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Facile preparation of ionic porous networks (IPNs) with large and permanent porosity is highly desirable for CO2 capture and transformation but remains a challenge. Here we report a one-pot base-mediated construction of nitrogen-rich IPNs through a combination of nucleophilic substitution and quaternisation chemistry from H-imidazole. This strategy, as proven by the model reactions of 1H-imidazole or 1-methyl-1H-imidazole with cyanuric chloride, allows for fine regulation of porosity and physicochemical properties, leading to nitrogen-rich IPNs featuring abundant ionic units and radicals. The as-prepared networks, termed IPN-CSUs, efficiently capture CO2 (80.1 cc g−1 at 273 K/1 bar) with an ideal CO2/N2 selectivity of 139.7. They can also effectively catalyse the cycloaddition reaction between CO2 and epoxides with high yields of up to 99% under mild conditions (0.1 MPa, 298 K), suggesting their possible applications in the fields of both selective molecular separation and conversion. Unlike the previously known strategies generally involving single coupling chemistry, our strategy combining two coupling routes in one pot appears to be unique and potentially applicable to other building blocks., A scale-up strategy through combing nucleophilic substitution and quaternisation chemistry was developed to build highly porous ionic networks with high CO2 storage capacity and high catalytic efficiency for CO2 conversion even under 1800 ppm CO2.

The goal of this study was to develop intraoperative biomaterials for use in endoscopic submucosal dissection (ESD) procedures that are stable during storage, easy to use, and effective in clinical practice. Therefore, injectable thermosensitive hydrogels were developed based on lactobionic acid-modified chitosan/chitosan/β-glycerophosphate (CSLA/CS/GP) hydrogel lyophilizate powders, and their properties were compared with original hydrogels that had not been freeze-dried. The results indicated that the lyophilizate powders retained their thermosensitive properties, and gels could be formed within 5 min at 37 °C. Compared to the original hydrogels, the injectability of the hydrogels derived from lyophilizate powders increased significantly. These novel materials maintained their original porous network lamellar structure but exhibited improved mechanical strength and tissue adhesion. Their application with L929 and GES-1 cells revealed that the lyophilizate powder hydrogels demonstrated good cytocompatibility and clearly protected the cells in an acidic environment. The results of submucosal injection experiments involving porcine stomach tissue indicated that the heights of the cushions created by CSLA/CS/GP lyophilizate powder hydrogels lasted longer than those generated with normal saline. The thermosensitive hydrogels based on lyophilizate powders may contribute to practical clinical applications involving ESD, and may also have potential value for other applications in the digestive tract.

Covalent organic frameworks (COFs) are innovative and remarkable crystalline/porous macrocyclic materials that are composed of purely organic building blocks with strong covalent linkages between light atoms. These newly developed crystals with tailor-made constructions have attracted widespread attention due to low density, promising stabilities, great surface area, ordered and regular porous networks, unique functionalities, as well as proper crystallinity. Impressively, in comparison with other giant molecules, these materials are synthetically manageable and fully organizationally pre-designable. The unique features have permitted COFs to be advanced in combination with other materials such as polymeric, metallic, and carbonaceous materials for designing and discovering novel promising systems in numerous utilizations. Herein, this review highlights the advancement of COF hybrid-based materials for diverse industrial applications. First, a summary of the latest achievements of COFs in various fields is presented, and then hybrids of these materials and their unique applications are considered.

A simple, yet efficient synthetic approach for the construction of vinylene-linked conjugated porous networks was developed. Based on the Horner–Wadsworth–Emmons reaction, the condensation polymerization for the formation of an sp2 carbon-linkage can be achieved at room temperature. The resulting vinylene-linked frameworks exhibit a promising porous nature with the best surface area of up to 1373 m2 g−1. Their intrinsic conjugated architectures and semiconducting properties lead to photocatalytic evolution of hydrogen from water under visible light irradiation. This new synthesis method provides a facile means to prepare attractive sp2 carbon linked porous organic frameworks.

A sulfonic acid functionalized tetraphenylethylene-based hypercrosslinked polymer (THP-SO3H) with a well-developed porous network and accessible sulfonic acid sites was synthesized and characterized by different analytical techniques. The catalytic prowess of the synthesized material THP-SO3H was investigated in a challenging dual C–C bond-breaking reaction for the synthesis of symmetrical triarylmethanes (TRAMs) in high yield. The scope of the developed metal-free method was also explored with a wide variety of substrates. The organocatalyst can be easily recovered by filtration and reused up to five consecutive cycles without substantial loss in its catalytic efficacy.

In this work, the graphene hydrogel (GH) was fabricated, and its adsorption behavior toward Th(IV) was studied. The GH displayed a porous network structure, with a controllable size and structure. The adsorption experimental results demonstrated that the adsorption of Th(IV) on GH fitted well with pseudo-second-order kinetic model and Freundlich isotherm model, with a maximum adsorption capacity of 190.28 mg/g at pH 3.0. The adsorption of Th(IV) on GH in inner-sphere surface complexation. Solution pH has an important influence on Th(IV) adsorption of GH. In addition, the GH exhibits an excellent reusability in Th(IV) adsorption.

Sodium-ion batteries (SIBs) have been attracting considerable attention as a promising candidate for large-scale energy storage because of the abundance and low-cost of sodium resources. However, lack of appropriate anode materials impedes further applications. Herein, a novel self-template strategy is designed to synthesize uniform flowerlike N-doped hierarchical porous carbon networks (NHPCN) with high content of N (15.31 at.%) assembled by ultrathin nanosheets via a self-synthesized single precursor and subsequent thermal annealing. Relying on the synergetic coordination of benzimidazole and 2-methylimidazole with metal ions to produce a flowerlike network, a self-formed single precursor can be harvested. Due to the structural and compositional advantages, including the high N doping, the expanded interlayer spacing, the ultrathin two-dimensional nano-sized subunits, and the three-dimensional porous network structure, these unique NHPCN flowers deliver ultrahigh reversible capacities of 453.7 mAh·g−1 at 0.1 A·g−1 and 242.5 mAh·g−1 at 1 A·g−1 for 2,500 cycles with exceptional rate capability of 5 A·g−1 with reversible capacities of 201.2 mAh·g−1. The greatly improved sodium storage performance of NHPCN confirms the importance of reasonable engineering and synthesis of hierarchical carbon with unique structures.

As compared to porous network solids, including metal-organic frameworks, covalent-organic frameworks, porous aromatic frameworks, and zeolites, porous molecular materials are relatively unexplored. Additionally, within porous molecular space, porous organic cages (POCs) have been the most widely reported over the past decade. Relatively recently, however, porous hybrid metal-organic molecular complexes have received considerable attention with a large fraction of surface areas for these coordination cages reported over the past three years. This review focuses on advances in this area. We highlight the recent work with permanently microporous metal-organic polyhedra (MOPs). Analogous to early work in the area of MOFs, the vast majority of MOPs for which surface areas have been reported have been based on paddlewheel building units and carboxylate ligands. We describe the synthesis of porous cages and highlight those based on monometallic, bimetallic, trimetallic, tetrametallic, and higher nuclearity clusters. Finally, we showcase work wherein the porosity of MOPs has been leveraged for applications related to the storage and separation of small molecules and the incorporation of these porous and potentially porous cages into membranes.

Self-assembly of AgPF6 with a new C3-symmetric tridentate N-donor ligand gives rise to unusual pseudo-2D porous networks with open channels via the interpenetration of 1D zigzag ladders. The open-c...

Herein, we present a rational strategy for the development of π-electron-enriched conjugated microporous polymers (CMPs) under mild conditions, aiming for the super-adsorption of iodine. Among them, TBTT-CMP@1 exhibits a superior iodine uptake up to 442 wt%. In addition, TBTT-CMP@3 displays outstanding CO2 adsorption capacity with uptake up to 1578 mg g−1 under 70 bar and 318 K conditions.

Selective sensing of biothiols holds immense importance due to the adverse roles of abnormal concentrations of biothiols in several diseases, henceforth demanding widespread research for developing a sensory receptor towards the selective detection of biothiols. Herein the designed synthesis of a simple 3D porous coordination polymer, PCP-1 has been carried out following a conventional solvothermal reaction route that shows selective sensing of biothiols (Cys & Hcy) at the nanomolar level with a very short response time carrying enormous importance for simplistic biological studies. Due to the presence of paramagnetic metal centres, MnII-MOF itself remains in a quenched state that shows selective “turn-on” fluorescence response in the presence of electron-rich biothiols which was thoroughly studied by DFT. In continuation, the sensor PCP-1 was equally responsive in different biological matrices such as fresh bovine serum and human urine showing the bio-applicability of the porous network which is of immense importance in analytical domains in the modern era. Thus, the detection of biothiols from human urine would be enormously helpful in preparing a paediatric reference range for clinical use. As a result, the detection of either cystinuria or homocystinuria in patients will be done with ease. Additionally, PCP-1 has selective adsorption capability of CO2 over N2 at low temperature with the aid of the size-exclusion effect of interstitial channels along with the dipole–induced dipole interaction. The magnetic properties of the framework, PCP-1 indicate weak anti-ferromagnetic coupling between the MnII centres of the trinuclear building block. These two hidden potentials may be properly utilised in the domain of GHG mitigating agents and spintronic applications, respectively.

International audience; This study investigated the bioreceptivity of two Lutetian limestones (Courville and Ditrupa), mainly used in the north-eastern region of France, and of their restoration stone (Savonnieres). Samples of the three stones were exposed outdoor for 2.5 years to determine if the replacement of Lutetian stones by Savonnieres was relevant regarding their intrinsic properties and their susceptibility to microbial colonisation. Cultivation assays revealed the presence of similar strains for all stones, but the number of bacteria changed and reached 703.5 CFU/cm2 for Courville, 964.5 CFU/cm2 for Ditrupa and 254.8 CFU/cm2 for Savonnieres. A significant colour change of the surfaces was noticed during the first winter, especially for Savonnieres (ΔE*ab = 18.3). It was associated with a net increase of the chl. a fluorescence and of the pigment content, which suggested a clear growth of phototrophic microorganisms. The Hg porosimetry showed that the porous network of Courville was only slightly impacted by biocolonisation, in contrast to Ditrupa and Savonnieres, where the macropores were obstructed. Savonnieres stone had a weaker bioreceptivity for bacteria than Lutetian stones, but it strongly promoted the colonisation by other microorganisms which could induce more severe bioweathering than on the Lutetian stones.

A prominent characteristic of two-dimensional higher-order topological insulators (2D-HOTIs) is the topologically protected corner modes associated with gapped edge states. Opening the gap of bulk and edge states is a key to realizing 2D-HOTIs. In this paper, we theoretically propose that 2D-HOTIs can be realized on porous network models. We consider two porous network models, the graphenylenelike and the porous-honeycomb models, which respectively contain 12 and 18 atoms in supercells. These superstructures can open the bulk gap as well as the edge gap and induce HOTIs. Experimentally, graphene nanomesh, other 2D porous materials, and organic molecules naturally host supercells with regular nanoholes, which can be candidates to realizing HOTIs. Our studies reveal that 2D-HOTIs can be realized on some 2D porous network models and provide a promising route to explore HOTI states in real materials.

To achieve rapid and highly efficient recovery of Li+ from seawater, a series of H2TiO3/cellulose aerogels (HTO/CA) with a porous network were prepared by a simple and effective method. The as-prepared HTO/CA were characterized and their Li+ adsorption performance was evaluated. The obtained results revealed that the maximum capacity of HTO/CA to adsorb Li+ was 28.58 ± 0.71 mg g−1. The dynamic k2 value indicated that the Li+ adsorption rate of HTO/CA was nearly five times that of HTO powder. Furthermore, the aerogel retained extremely high Li+ selectivity compared with Mg2+, Ca2+, K+, and Na+. After regeneration for five cycles, the HTO/CA retained a Li+ adsorption capacity of 22.95 mg g−1. Moreover, the HTO/CA showed an excellent adsorption efficiency of 69.93% ± 0.04% and high selectivity to Li+ in actual seawater. These findings confirm its potential as an adsorbent for recovering Li+ from seawater.

Two-dimensional (2D) porous networks are of great interest for the fabrication of complex organized functional materials for potential applications in nanotechnologies and nanoelectronics. This review aims at providing an overview of bottom-up approaches towards the engineering of 2D porous networks by using biomacromolecules, with a particular focus on nucleic acids and proteins. The first part illustrates how the advancements in DNA nanotechnology allowed for the attainment of complex ordered porous two-dimensional DNA nanostructures, thanks to a biomimetic approach based on DNA molecules self-assembly through specific hydrogen-bond base pairing. The second part focuses the attention on how polypeptides and proteins structural properties could be used to engineer organized networks templating the formation of multifunctional materials. The structural organization of all examples is discussed as revealed by scanning probe microscopy or transmission electron microscopy imaging techniques.

The extracellular matrix (ECM)-inspired electrospinning scaffolds have a good cytocompatibility. Hyaluronic acid (HA) is one of the main components in the bladder ECM, but it is hard to be made by electrospinning alone. In this study, it is shown that coaxial electrospinning can fabricate poly(l-lactide)/poly(e-caprolactone) (PLCL)/HA nanofibers with the core-shell structure. The HA coating nanofibers have more hydrophilicity, which can promote cell proliferation and migration by filopodial outgrowth. We also fabricated domed PLCL/HA nanofiber scaffolds used in bladder regeneration by improving bladder capacity and facilitating smooth muscle proliferation.

The morphology and crystallographic surface can influence the catalytic HER activity of electrocatalyst. With sufficient active sites and surface area, nanoporous materials with three-dimensional interconnected porous networks have shown the promising application in electrocatalyst. In this work, we report a simple method that can synthesize the self-supported nanoporous cobalt phosphosulfate (CoP|S) electrocatalyst. Theoretical calculation shows that the phosphorus substitution by sulfur can control the electronic structures of the active sites and accelerate charge transfer of CoP, therefore improving HER activity. The experimental study shows that nanoporous CoP|S electrodes present the improved HER performance compared with CoP in alkaline media and acidic media, respectively.

In this study, porous network-like α-Fe2O3 and α/γ-Fe2O3 nanoparticles (NPs) were synthesized by auto-combustion method and their photocatalytic performance was evaluated using methylene blue (MB) as a dye model. Calcination of the synthesized nanoparticles resulted in α/γ-Fe2O3 heterophase magnetite material at 450°С and pure α-Fe2O3 at 700 and 800°С. The magnetic property of α/γ-Fe2O3 makes the photocatalyst to be easily collected from the photocatalytic system and increases its potential in industrial applications. The α/γ-Fe2O3 heterophase material showed a photocatalytic performance almost similar to that of the α-Fe2O3 NPs calcined at 800°С, but higher than that of the α-Fe2O3 NPs calcined at 700°С. The cliff-like band structure between α-Fe2O3 and γ-Fe2O3 reduced recombination of photoelectrons and photoholes, thereby improving photocatalytic performance of the α/γ-Fe2O3 heterophase material.

The self-assembly of 3,10-dibromo-perylo[1,12-b,c,d]thiophene on Ag(111) leads to three types of ordered porous networks: honeycomb PN1, Kagome PN2, and hybrid PN3. Detailed experimental and theore...

Microporous networks based on boronate ester-capped iron(ii) clathrochelate complexes are described. The networks were obtained by covalent cross-linking of tetrabrominated clathrochelate complexes via Suzuki-Miyaura polycross-coupling reactions with diboronic acids, or by Sonogashira-Hagihara polycross-coupling of clathrochelate complexes with terminal alkyne functions and 1,3,5-tribromobenzene. The networks display permanent porosity with apparent Brunauer-Emmett-Teller surface areas of up to SABET = 593 m2 g-1. A clathrochelate complex based on an enantiopure dioximato ligand was used to prepare chiral networks. One of these networks was shown to preferentially absorb d-tryptophan over l-tryptophan.

Superhydrophobic films that are simple, inexpensive, corrosion-resistant and multifunctional are in high demand for industrial applications. We propose a simple and economical phase separation method for fabricating superhydrophobic films using polylactic acid (PLA), nano-SiO2 and a mixture of good and poor solvents to construct a rough surface with a nano/microstructured morphology. The phase separation-induced superhydrophobic PLA/SiO2 composite film with a porous network structure has a water contact angle greater than 164°. This method can be applied to a variety of surfaces or used in large-scale industrial production. The fabricated superhydrophobic films may be applied in biological fields because PLA is a good biodegradable material.

In this study, the CS-DAS aerogels were prepared using chitosan (CS) crosslinked by dialdehyde starch (DAS), with the best absorption and mechanical properties at the weight ratio of CS to DAS being 7:3. The copper nanoparticles (CuNPs) were first prepared by green reduction method, then encapsulated by liposomes (Lip-CuNPs) for controlling their sudden release. The antibacterial aerogels (CD/Lip-CuNPs) were developed by incorporating the Lip-CuNPs into the aerogel (7:3). The porous network structure of aerogels realized the further gradual release of CuNPs. The CD/Lip-CuNPs aerogels had good antimicrobial properties, which could preserve fresh pork for 14 d at 4 °C without spoilage. Moreover, the CuNPs migrated from the aerogels into fresh pork was at a safe level of 3.38 mg/kg after 14 d at 4 °C. The obtained antibacterial CD/Lip-CuNPs aerogels had the potential for extending the shelf life of fresh meat.

Electrochemical reduction of CO2 to value-added chemicals is a promising strategy for making use of excess CO2. Here, we synthesized a porous network zinc catalyst by electrodeposition of Zn(NO3)2 on Zn foil. The material exhibited excellent catalytic activity, being able to reduce CO2 to CO with ~80% Faradaic efficiency (FECO) at −1.1 V vs RHE. Control experiments suggested that the high activity of the Zn porous network can be attributed to its unique nanostructured surface with a large active surface area. Keywords: Electrochemical reduction of CO2, Selectivity, Porous network Zn catalyst, CO production

Aerogels are lightweight, low-density materials derived from organic, inorganic, or hybrid molecular precursors. Aerogels are 99.8% air. Hence, they are solid gels with a porous network that contain air pockets. Though there are abundant synthetic aerogels available, there are natural aerogels also that are playing important role in the process of pollutant removal. Some of the important natural aerogels are starch, cellulose and other polysaccharides, and natural proteins. Oil removal and separation in case of accidental oil leakage and spillage in oil industries are of great importance. The untreated waste in the form of oil and other contaminants not only results in unnecessary economic loss but are also dangerous to the ecology system. Naturally occurring cotton cellulose aerogel has proven to be a great purifier in such scenarios. The action takes place by absorption mechanism. Cellulose also finds application in the textile industry. The natural proteins like egg white also act as aerogels for applications in the food industry. Use of these natural aerogels has a more significant impact on the purification of air and environment as a whole at this time of contamination being at its peak and growing. This chapter talks in detail about the natural aerogels, their chemical and physical properties, and mechanism of their action as pollutant removers.

Block copolymer–based porous carbon fibers show ultrahigh capacity and rate for capacitive deionization., Capacitive deionization (CDI) is energetically favorable for desalinating low-salinity water. The bottlenecks of current carbon-based CDI materials are their limited desalination capacities and time-consuming cycles, caused by insufficient ion-accessible surfaces and retarded electron/ion transport. Here, we demonstrate porous carbon fibers (PCFs) derived from microphase-separated poly(methyl methacrylate)-block-polyacrylonitrile (PMMA-b-PAN) as an effective CDI material. PCF has abundant and uniform mesopores that are interconnected with micropores. This hierarchical porous structure renders PCF a large ion-accessible surface area and a high desalination capacity. In addition, the continuous carbon fibers and interconnected porous network enable fast electron/ion transport, and hence a high desalination rate. PCF shows desalination capacity of 30 mgNaCl g−1PCF and maximal time-average desalination rate of 38.0 mgNaCl g−1PCF min−1, which are about 3 and 40 times, respectively, those of typical porous carbons. Our work underlines the promise of block copolymer–based PCF for mutually high-capacity and high-rate CDI.

Spontaneous bone regeneration is heavily restricted because of bone defects, and external mediation is required to enhance repair and regeneration. Bone tissue engineering (BTE) is a multidisciplinary field that offers promising substitutes to traditional methods-namely, autografts, allografts, and xenografts. Amidst the various scaffolds for BTE applications, it has been demonstrated that hydrogels are promising templates for bone regeneration owing to their similarities to the natural extracellular matrix. Regardless of the development of a variety of biomaterials, chitosan (CS) as a natural biopolymer has drawn tremendous attention in recent years for its use as a valuable graft material to form thermo/pH-responsive injectable hydrogels. Formulations of CS-based injectable hydrogels are advantageous in terms of their high-water imbibing capability, minimal invasiveness, porous networks, and ability to mold perfectly into an irregular defect. In this review, the physicochemical properties and applications of thermo/pH-responsive CS-based hydrogels and their future perspectives in BTE are briefly outlined.

Aerogels of cellulose exhibit remarkable mechanical properties as a function of density. Modifying the pore volume in classical cellulose aerogels using sacrificial template methods provide scaffold like microstructure. In the present study, we have developed aerogels of cellulose scaffolds having almost same density values but differ in microstructure and analysed the influence on the mechanical properties of bulk materials. This study can give an insight into the materials design for advanced engineering materials. Employing four surfactants having difference in hydrophilic-lipophilic balance (HLB), namely polyoxyethylene tert-octylphenyl ether (PT), polyoxyethylene (20) oleyl ether (PO), polyoxyethylene (40) nonylphenyl ether (PN) and polyoxyethylene (100) stearyl ether (PS), the cellulose scaffolds with hierarchical porous structures were developed. The mechanical properties of cellulose scaffolds were compared with classical pure cellulose aerogels. The results indicate that the solid fraction of cellulose nanofibers per unit volume of cell walls of scaffolds plays an important role in determining the elastic properties and strength. As the nanofibrils support the cell walls of scaffolds, Young’s modulus can be improved if the concentration of cellulose nanofibers is high at the cell walls or cell wall thickness is larger. The scaffold materials of this kind could be used as supporting materials with desired properties for filter, catalysis and biomedicine.

Four new Zn(II) and Cd(II) coordination complexes, [Zn(p-pda)(m-bib)]·H2O (1), [Zn(m-pda)(o-bib)]·H2O (2), [Cd(o-pda)(o-bib)] (3), [Cd(m-pda)(o-bib)]·H2O (4), (H2pda = phenylenediacetic acid, bib = 1,4-bis(imidazol-1-ylmethyl)benzene), have been synthesized, and structurally characterized by elemental analysis, IR spectroscopy, single-crystal X-ray crystallography. Complex 1 exhibits a 3D porous network based on 2D loop-containing layer. Complex 2–4 possesses a 3D network extended by 2D net. Differently, in complex 3, the 2D network stack in an ABAB mode, while equivalent wave-like 2D networks mutually interpenetrated with each other to generate a 2D → 3D entangled system in 2 and 4. Furthermore, the relationship between molecular conformation, packing modes and fluorescence properties have also been investigated.

In real crude-oil pipelines, the formed wax deposits could be heterogeneous along the radial or axial directions. However, studies on this aspect are scarce. In this paper, the effect of the polyoctadecyl acrylate (POA) wax inhibitor on the wax deposition of 10 wt % model waxy oil was investigated with the aid of an in-house wax deposition device, differential scanning calorimetry test, high-temperature gas chromatography–Fourier transform infrared analysis, and microscopic observation. The results showed that adding POA in the model waxy oil greatly modifies the morphology of precipitated wax crystals, thus greatly changing the wax deposition behavior of the oil. For oil sample 1 (without POA), the precipitated wax crystals (needle-like) more easily form porous network structures, causing the formation of a thick and porous wax deposit with relatively low WAT, wax conten,t and critical carbon number (CCN). With the increase of POA concentration (oil samples 2–5), the precipitated wax crystals become more...

A novel strategy for producing three-dimensional (3D) porous Ti3C2Tx(MXene) networks by alkali-induced crumpling of Ti3C2Txnanosheets is presented. These networks display high capacity and good rate performance as anode materials for sodium-ion batteries.

Porous bioglass (BG) scaffolds are of great importance in tissue engineering because of their excellent osteogenic properties for bone regeneration. Herein, we reported for the first time the use of amino-modified bacterial cellulose (NBC) as a template to prepare a three-dimensional (3D) nanofibrous BG scaffold by a facile modified sol–gel approach under ultrasonic treatment. The results suggested that the amino groups on the BC template could effectively promote the absorption of the deposited CaO and SiO2 precursors, and the as-obtained BG scaffold showed a 3D interconnected porous network structure consisting of nanofibers with a diameter of about 20 nm. Furthermore, the as-obtained BG scaffold showed very good bioactivity after being immersed in SBF for 7 days. This research provides a facile and efficient way to prepare a nanofibrous BG scaffold with 3D porous structure, which can be used as a promising candidate for biomedical applications.

This paper presents an experimental research on the effect of carbonation on the chloride penetration in mortars exhibiting a refined porous network and high chloride-binding capacity. The research was focused on the use of metakaolin combined with nanosilica , evaluating the influence of the surface area of the nanoadditions. It was observed that the addition of nanosilica reduces the binding capacity of metakaolin, this reduction was influenced by the type of nanosilica. The analysis of the carbonated samples following carbonation periods of three and six months allowed observing that the free chloride content as well as the bound chloride content are diminished with carbonation. Thence, it can be concluded that the carbonation process hinders the chloride penetration, which can lead to a reduction with time in the chloride concentration of samples.

By studying the hydration of casein micelles using a variety of techniques, a distinction could be made between water that appeared bound by the protein (∼0.5 g g−1 protein), water associated with the κ-casein brush (∼1.0 g g−1 protein) and water entrapped in the casein micelles (∼1.8 g g−1 protein), yielding a total micellar hydration of ∼3.3 g g−1 protein, in line with casein micelle voluminosity derived from intrinsic viscosity measurements. For caseinate particles, however, the main contributor to intrinsic viscosity was not protein hydration but the non-spherical particle shape. These non-spherical particles in caseinate are likely to be naturally present as primary casein particles (PCP) in casein micelles. PCP could be used to build casein micelles by controlled introduction of micellar salts. Based on the findings of this study, casein micelles could be described as a porous network of non-spherical PCP linked by calcium phosphate nanoclusters.

Composite scaffolds were prepared from the mixture of chitosan (C), gelatin (G) and nanodiopside (nDP) in different inorganic/organic weight ratios using the freeze-drying method. The prepared nDP and composite scaffolds were investigated using BET, FT-IR, SEM and XRD techniques. The composite scaffolds had 70–81% porosities with interlinked porous networks. Moreover, investigation of the cell proliferation, adhesion and viability using MTT test and mouse preosteoblast cell proved the cytocompatible nature of the composite scaffolds with improved cell attachment and proliferation. All these results essentially illustrated that this composite could have a potential ability for the tissue engineering applications.

The paper concerns application of two types of organic materials – porous aromatic frameworks (PAFs) with diamond-like structure and the ordered mesoporous phenol-formaldehyde polymers (MPFs) – as supports for metal and metal sulfide nanoparticles. The obtained hybrid materials were tested in hydrogenation of various unsaturated and aromatic compounds. Ruthenium catalyst, based on PAF (Ru-PAF-30), possessed high activity in exhaustive hydrogenation of phenol into cyclohexanol with TOF value of 2700 h−1. Platinum catalyst, based on modified with sulfo-groups MPF (MPF-SO3H-Pt), was selective in semi-hydrogenation of terpenes, [α-terpinene, γ-terpinene, terpinolene, (s)-limonene]. Bimetallic Ni–W sulfide catalysts, prepared by in situ decomposition of [(n-Bu)4N]2Ni(WS4)2 within the pores of MPFs and PAFs, possessed high efficiency in hydrogenation-hydrocracking of naphthalenes as model substrates.

Hypercrosslinked polymers for selective CO2 capture have been successfully synthesized from highly rigid contorted blocks via a low-cost versatile strategy. Such amorphous materials with improved porosities achieve high specific surface areas of up to 1616 m2 g−1 and substantially improved pore volumes (1.53 cm3 g−1). The polymer networks feature hierarchically porous structures ranging from ultramicropores to mesopores (0.50 to 3.80 nm) as well as high physicochemical stability. They can uptake 15.9 wt% CO2 at 273 K/1 bar, surpassing nearly all polymers of intrinsic microporosity (PIMs) and most known hypercrosslinked polymers (HCPs). The abundant ultramicropores with pore diameters centered at around 0.50 nm allow selective CO2 uptake against N2 (ideal selectivity: 69.7) and CH4 (15.8). These results are significant for molecular design and emphasize the importance of utilizing rigid contorted blocks to build hierarchically porous networks for effective CO2 capture applications.

Organic π-conjugated linear and network polymers, owing to their large synthetic variety of finely tunable structures and properties, are promising semiconducting materials for optoelectronic devices and light harvesting applications. A vast library of such π-conjugated systems has been synthesized through conventional tools of coupling (e.g. Suzuki coupling, Stille coupling) which involves tedious preactivation of C-H bonds using highly toxic and flammable reagents. In recent years an emerging synthetic technique called direct C–H arylation has been extensively studied as a facile, atom-efficient and environmentally benign pathway for the synthesis of conjugated polymers and small molecules. In this thesis, direct arylation has been applied to rationally chosen monomers to produce conjugated small molecules, linear polymers as well as 2D/ 3D porous polymers that exhibit performances comparable with those made from conventional reactions. In this thesis, we use naphthodithiophenediimide (NDTI) – a new electron-accepting building block that has shown high performance in ambi-polar organic field-effect transistors to synthesize polymers and small molecules by direct arylation. To examine its regioselectivity, NDTI was used to synthesize small molecules by coupling with 2-bromo-9,9-dihexylfluorene. Two NDTI-based narrow bandgap polymers, one with benzothiadiazole and the other with 9,9-dioctylfluorene, were synthesized via polymerization (DAP). The chemical structures and optoelectronic properties of these molecules and polymers were characterized. Benzo[1,2-c:4,5-c′]dithiophene-4,8-dione (BDTD) is another electron-accepting building block which has demonstrated outstanding performance in organic bulk heterojunction (BHJ) solar cells. We use DAP to synthesize a series of wide bandgap D-A copolymers with a common acceptor building block of BDTD and study the structure-property relationship in these polymers. We also present the device performances of these polymers in both thin-film field-effect transistors and organic solar cells using BDTD-based polymers as the electron donors and fullerene derivatives as the electron acceptors. In this thesis, we have also demonstrated direct arylation as an efficient synthetic tool for conjugated porous polymers (CPPs). A series of narrow bandgap conjugated porous polymers have been synthesized by facile direct arylation polymerization of thiophene-flanked thienothiadiazole (TTD) with multi-brominated monomers with different geometries. The polymer products show strong light absorption in the near infrared region, corresponding to narrow optical bandgaps below 1.3 eV. Under the same polymerization conditions, the morphologies, porosities and optoelectronic properties of the resulting polymers are determined by the chemical structures of the aryl bromides. In order to extend the library of thiophene-containing CPPs synthesized by direct arylation, we chose three thiophene-flanked monomers – bithiophene (BT), 4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole (DTBT) and 2,5-bis(2-octyldodecyl)-3,6-di(thiophen-2-yl)-2,5-pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (DPP) with active C-H bonds and polymerized them with tri- and tetra-brominated monomers. This modular design has allowed us to study the effect of thiophene monomers on the morphology, porosity and optical properties of the CPPs. In our final research work, we present the direct arylation synthesis of a new series of conjugated porous polymers (CPPs) containing triazine. We used 2,4,6-(tri-2-thienyl)-1,3,5-triazine (TTT) to synthesize a series of robust triazine-core polymers by with DAP without need for preactivating the C–H bonds in the arene monomers. The resulting triazine-core polymers were used to catalyze the photo-oxidation of benzylamines and the polymers containing the highest fraction of triazine units showed > 99% conversion with a relatively low loading of the catalyst. Doctor of Philosophy

The ability to create extended porous networks, such as those composed of metal-organic frameworks (MOFs), with tailored hydrophilic/hydrophobic character is crucial for adapting such widely used supports to different applications. To achieve this goal, direct polymer inclusion has proven to be a suitable strategy, and functional composite materials with multiple additional properties have been obtained in such a way. We have explored, by means of nuclear magnetic resonance diffusion experiments, the effect of polymer capping using a conducting polymer (polyaminobencylamine - PABA), which results in the positioning of -NH2 moieties on the otherwise eminently hydrophobic surface of Zn-based ZIF-8 MOF nanocrystals. Our results demonstrate that increasingly higher amounts of PABA can confer, aside from conductivity, an increased hydrophilic character to the porous network, while also allowing for the identification of different environments available for water molecule diffusion. Fil: Velasco, Manuel Isaac. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina. Universidad Nacional de Córdoba. Facultad de Matemática, Astronomía y Física; Argentina Fil: Acosta, Rodolfo Héctor. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina. Universidad Nacional de Córdoba. Facultad de Matemática, Astronomía y Física; Argentina Fil: Marmisollé, Waldemar Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina Fil: Azzaroni, Omar. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina Fil: Rafti, Matias. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina

Mitigation of the foreign body response (FBR) and successful tissue integration are essential to ensuring the longevity of implanted devices and biomaterials. The use of porous materials and coatings has been shown to have an impact, as the textured surfaces can mediate macrophage interactions with the implant and influence the FBR, and the pores can provide space for vascularization and tissue integration. In this study, we use a new class of implantable porous biomaterials templated from bicontinuous interfacially jammed emulsion gels (bijels), which offer a fully percolating, non-constricting porous network with a uniform pore diameter on the order of tens of micrometers, and surfaces with consistent curvature. We demonstrate that these unique morphological features, inherent to bijel-templated materials (BTMs), can enhance tissue integration and vascularization, and reduce the FBR. Cylindrical polyethylene glycol diacrylate (PEGDA) BTMs, along with PEGDA particle-templated materials (PTMs), and non-templated materials (NTMs), were implanted into the subcutaneous space of athymic nude mice. After 28 days, implants were retrieved and analyzed via histological techniques. Within BTMs, blood vessels of increased size and depth, changes in collagen deposition, and increased presence of pro-healing macrophages were observed compared to that of PTM and NTM implants. Bijel templating offers a new route to biomaterials that can improve the function and longevity of implantable devices. Statement of Significance All implanted biomaterials are subject to the foreign body response (FBR) which can have a detrimental effect on their efficacy. Altering the surface chemistry can decrease the FBR by limiting the amount of proteins adsorbed to the implant. This effect can be enhanced by including pores in the biomaterial to allow new tissue growth as the implant becomes integrated in the body. Here, we introduce a new class of self-assembled biomaterials comprising a fully penetrating, non-constricting pore phase with hyperbolic (saddle) surfaces for enhanced tissue integration. These unique morphological characteristics result in dense blood vessel formation and favorable tissue response properties demonstrated in a four-week implantation study.

Breaking away from the linear structure of previously reported peptide-based gelators, this study reports the first example of gel formation based on the use of cyclic peptides made of alternating d- and l-amino acids, known to self-assemble in solution to form long nanotubes. Herein, a library of cyclic peptides was systemically studied for their gelation properties in various solvents, uncovering key parameters driving both organogel and hydrogel formation. The hierarchical nature of the self-assembly process in water was characterised by a combination of electron microscopy imaging and small-angle X-ray scattering, revealing a porous network of entangled nanofibres composed by the aggregation of several cyclic peptide nanotubes. Rheology measurements then confirmed the formation of soft hydrogels.

Molecular self-assembly, taking advantage of reversible intermolecular interactions, represents an efficient method to prepare ultrathin films exhibiting minimal packing defects. The same protocol seems reasonable to fabricate hybrid monolayers yet typically results in segregated domains. Demonstrated herein is a host–guest concept in which guest molecules are hosted in homogeneously patterned voids at the liquid–solid interface. However, 2D open lattices with low packing densities often suffer poor stability. In this study, the concept is realized by a 2D porous network assembled via 1,3,5-tris(4-carboxyphenyl)benzene (BTB) whose stability is significantly enhanced by hosting spatially matched pentacene or its analogues. The conformal contact between the nearest neighbors optimizes intermolecular interactions. Simulation results of molecular mechanics for a simplified model suggest that the hybrid lattice is about 250 kcal/mol per BTB pore more stable than guests such as coronene and Cu-phthalocyanine.

Mn2O3 microcubes with three-dimensional (3D) micromesoporous network structure were synthesized by thermal decomposition of the as-prepared MnCO3 precursor. The structure, morphology, and textural property of the as-synthesized Mn2O3 microcubes were characterized. The electrochemical property and electrochemical sensing performance toward nitrite detection were investigated. Owing to the unique 3D micromesoporous network structure, the Mn2O3 microcubes could provide electrochemical sensing of nitrite with high sensitivity, selectivity, and reliability.