance to the acidic environment unlike an immobilization by n-butylamine. These results present a theoretical framework for the rationalization of observed product distributions while also providing inspiration and guidance for the preparation of functionalized heterogeneous SBA-15/dirhodium catalyst systems.

Molecular bridge-mediated ultralow-power gas sensing

We report the electrical detection of captured gases through measurement of the quantum tunneling characteristics of gas-mediated molecular junctions formed across nanogaps. The gas-sensing nanogap device consists of a pair of vertically stacked gold electrodes separated by an insulating 6 nm spacer (~1.5 nm of sputtered α-Si and ~4.5 nm ALD SiO2), which is notched ~10 nm into the stack between the gold electrodes. The exposed gold surface is functionalized with a self-assembled monolayer (SAM) of conjugated thiol linker molecules. When the device is exposed to a target gas (1,5-diaminopentane), the SAM layer electrostatically captures the target gas molecules, forming a molecular bridge across the nanogap. The gas capture lowers the barrier potential for electron tunneling across the notched edge region, from ~5 eV to ~0.9 eV and establishes additional conducting paths for charge transport between the gold electrodes, leading to a substantial decrease in junction resistance. We demonstrated an output resistance change of >108 times upon exposure to 80 ppm diamine target gas as well as ultralow standby power consumption of <15 pW, confirming electron tunneling through molecular bridges for ultralow-power gas sensing.

Graphene FET Sensors for Alzheimer's Disease Protein Biomarker Clusterin Detection.

We report on the fabrication and characterisation of graphene field-effect transistor (GFET) biosensors for the detection of Clusterin, a prominent protein biomarker of Alzheimer’s disease (AD). The GFET sensors were fabricated on Si/SiO2 substrate using photolithographic patterning and metal lift-off techniques with evaporated chromium and sputtered gold contacts. Raman Spectroscopy was performed on the devices to determine the quality of the graphene. The GFETs were annealed to improve their performance before the channels were functionalized by immobilising the graphene surface with linker molecules and anti-Clusterin antibodies. Concentration of linker molecules was also independently verified by absorption spectroscopy using the highly collimated micro-beam light of Diamond B23 beamline. The detection was achieved through the binding reaction between the antibody and varying concentrations of Clusterin antigen from 1 to 100 pg/mL, as well as specificity tests using human chorionic gonadotropin (hCG), a glycoprotein risk biomarker of certain cancers. The GFETs were characterized using direct current (DC) 4-probe electrical resistance (4-PER) measurements, which demonstrated a limit of detection of the biosensors to be ∼ 300 fg/mL (4 fM). Comparison with back-gated Dirac voltage shifts with varying concentration of Clusterin show 4-PER measurements to be more accurate, at present, and point to a requirement for further optimisation of the fabrication processes for our next generation of GFET sensors. Thus, we have successfully fabricated a promising set of GFET biosensors for the detection of Clusterin protein biomarker. The developed GFET biosensors are entirely generic and also have the potential to be applied to a variety of other disease detection applications such as Parkinson’s, cancer, and cardiovascular.

Molecular Oxygen Activation by Redox-Switchable Anthraquinone-Based Metal-Organic Frameworks.

A dipyridyl-substituted anthraquinone (2,6-di(pyridin-4-yl)-9,10-anthraquinone, DPAq) was incorporated as a redox-active linker molecule into crystalline coordination networks. The oxidation state of the organic linker can be selectively controlled prior to framework formation and furthermore be maintained in the solid state. Hydrogen bonding is identified to be a substantial stabilization factor. Additionally, it is shown that the anthraquinone-anthrahydroquinone redox pair can be switched reversibly even after incorporation in the solid state by a thermal treatment/soaking procedure-going along with the formation of hydrogen peroxide from molecular oxygen (air) during the oxidation process.

Synthesis of fluorescently-labelled poly(2-ethyl-2-oxazoline)-protected gold nanoparticles

Gold nanoparticles (GNPs) protected by poly(2-ethyl-2-oxazoline) (POZ) of different molecular weights (Mw = 5, 50, 200 and 500 kDa) were synthesised and characterised by dynamic light scattering, nanoparticle tracking analysis, zeta potential measurement and transmission electron microscopy. It was established that the use of POZ with 50 kDa resulted in formation of GNPs with low polydispersity while POZ with greater molecular weights led to formation of more polydisperse GNPs. Fluorescent labelling of these nanoparticles was achieved through their reaction with polyethyleneglycol dithiol (8-12 kDa) as a linker molecule with subsequent reaction with 6-(iodoacetamido) fluorescein. The fluorescent nature of obtained GNPs was confirmed by the appearance of the fluorescence peak at 510 nm that is typical for fluorescein molecules and glowing of the aqueous solution under the UV irradiaton. The fluorescently-labelled GNPs are promising tool in biomedical application to monitor the biological systems using fluorescent microscopy.

New Bifunctional Chelators Incorporating Dibromomaleimide Groups for Radiolabeling of Antibodies with Positron Emission Tomography Imaging Radioisotopes.

Positron Emission Tomography (PET) imaging with antibody-based contrast agents frequently uses the radioisotopes [64Cu]Cu2+ and [89Zr]Zr4+. The macrobicyclic chelator commonly known as sarcophagine (sar) is ideal for labeling receptor-targeted biomolecules with [64Cu]Cu2+. The siderophore chelator, desferrioxamine-B (dfo), has been widely used to incorporate [89Zr]Zr4+ into antibodies. Here, we describe new bifunctional chelators of sar and dfo: these chelators have been functionalized with dibromomaleimides (dbm), that enable site-specific and highly stable attachment of molecular cargoes to reduced, solvent-accessible, interstrand native disulfide groups. The new sar–dbm and dfo–dbm derivatives can be easily conjugated with the IgG antibody trastuzumab via reaction with reduced interstrand disulfide groups to give site-specifically modified dithiomaleamic acid (dtm) conjugates, sar–dtm–trastuzumab and dfo–dtm–trastuzumab, in which interstrand disulfides are rebridged covalently with a small molecule linker. Both sar– and dfo–dtm–trastuzumab conjugates have been radiolabeled with [64Cu]Cu2+ and [89Zr]Zr4+, respectively, in near quantitative radiochemical yield (>99%). Serum stability studies, in vivo PET imaging, and biodistribution analyses using these radiolabeled immunoconjugates demonstrate that both [64Cu]Cu-sar–dtm–trastuzumab and [89Zr]Zr-dfo–dtm–trastuzumab possess high stability in biological milieu. Dibromomaleimide technology can be easily applied to enable stable, site-specific attachment of radiolabeled chelators, such as sar and dfo, to native interstrand disulfide regions of antibodies, enabling tracking of antibodies with PET imaging.

Peptide nucleic acid Hoogsteen strand linker design for major groove recognition of DNA thymine bases

Sequence-specific targeting of double-stranded DNA and non-coding RNA via triple-helix-forming peptide nucleic acids (PNAs) has attracted considerable attention in therapeutic, diagnostic and nanotechnological fields. An E-base (3-oxo-2,3-dihydropyridazine), attached to the polyamide backbone of a PNA Hoogsteen strand by a side-chain linker molecule, is typically used in the hydrogen bond recognition of the 4-oxo group of thymine and uracil nucleic acid bases in the major groove. We report on the application of quantum chemical computational methods, in conjunction with spatial constraints derived from the experimental structure of a homopyrimidine PNA·DNA-PNA hetero-triplex, to investigate the influence of linker flexibility on binding interactions of the E-base with thymine and uracil bases in geometry-optimised model systems. Hydrogen bond formation between the N2 E-base atom and target pyrimidine base 4-oxo groups in model systems containing a β-alanine linker (J Am Chem Soc 119:11116, 1997) was found to incur significant internal strain energy and the potential disruption of intra-stand aromatic base stacking interactions in an oligomeric context. In geometry-optimised model systems containing a 3-trans olefin linker (Bioorg Med Chem Lett 14:1551, 2004) the E-base swung out away from the target pyrimidine bases into the solvent. These findings are in qualitative agreement with calorimetric measurements in hybridisation experiments at T-A and U-A inversion sites. In contrast, calculations on a novel 2-cis olefin linker design indicate that it could permit simultaneous E-base hydrogen bonding with the thymine 4-oxo group, circumvention and solvent screening of the thymine 5-methyl group, and maintenance of triplex intra-stand base stacking interactions.

A mathematical model for bleb regulation in zebrafish primordial germ cells.

Blebs are cell protrusions generated by local membrane-cortex detachments followed by expansion of the plasma membrane. Blebs are formed by some migrating cells, e.g. primordial germ cells of the zebrafish. While blebs occur randomly at each part of the membrane in unpolarized cells, a polarization process guarantees the occurrence of blebs at a preferential site and thereby facilitates migration toward a specified direction. Little is known about the factors involved in the controlled and directed bleb generation, yet recent studies revealed the influence of an intracellular flow and the stabilizing role of the membrane-cortex linker molecule Ezrin. Based on this information, we develop and analyse a coupled bulk-surface model describing a potential cellular mechanism by which a bleb could be induced at a controlled site. The model rests upon intracellular Darcy flow and a diffusion-advection-reaction system, describing the temporal evolution from a homogeneous to a strongly anisotropic Ezrin distribution. We prove the well-posedness of the mathematical model and show that simulations qualitatively correspond to experimental observations, suggesting that indeed the interaction of an intracellular flow with membrane proteins can be the cause of the Ezrin redistribution accompanying bleb formation.

Aluminum textile-based binder-free nanostructured battery cathodes using a layer-by-layer assembly of metal/metal oxide nanoparticles

Despite considerable interest in textile-based battery electrodes with large surface areas and mechanical flexibility, issues have restricted further advances in the energy performance of textile electrodes. These issues include the ineffective incorporation of conductive and/or active components into textile frameworks, the poor charge transfer between energy materials, and the formation of numerous unstable interfaces within textile electrodes. Herein, we introduce an aluminum textile-based lithium-ion battery cathode with remarkable areal capacity, high rate performance, and good cycling stability. Ligand exchange reaction-induced layer-by-layer (LbL) assembly of metal nanoparticles and small molecule linkers, with subsequent metal electroplating, perfectly converted polyester textiles to 3D-porous aluminum textiles that can be used as current collectors and high-energy reservoirs. The consecutive LbL assembly of high-energy LiFePO4 and conductive indium tin oxide nanoparticles onto the aluminum textiles using small organic linkers significantly increased the areal capacity and cycling stability (at least 580 cycles) of the resultant cathode, allowing facile charge transfer within the textile electrodes. Furthermore, the areal capacity of these textile electrodes increased from 1.07 to 3.28 mA h cm−2, with an increase in the folding number from 0 to 2.

Systematic investigation of new alkaline earth phosphonates based on the linker molecule N,N’‐4,4’‐bipiperidine‐bis(methylenephosphonic acid)

AbstractA systematic study of the systems M2+/H4L/KOH/H2O, with M2+=Mg2+, Ca2+, Sr2+, Ba2+ and H4L=N,N’‐4,4’‐bipiperidine‐bis(methylenephosphonic acid) was carried out using high‐throughput methods, including a temperature gradient oven. Overall, six new alkaline earth phosphonates were discovered and structurally characterised by single‐crystal and powder X‐ray diffraction. At room temperature the compounds of composition [Mg2(H2O)8(L)] (1), [Ca2(H2O)6(L)] (2), [Sr2(H2O)4(L)] (3) and [Ba2(H2O)9(L)] ⋅ H2O (4) were discovered. They exhibit the same metal to linker ratio, but differ in their water content. Distinct structural changes are observed with an increase in dimensionality of the coordination polymer with increasing ionic radius of the metal ion. At elevated reaction temperatures the two new metal phosphonates [Mg2(H2O)5(L)] (5) and [Ba2(H2O)2(L)] ⋅ 2 H2O (6) were obtained either from the same reaction mixture as for 1 and 4, respectively, or by solid state transformation. The detailed characterisation of the all materials is also reported.

A Flexible and Porous Ferrocene‐Based Gallium MOF with MIL‐53 Architecture

AbstractA new gallium based metal‐organic framework, denoted as Ga‐MIL‐53‐FcDC, with the chemical formula [Ga(OH)(FeC12H8O4)] was synthesized using the ferrocene containing linker molecule 1,1’‐ferrocenedicarboxylic acid (H2FcDC, FeC12H10O4). The porous nature of the compound could be confirmed by nitrogen sorption and a specific surface area of 270 m2/g was determined. The persistence of the ferrocene complex inside the structure was confirmed by Mössbauer‐, EPR and UV/VIS‐spectroscopy. Ga‐MIL‐53‐FcDC shows structural flexibility depending on which guest molecule is located in the pores of the compound. The mechanism of structural flexibility was analyzed by means of powder X‐ray diffraction adsorbing pyrazine or iodine. The flexibility of the crystal structure can be attributed to the torsion of the GaO6 octahedra in the IBU respective to each other and the torsion of the carboxylate groups of FcDC2− relative to the aromatic ring.

Colloidal Nanocrystal Gels from Thermodynamic Principles.

Gels assembled from solvent-dispersed nanocrystals are of interest for functional materials because they promise the opportunity to retain distinctive properties of individual nanocrystals combined with tunable, structure-dependent collective behavior. By incorporating stimuli-responsive components, these materials could also be dynamically reconfigured between structurally distinct states. However, nanocrystal gels have so far been formed mostly through irreversible aggregation, which has limited the realization of these possibilities. Meanwhile, gelation strategies for larger colloidal microparticles have been developed using reversible physical or chemical interactions. These approaches have enabled the experimental navigation of theoretically predicted phase diagrams, helping to establish an understanding of how thermodynamic behavior can guide gel formation in these materials. However, the translation of these principles to the nanoscale poses both practical and fundamental challenges. The molecules guiding assembly can no longer be safely assumed to be vanishingly small compared to the particles nor large compared to the solvent.In this Account, we discuss recent progress toward the assembly of tunable nanocrystal gels using two strategies guided by equilibrium considerations: (1) reversible chemical bonding between functionalized nanocrystals and difunctional linker molecules and (2) nonspecific, polymer-induced depletion attractions. The effective nanocrystal attractions, mediated in both approaches by a secondary molecule, compete against stabilizing repulsions to promote reversible assembly. The structure and properties of the nanocrystal gels are controlled microscopically by the design of the secondary molecule and macroscopically by its concentration. This mode of control is compelling because it largely decouples nanocrystal synthesis and functionalization from the design of interactions that drive assembly. Statistical thermodynamic theory and computer simulation have been applied to simple models that describe the bonding motifs in these assembling systems, furnish predictions for conditions under which gelation is likely to occur, and suggest strategies for tuning and disassembling the gel networks. Insights from these models have guided experimental realizations of reversible gels with optical properties in the infrared range that are sensitive to the gel structure. This process avoids time-consuming and costly trial-and-error experimental investigations to accelerate the development of nanocrystal gel assemblies.These advances highlight the need to better understand interactions between nanocrystals, how interactions give rise to gel structure, and properties that emerge. Such an understanding could suggest new approaches for creating stimuli-responsive and dissipative assembled materials whose properties are tunable on demand through directed reconfiguration of the underlying gel microstructure. It may also make nanocrystal gels amenable to computationally guided design using inverse methods to rapidly optimize experimental parameters for targeted functionalities.

Influence of DVB as linker molecule on the micropore formation in polymer-derived SiCN ceramics

In this work, the formation of transient microporosity during the polymer-to-ceramic conversion in polymer-derived ceramics was studied using a commercially available poly(vinyl)silazane precursor which was modified with divinylbenzene (DVB) as linker molecule during crosslinking. After pyrolysis treatments between 400 and 700 °C, the resulting materials not only showed distinct changes in elemental composition and structural features upon introduction of the linker molecule, but also a shift in micropore size, e.g. shifting from 0.84 nm to 0.70 nm after pyrolysis at 600 °C. Due to hindrance of transamination reactions in the low-temperature region, the nitrogen content in linker-containing samples was significantly higher, leading to a different composition of micropore-forming entities and, in case of the system studied, to smaller pores. These findings are a first step towards the clarification of the mechanisms leading to the pore formation in PDCs during pyrolytic conversion, which is essential for their use in prospective applications.