Reversible Uptake Research Articles

Reversible Sol-Gel Transitions Mediated Organics Selective Uptake and Release for Simultaneous Water Purification and Chemicals Recovery.

The separation and recovery of useful organics from wastewater have been a promising alternative to tackling water pollution and resource shortages, while strategies that truly work have rarely been explored. Herein, a reversible CO2 triggered sol-gel state transformation mediated selective organics uptake-release system using a surface modified carbonitride (S-CN) is proposed and exhibits remarkable organics recovery performance from wastewater. Results show that CO2 can serve as a cross-linker for linking S-CN particles to form a hydrogel by electrostatic interaction and hydrogen bonding, which can be recycled to the pristine sol state simply by removing the cross-linked CO2 with Ar purging. The reversible sol-gel transformation achieves nearly complete uptake of valuable organics from wastewater with high selectivity at the first sol-to-gel stage through electrostatic interaction, hydrogen bonding, and π-π interactions together, and it recovers 90% of the organics uptaked by releasing them into a concentrated solution at the second gel-back-to-sol stage.

Development and evaluation of deuterated [18F]JHU94620 isotopologues for the non-invasive assessment of the cannabinoid type 2 receptor in brain.

The cannabinoid type 2 receptors (CB2R) represent a target of increasing importance in neuroimaging due to its upregulation under various neuropathological conditions. Previous evaluation of [18F]JHU94620 for the non-invasive assessment of the CB2R availability by positron emission tomography (PET) revealed favourable binding properties and brain uptake, however rapid metabolism, and generation of brain-penetrating radiometabolites have been its main limitations. To reduce the bias of CB2R quantification by blood-brain barrier (BBB)-penetrating radiometabolites, we aimed to improve the metabolic stability by developing -d4 and -d8 deuterated isotopologues of [18F]JHU94620. The deuterated [18F]JHU94620 isotopologues showed improved metabolic stability avoiding the accumulation of BBB-penetrating radiometabolites in the brain over time. CB2R-specific binding with KD values in the low nanomolar range was determined across species. Dynamic PET studies revealed a CB2R-specific and reversible uptake of [18F]JHU94620-d8 in the spleen and to a local hCB2R(D80N) protein overexpression in the striatal region in rats. These results support further investigations of [18F]JHU94620-d8 in pathological models and tissues with a CB2R overexpression as a prerequisite for clinical translation.

Trimodal thermal energy storage material for renewable energy applications.

The global aim to move away from fossil fuels requires efficient, inexpensive and sustainable energy storage to fully use renewable energy sources. Thermal energy storage materials1,2 in combination with a Carnot battery3-5 could revolutionize the energy storage sector. However, a lack of stable, inexpensive and energy-dense thermal energy storage materials impedes the advancement of this technology. Here we report the first, to our knowledge, 'trimodal' material that synergistically stores large amounts of thermal energy by integrating three distinct energy storage modes-latent, thermochemical and sensible. The eutectic mixture of boric and succinic acids undergoes a transition at around 150 °C, with a record high reversible thermal energy uptake of 394 ± 5% J g-1. We show that the transition involves melting of the boric acid component, which simultaneously undergoes dehydration into metaboric acid and water that dissolve into the liquid. Being retained in the liquid state allows the metaboric acid to readily rehydrate to re-form boric acid on cooling. Thermal stability is demonstrated over 1,000 heating-cooling cycles. The material is very low cost, environmentally friendly and sustainable. This combination of a solid-liquid phase transition and a chemical reaction demonstrated here opens new pathways in the development of high energy capacity materials.

In Situ Generation of Microwire Heterojunctions with Flexible Optical Waveguide and Hydration‐Mediated Photochromism

AbstractFlexible heterojunctions based on molecular systems are in high demand for applications in photonics, electronics, and smart materials, but fabrication challenges have hindered progress. Herein, we present an in situ approach to creating optical heterojunctions using hydration‐mediated flexible molecular crystals. These hydrated multi‐component molecular solids display strong blue emitting optical waveguides with minimal optical loss (0.005 dB/μm) and excellent flexibility (elastic modulus: 3.87 GPa). The water‐mediated process enables the molecular microwires with tunable elastic and plastic deformation, as well as reversible uptake and release of lattice water, facilitating the formation of flexible heterojunctions. Spectral analysis and theoretical modeling reveal that these microwires exhibit both photochromism and color‐tunable dual emission (fluorescence and phosphorescence), expanding their utility in photonic information encoding. Therefore, this work introduces a hydration‐mediated molecular engineering strategy for fabricating crystalline heterojunctions with on‐demand processability and controllable emission sequences, enabling optical signal manipulation at the micro/nanoscale.

In Situ Generation of Microwire Heterojunctions with Flexible Optical Waveguide and Hydration-Mediated Photochromism.

Flexible heterojunctions based on molecular systems are in high demand for applications in photonics, electronics, and smart materials, but fabrication challenges have hindered progress. Herein, we present an in situ approach to creating optical heterojunctions using hydration-mediated flexible molecular crystals. These hydrated multi-component molecular solids display strong blue emitting optical waveguides with minimal optical loss (0.005 dB/μm) and excellent flexibility (elastic modulus: 3.87 GPa). The water-mediated process enables the molecular microwires with tunable elastic and plastic deformation, as well as reversible uptake and release of lattice water, facilitating the formation of flexible heterojunctions. Spectral analysis and theoretical modeling reveal that these microwires exhibit both photochromism and color-tunable dual emission (fluorescence and phosphorescence), expanding their utility in photonic information encoding. Therefore, this work introduces a hydration-mediated molecular engineering strategy for fabricating crystalline heterojunctions with on-demand processability and controllable emission sequences, enabling optical signal manipulation at the micro/nanoscale.

Metabolism and retention of verapamil dictate microneedle-based drug delivery: analytical and numerical study

This study systematically investigates, both analytically and numerically, transdermal drug delivery using a microneedle (MN) array. The drug released from the MN tip disperses through the viable skin before being absorbed in the blood compartment. Reversible uptake kinetics between the blood and tissue compartments, together with reversible specific binding of the drug with its receptors in the tissue, have been taken into account. The governing equations are solved analytically and numerically in an explicit manner. Simulations predict that the metabolism in the viable skin, irreversible uptake and specific binding have a stabilizing effect on the free and bound verapamil concentrations. In addition, a longer MN and a larger skin–blood interface area contribute to higher concentrations of all drug forms in the blood and tissue compartments. The results suggest that the lack of binding in the tissue compartment might overestimate the transdermal delivery of verapamil. A thorough sensitivity analysis has been performed to account for uncertainties in some of the parameters involved. The analysis of verapamil retention in the tissue and its relationship to the length of the MN, the time of application, the area of the skin–blood interface, the rate of metabolism and the reversible uptake kinetics between compartments constitute the novel aspect of this analytical and numerical work. Our reduced model is in excellent agreement with the results available in the literature.

Host-Guest Interactions Facilitated by Chalcogen Bonding within Selenadiazole Functionalised Porphyrin Nanotubes.

The structural rigidity of tetrakis(4-pyridyl)porphyrin (TPyP) has been utilised to prepare a robust novel porous coordination polymer of composition Cd2(TPyP)(sez)2 (TPyP=5,10,15,20-tetra(4-pyridyl)porphyrin, sez=1,2,5-benzoselenadiazole-5-carboxylate). The coordination polymer may be described as a hexagonal porphyrin nanotube (PNT) and has the potential to bind guest molecules through chalcogen bonding. Single crystal X-ray diffraction (SCXRD) data indicate an internal pore diameter ~9 Å which represents ~35 % of the crystal volume. Immersion of the PNTs in solvents such as DMSO and CS2 result in the incorporation of these molecules within the nanotubes with chalcogen bonding between host and guest. The crystallographic guest-inclusion investigations are complemented by solid-state 77Se, 13C, 113Cd and 2H NMR studies which provide insights into dynamic behaviour. The porosity of the crystals was further explored using gas adsorption experiments, indicating the reversible uptake of CO2, CH4, H2 and N2. Structure-function relationships are clearly established from complementary crystallographic, NMR and adsorption investigations.

Optimizing hydrogen storage in magnesium hydride using carbon-based catalysts

Abstract The utilization of fossil fuels, including coal, crude oil, and natural gas, has long been recognized as a significant contributor to environmental degradation, primarily due to their non-renewable nature and harmful emissions. The transition to renewable energy sources becomes imperative, and energy storage technologies are of paramount importance. In this context, hydrogen as chemical energy storage emerges represent a promising solution, offering both sustainability and environmental friendliness. However, the practical storage of hydrogen presents several challenges, primarily due to its light weight and gaseous nature. Among various storage methods, magnesium hydride (MgH2) has gained considerable attention due to its high hydrogen storage capacity, reversible uptake and release, and potential for safe handling and transportation. Nevertheless, magnesium hydride face inherent drawbacks, including low sorption and desorption kinetics, high hydrogen release temperatures, and the formation of undesirable gases during cycling. To overcome these challenges, various strategies have been proposed, with catalytic enhancement showing significant promise. Carbon-based materials and carbon-based composite materials have emerged as effective catalysts in improving the kinetics and efficiency of hydrogen storage in magnesium hydride. In this paper, that is a review of the existing literature, the role of these carbon-based catalysts in enhancing the performance of magnesium hydride for hydrogen storage will be explored, focusing on recent advancements and potential solutions to overcome existing limitations.

Sustainable di-functional stimuli-responsive imprinted nanozymes for reversible colorimetric sensing of tetracycline

Regenerable nanozymes with high catalytic specificity and sustainability may serve as substitutes for naturally occurring enzymes, but their application is hindered by inadequate and nonselective catalytic activity. In this study, we constructed a photo-responsive molecularly imprinted layer on the Fe3O4 nanozyme surface (P-MIPs) using an ATRP method and obtained high-specificity reversible colorimetric sensing of tetracycline (TC). Due to the photo-responsive properties of P-MIPs, the imprinted nanozyme undergoes reversible release and uptake of TC under alternating irradiation at 365/440 nm based on the photo-regulated conformational transformation of the 4-[(4-methacryloyloxy)phenylazo] benzenesulfonic acid (MAPASA) at the polymer receptor sites, which may be confirmed by calculating the electron densities of the trans-/cis-MAPASA forms. Simultaneously, these processes can be visualized through the change in the color of the substrates. Highly specific P-MIPs-based nanozyme also exhibit adequate stability and sustainable catalytic activity after multiple cycles. This method can be used to achieve nanozymes with high selectivity for the enrichment, separation, and detection of hazardous substances and contribute to material sustainability.

Nanoarchitectonics of Methyl and Aldehyde Group-Decorated SOD-Type Metal-Azolate Framework for SF6 Capture and Recovery.

Sulfur hexafluoride (SF6) is widely used as an insulating gas, being an etchant and contrast agent in the electrical, semiconductor, and medical industries. However, due to its long lifetime and high global warming potential in the atmosphere, SF6 must be carefully handled to prevent leakage during production and usage. Herein, we report a sod-net metal-azolate framework (MAF) named MAF-stu-111, which decorates methyl and aldehyde groups in the porous windows, showing high adsorption affinity for SF6 at low pressure. Stability tests, gas adsorption, and breakthrough experiments demonstrated that MAF-stu-111 possesses excellent water and chemical stability, fully reversible SF6 uptake, high SF6/N2 separation selectivity (10:90, 285.2), good reusability, and high SF6 recovery purity (99.03%). Theoretical calculations revealed that hydrogen atoms of methyl and aldehyde groups can form multiple hydrogen bonds with SF6 molecules, which ensure that SF6 molecules are firmly held within the MAF-stu-111 framework, playing a key role in the selective separation of SF6/N2.

Reversible Adsorption of Ammonia in the Crystalline Solid of a CO2H-Functionalized Cyclic Oligophenylene.

Ammonia (NH3) is a viable candidate for the storage and distribution of hydrogen (H2) due to its exceptional volumetric and gravimetric hydrogen energy density. Therefore, it is desirable to develop NH3 storage materials that exhibit robust stability across numerous adsorption-desorption cycles. While porous materials with polymeric frameworks are often used for NH3 capture, achieving reversible NH3 uptake remains a formidable challenge, primarily due to the high reactivity of NH3. Here, we advocate the use of CO2H-functionalized cyclic oligophenylene 1a with high chemical stability as a novel single-molecule-based adsorbent for NH3. Simple reprecipitation of 1a selectively yielded microporous crystalline solid 1a (N). Crystalline 1a (N) adsorbs up to 8.27 mmol/g of NH3 at 100 kPa and 293 K. Adsorbed NH3 in the pore of 1a (N) has a packing density of 0.533 g/cm3 at 293 K, which is close to the density of liquid NH3 (0.681 g/cm3 at 240 K). Crystalline 1a (N) also exhibits reversible NH3 adsorption over at least nine cycles, sustaining its storage capacity (1st cycle: 8.27 mmol/g; 9th cycle: 8.25 mmol/g at 100 kPa and 293 K) and crystallinity. During each desorption cycle, NH3 was removed from 1a (N) under reduced pressure (∼65 Pa), leaving <3% of the total uptake, and 1a (N) was fully purged under dynamic vacuum conditions (∼5 × 10-4 Pa at 293 K for 1 h) before the subsequent adsorption cycles. Thus, microporous crystalline 1a (N) can reliably adsorb and desorb NH3 repeatedly, which avoids the need for heat-based activation between cycles.

Dynamic role of GlyT1 as glycine sink or source: Pharmacological implications for the gain control of NMDA receptors

Glycine transporter 1 (GlyT1) mediates the termination of inhibitory glycinergic receptor signaling in the spinal cord and brainstem, and is also present diffusely in the forebrain. Here, it regulates the ambient glycine concentration and influences the ‘glycine’ site occupancy of N-methyl-d-aspartate receptors (NMDARs). GlyT1 is a reversible transporter with a substantial, but not excessive, sodium-motive force for uphill transport. This study investigates its role as a potential source of glycine supply, either by reverse uptake or heteroexchange. Indeed, glutamate alone does not induce NMDAR current in “naive” oocytes co-expressing GluN1/GluN2A and GlyT1, a previously characterized cellular model. However, after substantial intracellular glycine accumulation, GlyT1 reverses its transport mode, and begins to release glycine into the external compartment, allowing NMDAR activation by glutamate alone. These uptake-dependent glutamate currents were blocked by ALX-5407 and potentiated by sarcosine, a specific inhibitor and substrate of GlyT1, respectively, suggesting a higher occupancy of the co-agonist site when GlyT1 functions as a glycine source either by reversed-uptake or by heteroexchange. These two glycine release mechanisms can be distinguished by their voltage dependence, as the reversed-uptake cycle decreases at hyperpolarized potentials, whereas heteroexchange electroneutrality preserves glycine efflux and NMDAR activation at these potentials. These results establish GlyT1-mediated efflux as a positive regulator of NMDAR coagonist site occupancy, and demonstrate the efficacy of sarcosine heteroexchange in enhancing coagonist site occupancy. Because NMDAR facilitation by GlyT1-inhibitors and sarcosine relies on different transport mechanisms, their actions may be a source of variability in reversing NMDAR hypofunction in schizophrenia.

Organomagnesia: Reversibly High Carbon Dioxide Uptake by Magnesium Pyrazolates.

A series of new pyrazolate and mixed pyrazolate/pyrazole magnesium complexes is described and their reactivity toward carbon dioxide is examined. The dimeric complex [Mg(pzt Bu, t Bu)2]2 inserts CO2 instantly and quantitatively forming the tetrameric complex [Mg(CO2·pzt Bu, t Bu)2]4 and monomeric donor-stabilized [Mg(CO2·pzt Bu, t Bu)2(thf)2]. Complexes of the type [Mgx(pzR,R)2 x(HpzR,R)y]n (R = iPr, tBu) engage in similar insertion reactions involving dissociation of the carbamic acid HOOCpzR,R. Even solid polymeric derivatives [Mg(pzR,R)2]n (R = Me, H) react instantaneously and exhaustively with CO2, the resulting [Mg(CO2·pz)2]m featuring a CO2 capacity of 35.7wt% (8.2mmol g-1). All described magnesium pyrazolates display completely reversible CO2 uptake in solution and in the solid state, respectively, as monitored via VT 1H NMR and in situ FTIR spectroscopy as well as thermogravimetric analysis. Fluorinated [Mg2(pzCF3,CF3)4(thf)3] does not yield any isolable CO2 insertion product but exhibits the highest activity in the catalytic transformation of epoxides and CO2 to cyclic carbonates.

Sodium-Controlled Interfacial Resistive Switching in Thin Film Niobium Oxide for Neuromorphic Applications.

A double layer 2-terminal device is employed to show Na-controlled interfacial resistive switching and neuromorphic behavior. The bilayer is based on interfacing biocompatible NaNbO3 and Nb2O5, which allows the reversible uptake of Na+ in the Nb2O5 layer. We demonstrate voltage-controlled interfacial barrier tuning via Na+ transfer, enabling conductivity modulation and spike-amplitude- and spike-timing-dependent plasticity. The neuromorphic behavior controlled by Na+ ion dynamics in biocompatible materials shows potential for future low-power sensing electronics and smart wearables with local processing.

A Membrane-Free Rechargeable Seawater Battery Unlocked by Lattice Engineering.

Seawater batteries that directly utilize natural seawater as electrolytes are ideal sustainable aqueous devices with high safety, exceedingly low cost, and environmental friendliness. However, the present seawater batteries are either primary batteries or rechargeable half-seawater/half-nonaqueous batteries because of the lack of suitable anode working in seawater. Here, a unique lattice engineering to unlock the electrochemically inert anatase TiO2 anode to be highly active for the reversible uptake of multiple cations (Na+, Mg2+, and Ca2+) in aqueous electrolytes is demonstrated. Density functional theory calculationsfurther reveal the origin of the unprecedented charge storage behaviors, which can be attributed to the significant reduction of the cations diffusion barrier within the lattice, i.e., from 1.5 to 0.4eV. As a result, the capacities of anatase TiO2 with 2.4% lattice expansion are ≈100 times higher than the routine one in natural seawater, and ≈200 times higher in aqueous Na+ electrolyte. The finding will significantly advance aqueous seawater energy storage devices closer to practical applications.

Direct Observation of Enhanced Iodine Binding within a Series of Functionalized Metal-Organic Frameworks with Exceptional Irradiation Stability.

Optimization of active sites and stability under irradiation are important targets for sorbent materials that might be used for iodine (I2) storage. Herein, we report the direct observation of I2 binding in a series of Cu(II)-based isostructural metal-organic frameworks, MFM-170, MFM-172, MFM-174, NJU-Bai20, and NJU-Bai21, incorporating various functional groups (-H, -CH3, - NH2, -C≡C-, and -CONH-, respectively). MFM-170 shows a reversible uptake of 3.37 g g-1 and a high packing density of 4.41 g cm-3 for physiosorbed I2. The incorporation of -NH2 and -C≡C- moieties in MFM-174 and NJU-Bai20, respectively, enhances the binding of I2, affording uptakes of up to 3.91 g g-1. In addition, an exceptional I2 packing density of 4.83 g cm-3 is achieved in MFM-174, comparable to that of solid iodine (4.93 g cm-3). In situ crystallographic studies show the formation of a range of supramolecular and chemical interactions [I···N, I···H2N] and [I···C≡C, I-C═C-I] between -NH2, -C≡C- sites, respectively, and adsorbed I2 molecules. These observations have been confirmed via a combination of solid-state nuclear magnetic resonance, X-ray photoelectron, and Raman spectroscopies. Importantly, γ-irradiation confirmed the ultraresistance of MFM-170, MFM-174, and NJU-Bai20 suggesting their potential as efficient sorbents for cleanup of radioactive waste.

Chemically Reversible CO2 Uptake by Dendrimer-Impregnated Metal-Organic Frameworks.

Industrialization over the past two centuries has resulted in a continuous rise in global CO2 emissions. These emissions are changing ecosystems and livelihoods. Therefore, methods are needed to capture these emissions from point sources and possibly from our atmosphere. Though the amount of CO2 is rising, it is challenging to capture directly from air because its concentration in air is extremely low, 0.04%. In this study, amines installed inside metal-organic frameworks (MOFs) are investigated for the adsorption of CO2, including at low concentrations. The amines used are polyamidoamine dendrimers that contain many primary amines. Chemically reversible adsorption of CO2 via carbamate formation was observed, as was enhanced uptake of carbon dioxide, likely via dendrimer-amide-based physisorption. Limiting factors in this initial study are comparatively low dendrimer loadings and slow kinetics for carbon dioxide uptake and release, even at 80 °C.

Ni(II) triggered sensing and reversible uptake of ammonia by tetrazole based Ni(II) metallogel: A one-pot mechanistic approach

The release of ammonia gas and its removal through traditional approaches is a critical challenge inhibiting the sustainability of chemical industries. The quest to improve sustainability has triggered interest to develop chemoprobe and reusable adsorbent for toxic gases such as ammonia. The present study offers the first example of a novel one-pot synthesis of a stable Ni(II)metallogel (Ni(II)MG) from 1, 4 adiponitrile and sodium azide. The Ni(II)MG is composed of Ni(II) coordinated with four in-situ formed CN-Tz (5-(1H-tetrazol-5-yl)pentanenitrile) ligands and two water molecules forming predominant octahedral geometry. The Ni(II)MG has good strength, and viscoelastic, thixotropic, and self-healing properties. The Ni(II)MG and its xerogel (Ni(II)XG) have been thoroughly characterized and utilized for ammonia sensing and reversible adsorption at ambient condition. The mesoporous nature and presence of hydrogen-bonded water molecules in the pores make this material effective for reversible adsorption of ammonia. The lewis acidic Ni(II) increases the cloud network of hydrogen-bonded water molecules and triggers the coordinated water molecules to activate hydrogen-bonded water molecules for binding the ammonia molecules. The Ni(II) triggered extended hydrogen bonding through coordinated water molecule is also supported by DFT studies. The Ni(II)XG shows good ammonia adsorption capacity (8 mmol/gm) which is confirmed by TPD studies. The properties of Ni(II)XG are found to be intact after ammonia adsorption even after 20 cycles. Hence, it could be a promising low cost, sustainable and reusable material as a chemoprobe for removal of ammonia.

Universal Intercalation/Alloying Hybrid Mechanism with -ICOHP Criterion in MAX Toward Steadily Ascending Lithium-Ion Batteries.

Profiting from the unique atomic laminated structure, metallic conductivity, and superior mechanical properties, transition metal carbides and nitrides named MAX phases have shown great potential as anodes in lithium-ion batteries. However, the complexity of MAX configurations poses a challenge. To accelerate such application, a minus integrated crystal orbital Hamilton populations descriptor is innovatively proposed to rapidly evaluate the lithium storage potential of various MAX, along with density functional theory computations. It confirms that surface A-element atoms bound to lithium ions have odds of escaping from MAX. Interestingly, the activated A-element atoms enhance the reversible uptake of lithium ions by MAX anodes through an efficient alloying reaction. As an experimental verification, the charge compensation and SnxLiy phase evolution of designed Zr2SnC MAX with optimized structure is visualized via in situ synchrotron radiation XRD and XAFS technique, which further clarifies the theoretically expected intercalation/alloying hybrid storage mechanism. Notably, Zr2SnC electrodes achieve remarkably 219.8% negative capacity attenuation over 3200 cycles at 1Ag-1. In principle, this work provides a reference for the design and development of advanced MAX electrodes, which is essential to explore diversified applications of the MAX family in specific energy fields.

Photo-Controlled Reversible Uptake and Release of a Modified Sulfamethoxazole Antibiotic Drug from a Pillar[5]arene Cross-Linked Gelatin Hydrogel.

Pillararene cross-linked gelatin hydrogels were designed and synthesized to control the uptake and release of antibiotics using light. A suite of characterization techniques ranging from spectroscopy (FT-IR, 1H and 13C NMR, and MAS NMR), X-ray crystallographic analysis, scanning electron microscopy (SEM), and thermogravimetric analysis (TGA) was employed to investigate the physicochemical properties of hydrogels. The azobenzene-modified sulfamethoxazole (Azo-SMX) antibiotic was noncovalently incorporated into the hydrogel via supramolecular host-guest interactions to afford the A-hydrogel. While in its ground state, the Azo-SMX guest has a trans configuration structure and forms a thermodynamically stable inclusion complex with the pillar[5]arene motif in the hydrogel matrix. When the A-hydrogel was exposed to 365 nm UV light, Azo-SMX underwent a photoisomerization reaction. This changed the structure of Azo-SMX from trans to cis, and the material was released into the environment. The Azo-SMX released from the hydrogel was effective against both Gram-positive and Gram-negative bacteria. Importantly, the A-hydrogel exhibited a striking difference in antibacterial activity when applied to bacterial colonies in the presence and absence of UV light, highlighting the switchable antibacterial activity of A-hydrogel aided by light. In addition, all hydrogels containing pillar[5]arenes have demonstrated biocompatibility and effectiveness as scaffolds for biological and medical purposes.