Hierarchical conductive metal-organic framework films enabling efficient interfacial mass transfer.

Heterogeneous reactions associated with porous solid films are ubiquitous and play an important role in both nature and industrial processes. However, due to the no-slip boundary condition in pressure-driven flows, the interfacial mass transfer between the porous solid surface and the environment is largely limited to slow molecular diffusion, which severely hinders the enhancement of heterogeneous reaction kinetics. Herein, we report a hierarchical-structure-accelerated interfacial dynamic strategy to improve interfacial gas transfer on hierarchical conductive metal-organic framework (c-MOF) films. Hierarchical c-MOF films are synthesized via the in-situ transformation of insulating MOF film precursors using π-conjugated ligands and comprise both a nanoporous shell and hollow inner voids. The introduction of hollow structures in the c-MOF films enables an increase of gas permeability, thus enhancing the motion velocity of gas molecules toward the c-MOF film surface, which is more than 8.0-fold higher than that of bulk-type film. The c-MOF film-based chemiresistive sensor exhibits a faster response towards ammonia than other reported chemiresistive ammonia sensors at room temperature and a response speed 10 times faster than that of the bulk-type film.

Polarity and functionality tailored conjugated microporous polymer coatings on silica microspheres for enhanced pollutant adsorption.

Many sources of pollution that are generated by modern society are not addressable by conventional methods. Especially organic compounds, like pharmaceutics, are particularly hard to remove from waterbodies. Herein, a new approach is presented using conjugated microporous polymers (CMPs) to coat silica microparticles yielding specifically tailored adsorbents. The CMPs are generated with three different monomers: 2,6-dibromonaphthalene (DBN), 2,5-dibromoaniline (DBA) and 2,5-dibromopyridine (DBPN) respectively coupled to 1,3,5-triethynylbenzene (TEB) via Sonogashira coupling. By optimizing the polarity of the silica surface, all three CMPs were converted into microparticle coatings. The resulting hybrid materials feature the advantages of being adjustable in polarity and functionality, as well as morphology. Sedimentation allows facile removal of the coated microparticles after the adsorption. Further, the expansion of the CMP to a thin coating increases the accessible surface area compared to the bulk material. These effects were demonstrated by the adsorption of the model drug diclofenac. Thereby, the aniline-based CMP proved to be most advantageous due to a secondary crosslinking mechanism of amino and alkyne functionalities. An outstanding adsorption capacity of 228 mg diclofenac per gram of the aniline CMP within the hybrid material was achieved. This represents a five-fold increase compared to the value obtained by the pure CMP material underlining the advantages of the hybrid material.

SiO2 nanospheres as surfactant and template in aqueous dispersion polymerizations yielding highly nanoporous resin particles.

HYPOTHESIS: High nitrogen containing resins such as poly(melamine-co-formaldehyde) (PMF) are known for their very good adsorption properties. Until now, using an ecofriendly hard-templating approach with SiO2 nanospheres in water for synthesis, only yielded either highly porous particles with diameters up to 1 µm or non-porous particles with diameters above 1 µm. Small particles cannot be used as fixed bed adsorbents in columns because of the very high pressure occurring. EXPERIMENTS: To yield particles with high porosity and larger diameters for the use as fixed bed adsorbent, we investigated the influence of several synthesis parameters on porosity and particle morphology. FINDINGS: From all variations, we proposed a mechanism for the complex interplay between the PMF prepolymer and resin species with SiO2 nanoparticles acting both as Pickering-like surfactant and template particle. With this knowledge we were able to produce a suitable column material with high specific surface area up to 260 m2/g. We then proved the application of this material for aqueous dichromate adsorption in batch, yielding a maximum capacity of 138 mg/g with recyclability. In column experiments, the contamination of 5 mg/L dichromate in water was reduced to drinking water safe levels for an influent volume equal to over 160 bed volumes.

Tuning the pore structure of templated mesoporous poly(melamine-co-formaldehyde) particles toward diclofenac removal.

The increasing demand and implementation of pharmaceutics poses severe risk to different aquatic species as detectable contaminant in almost every surface water worldwide. Diclofenac (DCF) as one of the most common used analgesics was investigated as contaminant to be removed by adsorption onto nanoporous poly(melamine-co-formaldehyde) (PMF) particles featuring a very high amount of nitrogen functionalities. To achieve a high specific surface area (up to 416 m2/g) and a tunable pore system by hard templating, four different SiO2 nanoparticles were used as template. Differences in the pore formation and achieved pore structure were elucidated. For the first time, the adsorption of DCF onto PMF was tested. In batch adsorption experiments, impactful adsorption capacities as high as 76 µmol/g were achieved and complete removal at initial concentrations of 2 mg/L DCF. Differences in the connectivity and the micropore structure were decisive for uptake in low concentrations and the achieved adsorption capacity, respectively. As the presented PMF particles can be easily synthesized with the monomers formaldehyde and melamine combined with colloidal silica as sacrificial template and water as green solvent, this material presents a viable adsorbent for the removal of DCF at a larger scale. Our study further indicates a high potential for the removal of other pharmaceuticals.

Mesoporous Poly(melamine-co-formaldehyde) Particles for Efficient and Selective Phosphate and Sulfate Removal.

Due to the existence-threatening risk to aquatic life and entire ecosystems, the removal of oxyanions such as sulfate and phosphate from anthropogenic wastewaters, such as municipal effluents and acid mine drainage, is inevitable. Furthermore, phosphorus is an indispensable resource for worldwide plant fertilization, which cannot be replaced by any other substance. This raises phosphate to one of the most important mineral resources worldwide. Thus, efficient recovery of phosphate is essential for ecosystems and the economy. To face the harsh acidic conditions, such as for acid mine drainage, an adsorber material with a high chemical resistivity is beneficial. Poly(melamine-co-formaldehyde) (PMF) sustains these conditions whilst its very high amount of nitrogen functionalities (up to 53.7 wt.%) act as efficient adsorption sides. To increase adsorption capacities, PMF was synthesized in the form of mesoporous particles using a hard-templating approach yielding specific surface areas up to 409 m2/g. Different amounts of silica nanospheres were utilized as template and evaluated for the adsorption of sulfate and phosphate ions. The adsorption isotherms were validated by the Langmuir model. Due to their properties, the PMF particles possessed outperforming maximum adsorption capacities of 341 and 251 mg/g for phosphate and sulfate, respectively. Furthermore, selective adsorption of sulfate from mixed solutions of phosphate and sulfate was found for silica/PMF hybrid particles.

A Complementary and Revised View on the N-Acylation of Chitosan with Hexanoyl Chloride.

The modification of the biobased polymer chitosan is a broad and widely studied field. Herein, an insight into the hydrophobization of low-molecular-weight chitosan by substitution of amino functionalities with hexanoyl chloride is reported. Thereby, the influence of the pH of the reaction media was investigated. Further, methods for the determination of the degree of substitution based on 1H-NMR, FTIR, and potentiometric titration were compared and discussed regarding their accuracy and precision. 1H-NMR was the most accurate method, while FTIR and the potentiometric titration, though precise and reproducible, underlie the influence of complete protonation and solubility issues. Additionally, the impact of the pH variation during the synthesis on the properties of the samples was investigated by Cd2+ sorption experiments. The adjusted pH values during the synthesis and, therefore, the obtained degrees of substitution possessed a strong impact on the adsorption properties of the final material.

Simultaneous Ligand and Cation Exchange of Colloidal CdSe Nanoplatelets toward PbSe Nanoplatelets for Application in Photodetectors.

Cation exchange emerged as a versatile tool to obtain a variety of nanocrystals not yet available via a direct synthesis. Reduced reaction times and moderate temperatures make the method compatible with anisotropic nanoplatelets (NPLs). However, the subtle thermodynamic and kinetic factors governing the exchange require careful control over the reaction parameters to prevent unwanted restructuring. Here, we capitalize on the research success of CdSe NPLs by transforming them into PbSe NPLs suitable for optoelectronic applications. In a two-phase mixture of hexane/N-methylformamide, the oleate-capped CdSe NPLs simultaneously undergo a ligand exchange to NH4I and a cation exchange reaction to PbSe. Their morphology and crystal structure are well-preserved as evidenced by electron microscopy and powder X-ray diffraction. We demonstrate the successful ligand exchange and associated electronic coupling of individual NPLs by fabricating a simple photodetector via spray-coating on a commercial substrate. Its optoelectronic characterization reveals a fast light response at low operational voltages.

A Comparative Study on the Flocculation of Silica and China Clay with Chitosan and Synthetic Polyelectrolytes.

Flocculation is still one of the most important and efficient processes for water treatment. However, most industrial processes, such as in water treatment plants, still use huge amounts of synthetic polyelectrolytes for the flocculation process. Here we compare the flocculation of two different suspended particles, i.e., silica particles and china clay, with the biopolymer chitosan and two common strong synthetic polyelectrolytes. As a flocculant, chitosan featured a minimum uptake rate of 0.05 mg/g for silica and 1.8 mg/g for china clay. Polydiallyldimethylammonium chloride (PDADMAC) for comparison possessed a minimum uptake rate of 0.05 mg/g for silica and 2.2 mg/g for china clay. Chitosan as an environmentally friendly biopolymer competes with the synthetic polyelectrolytes and thus represents a beneficial economic alternative to synthetic flocculants.

Meso- and macroporous silica-based arsenic adsorbents: effect of pore size, nature of the active phase, and silicon release.

Arsenic pollution in ground and drinking water is a major problem worldwide due to the natural abundance of arsenic by dissolution from ground sediment or mining activities from anthropogenic activities. To overcome this issue, iron oxides as low-cost and non-toxic materials, have been widely studied as efficient adsorbents for arsenic removal, including when dispersed within porous silica supports. In this study, two head-to-head comparisons were developed to highlight the As(v)-adsorptive ability of meso- and macrostructured silica-based adsorbents. First, the role of the textural properties of a meso-(SBA15) and macrostructured (MOSF) silica support in affecting the structural-morphological features and the adsorption capacity of the active phase (Fe2O3) have been studied. Secondly, a comparison of the arsenic removal ability of inorganic (Fe2O3) and organic (amino groups) active phases was carried out on SBA15. Finally, since silica supports are commonly proposed for both environmental and biomedical applications as active phase carriers, we have investigated secondary silicon and iron pollution. The batch tests at different pH revealed better performance from both Fe2O3-composites at pH 3. The values of q m of 7.9 mg g-1 (53 mg gact -1) and 5.5 mg g-1 (37 mg gact -1) were obtained for SBA15 and MOSF, respectively (gact stands for mass of the active phase). The results suggest that mesostructured materials are more suitable for dispersing active phases as adsorbents for water treatment, due to the obtainment of very small Fe2O3 NPs (about 5 nm). Besides studying the influence of the pore size of SBA15 and MOSF on the adsorption process, the impact of the functionalization was analyzed on SBA15 as the most promising sample for As(v)-removal. The amino-functionalized SBA15 adsorbent (3-aminopropyltriethoxysilane, APTES) exhibited a q m of 12.4 mg g-1 and faster kinetics. Furthermore, issues associated with the release of iron and silicon during the sorption process, causing secondary pollution, were evaluated and critically discussed.

Orthopaedic Surgery Elicits a Systemic Anti-Inflammatory Signature.

Little information is available on the functional activity of leukocytes after arthroplasty or the expansion of populations with immune suppressive properties during the acute post-operative period. Synovial fluid and matched pre- and post-surgical blood samples were collected from total hip and knee arthroplasty patients (THA and TKA, respectively) to examine the impact of surgery on peripheral blood leukocyte frequency, bactericidal activity, and inflammatory mediator expression. For spinal surgeries, inflammatory mediator production by peripheral blood mononuclear cells (PBMCs) pre- and post-surgery was examined. An expansion of immune suppressive granulocytic myeloid-derived suppressor cells (G-MDSCs) was observed following arthroplasty, which correlated with significantly increased serum interleukin-10 (IL-10) levels. Analysis of synovial fluid from THA and TKAs revealed reduced granulocyte colony-stimulating factor (G-CSF) and soluble CD40 ligand (sCD40L) and increased interleukin-6 (IL-6), monocyte chemoattractant protein 2 (CCL2) and Fms-like tyrosine kinase 3 ligand (Flt-3L) compared to pre- and post-surgical serum. For the spinal surgery cohort, stimulation of PBMCs isolated post-surgery with bacterial antigens produced significantly less pro-inflammatory (IL-1α, IL-1ß, interleukin-1 receptor antagonist (IL-1RA), IL-12p40, growth-related oncogene-α/GRO-α (CXCL1) and 6Ckine (CCL21)) and more anti-inflammatory/tissue repair mediators (IL-10, G-CSF and granulocyte-macrophage colony-stimulating factor (GM-CSF)) compared to PBMCs recovered before surgery. The observed bias towards systemic anti-inflammatory changes without concomitant increases in pro-inflammatory responses may influence susceptibility to infection following orthopaedic surgery in the context of underlying co-morbidities or risk factors.

Solubility and Selectivity Effects of the Anion on the Adsorption of Different Heavy Metal Ions onto Chitosan.

The biopolymer chitosan is a very efficient adsorber material for the removal of heavy metal ions from aqueous solutions. Due to the solubility properties of chitosan it can be used as both a liquid adsorber and a solid flocculant for water treatment reaching outstanding adsorption capacities for a number of heavy metal ions. However, the type of anion corresponding to the investigated heavy metal ions has a strong influence on the adsorption capacity and sorption mechanism on chitosan. In this work, the adsorption capacity of the heavy metal ions manganese, iron, cobalt, nickel, copper, and zinc were investigated in dependence on their corresponding anions sulfate, chloride, and nitrate by batch experiments. The selectivity of the different heavy metal ions was analyzed by column experiments.

Tuning the Porosity and Photocatalytic Performance of Triazine-Based Graphdiyne Polymers through Polymorphism.

Crystalline and amorphous organic materials are an emergent class of heterogeneous photocatalysts for the generation of hydrogen from water, but a direct correlation between their structures and the resulting properties has not been achieved so far. To make a meaningful comparison between structurally different, yet chemically similar porous polymers, two porous polymorphs of a triazine-based graphdiyne (TzG) framework are synthesized by a simple, one-pot homocoupling polymerization reaction using as catalysts CuI for TzGCu and PdII /CuI for TzGPd/Cu . The polymers form through irreversible coupling reactions and give rise to a crystalline (TzGCu ) and an amorphous (TzGPd/Cu ) polymorph. Notably, the crystalline and amorphous polymorphs are narrow-gap semiconductors with permanent surface areas of 660 m2 g-1 and 392 m2 g-1 , respectively. Hence, both polymers are ideal heterogeneous photocatalysts for water splitting with some of the highest hydrogen evolution rates reported to date (up to 972 µmol h-1 g-1 with and 276 µmol h-1 g-1 without Pt cocatalyst). Crystalline order is found to improve delocalization, whereas the amorphous polymorph requires a cocatalyst for efficient charge transfer. This will need to be considered in future rational design of polymer catalysts and organic electronics.

Therapeutic and economic effects of multimodal back exercise: A controlled multicentre study.

To compare the cost-effectiveness of a multimodal back exercise programme for non-specific back pain with that of standard treatment. Medical costs were measured in euros (EUR) and effectiveness was measured using Graded Chronic Pain Status (GCPS). A controlled multicentre study (39 sites) with a 6-month intervention phase and follow-up at 6, 12 and 18 months. The study included 1,829 participants in an intervention group and 495 individuals in a control group. The multimodal back exercise programme comprises 36 exercise sessions for optimizing the spine stabilizing muscles and everyday motor func-tions. The patients were given a home training programme at the end of the intervention programme. The back exercise programme resulted in a significant reduction, of 0.4, in back pain grade on the GCPS after 2 years, compared with standard treat-ment, and reduced medical costs by 763 EUR. The exercise programme was therapeutically effective for GCPS back pain grades 1-4 and produced cost savings in the case of grade 4 GCPS. The multimodal back exercise programme was therapeutically effective for back pain (grades 1-2) and pain-related functional impairment (grades 3-4). It resulted in reduced costs for chronic back pain causing high pain-induced functional impairment (grade 4). The therapeutic and economic effects of the programme increase with the grade of back pain.

Exploring the "Goldilocks Zone" of Semiconducting Polymer Photocatalysts by Donor-Acceptor Interactions.

Water splitting using polymer photocatalysts is a key technology to a truly sustainable hydrogen-based energy economy. Synthetic chemists have intuitively tried to enhance photocatalytic activity by tuning the length of π-conjugated domains of their semiconducting polymers, but the increasing flexibility and hydrophobicity of ever-larger organic building blocks leads to adverse effects such as structural collapse and inaccessible catalytic sites. To reach the ideal optical band gap of about 2.3 eV, A library of eight sulfur and nitrogen containing porous polymers (SNPs) with similar geometries but with optical band gaps ranging from 2.07 to 2.60 eV was synthesized using Stille coupling. These polymers combine π-conjugated electron-withdrawing triazine (C3 N3 ) and electron donating, sulfur-containing moieties as covalently bonded donor-acceptor frameworks with permanent porosity. The remarkable optical properties of SNPs enable fluorescence on-off sensing of volatile organic compounds and illustrate intrinsic charge-transfer effects.

Fluorescent Sulphur- and Nitrogen-Containing Porous Polymers with Tuneable Donor-Acceptor Domains for Light-Driven Hydrogen Evolution.

Light-driven water splitting is a potential source of abundant, clean energy, yet efficient charge-separation and size and position of the bandgap in heterogeneous photocatalysts are challenging to predict and design. Synthetic attempts to tune the bandgap of polymer photocatalysts classically rely on variations of the sizes of their π-conjugated domains. However, only donor-acceptor dyads hold the key to prevent undesired electron-hole recombination within the catalyst via efficient charge separation. Building on our previous success in incorporating electron-donating, sulphur-containing linkers and electron-withdrawing, triazine (C3 N3 ) units into porous polymers, we report the synthesis of six visible-light-active, triazine-based polymers with a high heteroatom-content of S and N that photocatalytically generate H2 from water: up to 915 µmol h-1 g-1 with Pt co-catalyst, and-as one of the highest to-date reported values -200 µmol h-1 g-1 without. The highly modular Sonogashira-Hagihara cross-coupling reaction we employ, enables a systematic study of mixed (S, N, C) and (N, C)-only polymer systems. Our results highlight that photocatalytic water-splitting does not only require an ideal optical bandgap of ≈2.2 eV, but that the choice of donor-acceptor motifs profoundly impacts charge-transfer and catalytic activity.

The Influence of Salt Anions on Heavy Metal Ion Adsorption on the Example of Nickel.

The biodegradable polysaccharide chitosan possesses protonated and natural amino groups at medium pH values and has therefore been used as an adsorbing material for nickel salts in water treatment. Nickel is a problematic heavy metal ion which can cause various diseases and disorders in living organisms. Here, we show the influence of oxyanions (e.g., nitrate and sulfate) to the adsorption of nickel ions. Hence, simultaneously we are addressing the increasing global problem of nitrate and sulfate ion pollution in groundwater and surface water. A series of adsorption experiments was carried out in order to determine (i) the adsorption equilibrium, (ii) the adsorption capacity in dependence on the initial nickel ion concentration, and (iii) the influence of the anion presented in solution for the adsorption capacity. Surface morphology of chitosan flakes before and after the adsorption process has been studied with SEM-EDX analysis. The chitosan flakes exhibited promising adsorption capacities of 81.9 mg·g-1 and 21.2 mg·g-1 for nickel (sulfate) and nickel (nitrate), respectively. The calculated values of Gibbs free energy change ΔG° confirm the higher adsorption of nickel ions in presence of sulfate ions. Hence, higher anion valence leads to a higher adsorption capacity.

Complex calcium carbonate/polymer microparticles as carriers for aminoglycoside antibiotics.

Composite microparticles of CaCO3 and two pectin samples (which differ by the functional group ratio) or corresponding nonstoichiometric polyelectrolyte complexes with different molar ratios (0.5, 0.9 and 1.2) are obtained, characterized and tested for loading and release of streptomycin and kanamycin sulphate. The synthesized carriers were characterized before and after drug loading in terms of morphology (by SEM using secondary electron and energy selective backscattered electron detectors), porosity (by water sorption isotherms) and elemental composition (by elemental mapping using energy dispersive X-ray and FTIR spectroscopy). The kinetics of the release mechanism from the microparticles was investigated using Higuchi and Korsmeyer-Peppas mathematical models.

Twinned Growth of Metal-Free, Triazine-Based Photocatalyst Films as Mixed-Dimensional (2D/3D) van der Waals Heterostructures.

Design and synthesis of ordered, metal-free layered materials is intrinsically difficult due to the limitations of vapor deposition processes that are used in their making. Mixed-dimensional (2D/3D) metal-free van der Waals (vdW) heterostructures based on triazine (C3 N3 ) linkers grow as large area, transparent yellow-orange membranes on copper surfaces from solution. The membranes have an indirect band gap (Eg,opt = 1.91 eV, Eg,elec = 1.84 eV) and are moderately porous (124 m2 g-1 ). The material consists of a crystalline 2D phase that is fully sp2 hybridized and provides structural stability, and an amorphous, porous phase with mixed sp2 -sp hybridization. Interestingly, this 2D/3D vdW heterostructure grows in a twinned mechanism from a one-pot reaction mixture: unprecedented for metal-free frameworks and a direct consequence of on-catalyst synthesis. Thanks to the efficient type I heterojunction, electron transfer processes are fundamentally improved and hence, the material is capable of metal-free, light-induced hydrogen evolution from water without the need for a noble metal cocatalyst (34 µmol h-1 g-1 without Pt). The results highlight that twinned growth mechanisms are observed in the realm of "wet" chemistry, and that they can be used to fabricate otherwise challenging 2D/3D vdW heterostructures with composite properties.

Tailored Band Gaps in Sulfur- and Nitrogen-Containing Porous Donor-Acceptor Polymers.

Donor-acceptor dyads hold the key to tuning of electrochemical properties and enhanced mobility of charge carriers, yet their incorporation into a heterogeneous polymer network proves difficulty owing to the fundamentally different chemistry of the donor and acceptor subunits. A family of sulfur- and nitrogen-containing porous polymers (SNPs) are obtained via Sonogashira-Hagihara cross-coupling and combine electron-withdrawing triazine (C3 N3 ) and electron-donating, sulfur-containing linkers. Choice of building blocks and synthetic conditions determines the optical band gap (from 1.67 to 2.58 eV) and nanoscale ordering of these microporous materials with BET surface areas of up to 545 m2 g-1 and CO2 capacities up to 1.56 mmol g-1 . Our results highlight the advantages of the modular design of SNPs, and one of the highest photocatalytic hydrogen evolution rates for a cross-linked polymer without Pt co-catalyst is attained (194 µmol h-1 g-1 ).

Synthesis of mesoporous poly(melamine-formaldehyde) particles by inverse emulsion polymerization.

Mesoporous poly(melamine-formaldehyde) (MF) particles with surface areas of up to 200m2g-1 were synthesized by an inverse emulsion polymerization using dodecane and Span80® as continuous phase. The finer details of the shape control (using emulsion techniques) and the porosity control (using silica nanoparticles as hard-template) are discussed. The impact of phase-separation processes on the observable porosity of the 20-200µm sized spherical particles is analysed by gas sorption methods and electron microscopy. The high density of amine and triazine functional groups in the porous MF particles make the material a promising adsorber for heavy metal ions and methylene blue. In a preliminary column experiment, the synthesized material exhibited a total capacity of 2.54mmol/g (≙ 812.4mg/g) for the adsorption of methylene blue.