Red‐ to NIR‐Emitting,BODIPY‐Based,K+‐Selective Fluoroionophores and Sensing Materials

Optical sensing materials for the selective measurement of potassium ions (K⁺) in water are presented. The indicator dyes are based on an aza‐crown ether as a receptor and borondipyrromethenes (BODIPY) dyes as fluorophores. Fluorescence enhancement is caused by the reduction of photoinduced electron transfer (PET) upon complexation with K⁺ ions. The family of new indicators possesses tuneable optical properties (green to red excitation, red to NIR emission) and PET efficiencies. They exhibit high brightness with quantum yields between 0.20 and 0.47 in the “on” state and a molar absorption coefficient between 30 000 and 290 000 m ^?1 cm^?1. The new indicator dyes are immobilized in biocompatible hydrogel matrices to obtain stable nonleaching and fast responding (t₉₀ ≈ 10 s) sensing materials for continuous measurements of potassium. They are realized in various formats such as planar optodes, fiber‐optic sensors, and water‐dispersible polymer‐based nanoparticles. Apart from fluorescence intensity measurements, self‐referenced read‐out of fluorescence decay time is demonstrated. All sensor materials display a high K⁺/Na⁺ selectivity and are not influenced by pH within the physiologically relevant range. Practical applicability of the materials is emphasized by application of a fiber‐optic sensor to quantification of K⁺ in serum, which shows excellent correlation with the reference measurements.     

Tailoring Amino‐Functionalized Graphitic Carbon‐Encapsulated Gold Core/Shell Nanostructures for the Sensitive and Selective Detection of Copper Ions

The effective transfer of strong electromagnetic field from the gold core through the coating shell represents the most significant challenge for the applications of plasmonic nanoparticles. This study applies a one‐step arc discharge method to synthesize graphitic carbon‐encapsulated gold nanoparticles (Au@G NPs) functionalized with amino groups uniformly via adding NH₃ into He background gas. By tailoring the coating shell into few‐layered graphene, a strong localized surface plasmon resonance (LSPR) absorption band is achieved. The NH₃ introduces H radicals to strengthen the LSPR characteristic by etching the coating graphitic shell, as well as provides dissociated NH or NH₂ species to functionalize the surfaces with amino groups. With an LSPR‐based colorimetric method, it is demonstrated that trace Cu²⁺ ions can be detected rapidly with excellent sensitivity (as low as 10 × 10^‐9m linearly) and selectivity against other metal ions (Na⁺, K⁺, Mg²⁺, Ca²⁺, Co²⁺, Fe²⁺, Cd²⁺, Pb²⁺, and Hg²⁺ ions) by amino‐functionalized Au@G NPs in water samples.     

Dendrimer‐Functionalized Iron Oxide Nanoparticles for Specific Targeting and Imaging of Cancer Cells

We demonstrated a unique approach that combines a layer‐by‐layer (LbL) self‐assembly method with dendrimer chemistry to functionalize Fe₃O₄ nanoparticles (NPs) for specific targeting and imaging of cancer cells. In this approach, positively charged Fe₃O₄ NPs (8.4 nm in diameter) synthesized by controlled co‐precipitation of Fe^II and Fe^III ions were modified with a bilayer composed of polystyrene sulfonate sodium salt and folic acid (FA)‐ and fluorescein isothiocyanate (FI)‐functionalized poly(amidoamine) dendrimers of generation 5 (G5.NH₂‐FI‐FA) through electrostatic LbL assembly, followed by an acetylation reaction to neutralize the remaining surface amine groups of G5 dendrimers. Combined flow cytometry, confocal microscopy, transmission electron microscopy, and magnetic resonance imaging studies show that Fe₃O₄/PSS/G5.NHAc‐FI‐FA NPs can specifically target cancer cells overexpressing FA receptors. The present approach to functionalizing Fe₃O₄ NPs opens a new avenue to fabricating various NPs for numerous biological sensing and therapeutic applications.     

Gated Mesoporous SiO2 Nanoparticles Using K+‐Stabilized G‐Quadruplexes

The K⁺‐induced formation of G‐quadruplexes provides a versatile motif to lock or unlock substrates trapped in the pores of mesoporous SiO₂ nanoparticles, MP‐SiO₂ NPs. In one system, the substrate is locked in the MP‐SiO₂ NPs by K⁺‐ion‐stabilized G‐quadruplex units, and the pores are unlocked by the elimination of K⁺ ions using Kryptofix [2.2.2] (KP) or 18‐crown‐6‐ether (CE) from the G‐quadruplexes. In the second system, the substrate is locked in the pores by means of K⁺‐stabilized aptameric G‐quadruplex/thrombin units. Unlocking of the pores is triggered by the dissociation of the aptamer/thrombin complexes through the KP‐ or CE‐mediated elimination of the stabilizing K⁺ ions. In the third system, duplex DNA units lock the pores of MP‐SiO₂ NPs, and the release of the entrapped substrate is stimulated by the K⁺‐ion‐induced dissociation of the duplex caps through the formation of the K⁺‐stabilized G‐quadruplexes. The latter system is further implemented to release the anti‐cancer drug, doxorubicin, in the presence of K⁺ ions, from the MP‐SiO₂ NPs. Preliminary intracellular experiments reveal that doxorubicin‐loaded MP‐SiO₂ NPs lead to effective death of breast cancer cells.     

Highly Fluorescent Conjugated Polyelectrolyte Nanostructures: Synthesis,Self‐Assembly,and Al3+ Ion Sensing

A highly fluorescent triazine‐bridged polymer, poly[(diphenylamino‐s‐triazine)‐co‐(2‐methoxy‐5‐propyloxysulfonate‐1,4‐phenylene vinylene)] (DTMSPV), is synthesized from Wittig polycondensation of a triazine monomer with a water‐soluble p‐phenylene vinylene monomer. The fluorescent amphiphilic polymer in aqueous solution self‐assembled into nanoassemblies of micelle‐like nanostructure (MS) and π stacking nanostructure (πS), which have average sizes of 93 to 270 nm, depending on the concentration of DTMSPV. The micelle‐like nanostructure of DTMSPV (MS) shows blue emission at 457 and 488 nm with a high emission quantum yield (Φ_E) of 31% in aqueous solution. On the other hand, the Φ_E of π stacking structures (πS), formed in a highly concentrated solution, is lower than the MS. The MS exhibits fluorescence quenching as well as color change from blue to green/yellow, depending on the kinds of metal ions. The metal ion sensitivity is larger in the order of the main group ions (Na⁺, K⁺) < dicationic transition metal ions (Zn²⁺, Cd²⁺, Pb²⁺, Cu²⁺, Pd²⁺) < trivalent transition metal ions (Fe³⁺, Ru³⁺), with an exception of Al³⁺. In particular, the fluorescence of MS is dramatically quenched with color change to yellow in response to Al³⁺ concentrations. The selectivity and sensitivity of MS to Al³⁺ are unusually high even in the presence of competitive metal ions, which can be attributed to the specific interaction of triazine units with Al³⁺.     

Positive and Negative Lattice Shielding Effects Co‐existing in Gd (III) Ion Doped Bifunctional Upconversion Nanoprobes

Gadolinium (Gd) doped upconversion nanoparticles (UCNPs) have been well documented as T₁‐MR and fluorescent imaging agents. However, the performance of Gd³⁺ ions located differently in the crystal lattice still remains debatable. Here, a well‐designed model was built based on a seed‐mediated growth technique to systematically probe the longitudinal relaxivity of Gd³⁺ ions within the crystal lattice and at the surface of UCNPs. We found, for the first time, a nearly 100% loss of relaxivity of Gd³⁺ ions buried deeply within crystal lattices (> 4 nm), which we named a “negative lattice shielding effect” (n‐LSE) as compared to the “positive lattice shielding effect” (p‐LSE) for the enhanced upconversion fluorescent intensity. As‐observed n‐LSE was further found to be shell thickness dependent. By suppressing the n‐LSE as far as possible, we optimized the UCNPs' structure design and achieved the highest r₁ value (6.18 mM^?1s^?1 per Gd³⁺ ion) among previously reported counterparts. The potential bimodal imaging application both in vitro and in vivo of as‐designed nano‐probes was also demonstrated. This study clears the debate over the role of bulk and surface Gd³⁺ ions in MRI contrast imaging and paves the way for modulation of other Gd‐doped nanostructures for highly efficient T₁‐MR and upconversion fluorescent bimodal imaging.     

Well‐Defined Protein‐Based Supramolecular Nanoparticles with Excellent MRI Abilities for Multifunctional Delivery Systems

Protein‐based nanoparticles are widely used for effective biomedical applications. The objective of this work is to design series of magnetic resonance imaging (MRI)‐visible cationic supramolecular nanoparticles (PGEA@BSA‐Ad/Gd³⁺) based on bovine serum albumin (BSA) and β‐cyclodextrin‐cored star ethanolamine‐functionalized poly(glycidyl methacrylate) (CD‐PGEA) in the presence of Gd³⁺ ions for multifunctional delivery systems. CD‐PGEA is prepared via atom transfer radical polymerization and ring‐opening reaction. It is found that in the absence of Gd³⁺ ions, CD‐PGEA does not well interact with adamantine‐modified BSA (BSA‐Ad). The well‐defined PGEA@BSA‐Ad/Gd³⁺ supramolecular nanoparticles could be produced through the synergistic actions of the host–guest and electrostatic self‐assemblies by mixing aqueous solutions of CD‐PGEA, BSA‐Ad, and Gd³⁺. In comparison with CD‐PGEA assembly units, such kinds of uniform PGEA@BSA‐Ad/Gd³⁺ supramolecular nanoparticles exhibit better pDNA condensation ability, lower cytotoxicity, higher gene transfection, and easier cellular uptake. In addition, PGEA@BSA‐Ad/Gd³⁺ also produces outstanding MRI abilities, much better than Magnevist (Gd‐diethylenetriaminepentacetate acid). The present design of protein–polymer supramolecular nanoparticles with MRI contrast agents would provide a new way for multifunctional gene/drug delivery systems.     

Membrane‐Free Detection of Metal Cations with an Organic Electrochemical Transistor

Alkali‐metal ions, particularly sodium (Na⁺) and potassium (K⁺), are the messengers of living cells, governing a cascade of physiological processes through the action of ion channels. Devices that can monitor, in real time, the concentrations of these cations in aqueous media are in demand not only for the study of cellular machinery, but also to detect conditions in the human body that lead to electrolyte imbalance. In this work, conducting polymers are developed that respond rapidly and selectively to varying concentrations of Na⁺ and K⁺ in aqueous media. These polymer films, bearing crown‐ether‐functionalized thiophene units specific to either Na⁺ or K⁺, generate an electrical output proportional to the cation type and concentration. Using electropolymerization, the ion‐selective polymers are integrated as the gate electrode of an organic electrochemical transistor (OECT). The OECT current changes with respect to the concentration of the ion to which the polymer electrode is selective. Designed as a single, miniaturized chip, the OECT enables the selective detection of the cations within a physiologically relevant range. These electrochemical ion sensors require neither ion‐selective membranes nor a reference electrode to operate and have the potential to surpass existing technologies for the detection of alkali‐metal ions in aqueous media.     

Biomimetic Natural Killer Membrane Camouflaged Polymeric Nanoparticle for Targeted Bioimaging

In the present study, a biomimetic nanoconstruct (BNc) with a multimodal imaging system is engineered using tumor homing natural killer cell membrane (NKM), near‐infrared (NIR) fluorescent dye, and gadolinium (Gd) conjugate‐based magnetic resonance imaging contrast agent onto the surface of a polymeric nanoparticle. The engineered BNc is 110 ± 20 nm in size and showed successful retention of NKM proteins. The magnetic properties of the BNc are found to be tunable from 2.1 ± 0.17 to 5.3 ± 0.5 mm ^?1 s^?1 under 14.1 T, by adjusting the concentration of Gd‐lipid conjugate onto the surface of the BNc. Confocal imaging and cell sorting analysis reveal a distinguishable cellular interaction of the BNc with MCF‐7 cells in comparison to that of bare polymeric nanoparticles suggesting the tumor homing properties of NKM camouflage system. The in vitro cellular interaction results are further confirmed by in vivo NIR fluorescent tumor imaging and ex vivo MR imaging, respectively. Pharmacokinetics and biodistribution analysis of the BNc show longer circulation half‐life (≈9.5 h) and higher tumor accumulation (10% of injected dose) in MCF‐7 induced tumor‐bearing immunodeficient NU/NU nude mice. Owing to the proven immunosurveillance potential of NK‐cell in the field of immunotherapy, the BNc engineered herein would hold promises in the design consideration of nanomedicine engineering.     

Multifunctional Up‐Converting Nanocomposites with Smart Polymer Brushes Gated Mesopores for Cell Imaging and Thermo/pH Dual‐Responsive Drug Controlled Release

Multifunctional nanocarriers based on the up‐conversion luminescent nanoparticles of NaYF₄:Yb³⁺/Er³⁺ core (UCNPs) and thermo/pH‐coupling sensitive polymer poly[(N‐isopropylacrylamide)‐co‐(methacrylic acid)] (P(NIPAm‐co‐MAA)) gated mesoporous silica shell are reported for cancer theranostics, including fluorescence imaging, and for controlled drug release for therapy. The as‐synthesized hybrid nanospheres UCNPs@mSiO₂‐P(NIPAm‐co‐MAA) show bright green up‐conversion fluorescence under 980 nm laser excitation and the thermo/pH‐sensitive polymer is active as a “valve” to moderate the diffusion of the embedded drugs in‐and‐out of the pore channels of the silica container. The anticancer drug doxorubicin hydrochloride (DOX) can be absorbed into UCNPs@mSiO₂‐P(NIPAm‐co‐MAA) nanospheres and the composite drug delivery system (DDS) shows a low level of leakage at low temperature/high pH values but significantly enhanced release at higher temperature/lower pH values, exhibiting an apparent thermo/pH controlled “on‐off” drug release pattern. The as‐prepared UCNPs@mSiO₂‐P(NIPAm‐co‐MAA) hybrid nanospheres can be used as bioimaging agents and biomonitors to track the extent of drug release. The reported multifunctional nanocarriers represent a novel and versatile class of platform for simultaneous imaging and stimuli‐responsive controlled drug delivery.     

Harnessing Selectivity and Sensitivity in Ion Sensing via Supramolecular Recognition: A 3D Hybrid Gold Nanoparticle Network Chemiresistor

The monitoring of K⁺ in saliva, blood, urine, or sweat represents a future powerful alternative diagnostic tool to prevent various diseases. However, several K⁺ sensors are unable to meet the requirements for the development of point-of-care (POC) sensors. To tackle this grand-challenge, the fabrication of chemiresistors (CRs) based on 3D networks of Au nanoparticles covalently bridged by ad-hoc supramolecular receptors for K⁺, namely dithiomethylene dibenzo-18-crown-6 ether is reported here. A multi-technique characterization allows optimizing a new protocol for fabricating high-performing CRs for real-time monitoring of K⁺ in complex aqueous environments. The sensor shows exceptional figures of merit: i) linear sensitivity in the 10^–3 to 10^–6 m concentration range; ii) high selectivity to K⁺ in presence of interfering cations (Na⁺, Ca²⁺, and Mg²⁺); iii) high shelf-life stability ( > 45 days); iv) reversibility of K⁺ binding and release; v) successful device integration into microfluidic systems for real-time monitoring; vi) fast response and recovery times ( < 18 s), and v) K⁺ detection in artificial saliva. All these characteristics make the supramolecular CRs a potential tool for future applications as POC devices, especially for health monitoring where the determination of K⁺ in saliva is pivotal for the early diagnosis of diseases.     

Supramolecular Polymeric Fluorescent Nanoparticles Based on Quadruple Hydrogen Bonds

A facile approach for the preparation of supramolecular polymer‐based fluorescent nanoparticles (FNPs) is reported. FNPs with homogeneous shape and size distribution are fabricated from low‐molecular‐weight molecules, and thus, different compositional constituents can be efficiently incorporated via copolymerization. The emission color of the FNPs covers a wide region from blue to near infrared and can be easily tuned using efficient excitation energy transfer. The photoswitchable fluorescent nanoparticles with high on–off fluorescence contrast are also simply prepared by copolymerization of monomers containing a fluorophore and a photochromic unit. Our FNPs are successfully applied in living cell imaging and as fluorescent inks.     

Selective Zinc(II)‐Ion Fluorescence Sensing by a Functionalized Mesoporous Material Covalently Grafted with a Fluorescent Chromophore and Consequent Biological Applications

A highly ordered 2D‐hexagonal mesoporous silica material is functionalized with 3‐aminopropyltriethoxysilane. This organically modified mesoporous material is grafted with a dialdehyde fluorescent chromophore, 4‐methyl‐2,6‐diformyl phenol. Powder X‐ray diffraction, transmission electron microscopy, N₂ sorption, Fourier transform infrared spectroscopy, and UV‐visible absorption and emission have been employed to characterize the material. This material shows excellent selective Zn²⁺ sensing, which is due to the fluorophore moiety present at its surface. Fluorescence measurements reveal that the emission intensity of the Zn²⁺‐bound mesoporous material increases significantly upon addition of various concentrations of Zn²⁺, while the introduction of other biologically relevant (Ca²⁺, Mg²⁺, Na⁺, and K⁺) and environmentally hazardous transition‐metal ions results in either unchanged or weakened intensity. The enhancement of fluorescence is attributed to the strong covalent binding of Zn²⁺, evident from the large binding constant value (0.87 × 10⁴ M ^?1). Thus, this functionalized mesoporous material grafted with the fluorescent chromophore could monitor or recognize Zn²⁺ from a mixture of ions that contains Zn²⁺ even in trace amounts and can be considered as a selective fluorescent probe. We have examined the application of this mesoporous zinc(II) sensor to cultured living cells (A375 human melanoma and human cervical cancer cell, HeLa) by fluorescence microscopy.     

Constructing Na‐Ion Cathodes via Alkali‐Site Substitution

Na‐ion batteries have experienced rapid development over the past decade and received significant attention from the academic and industrial communities. Although a large amount of effort has been made on material innovations, accessible design strategies on peculiar structural chemistry remain elusive. An approach to in situ construction of new Na‐based cathode materials by substitution in alkali sites is proposed to realize long‐term cycling stability and high‐energy density in low‐cost Na‐ion cathodes. A new compound, [K_0.444(1)Na_1.414(1)][Mn_3/4Fe_5/4](CN)₆, is obtained through a rational control of K⁺ content from electrochemical reaction. Results demonstrate that the remaining K⁺ (≈0.444 mol per unit) in the host matrix can stabilize the intrinsic K‐based structure during reversible Na⁺ extraction/insertion process without the structural evolution to the Na‐based structure after cycles. Thereby, the as‐prepared cathode shows the remarkably enhanced structural stability with the capacity retention of >78% after 1800 cycles, and a higher average operation voltage of ≈3.65 V versus Na⁺/Na, directly contrasting the non‐alkali‐site‐substitution cathode materials. This provides new insights into alkali‐site‐substitution constructing advanced Na‐ion cathode materials.     

Preparation of Uniform,Water‐Soluble,and Multifunctional Nanocomposites with Tunable Sizes

Novel, thiol‐functionalized, and superparamagnetic, silica composite nanospheres (SH‐SSCNs) with diameters smaller than 100 nm are successfully fabricated through the self‐assembly of Fe₃O₄ nanoparticles and polystyrene₁₀₀‐block‐poly(acrylic acid)₁₆ and a subsequent sol‐gel process. The size and magnetic properties of the SH‐SSCNs can be easily tuned by simply varying the initial concentrations of the magnetite nanoparticles in the oil phase. By incorporating fluorescent dye molecules into the silica network, the composite nanospheres can be further fluorescent‐functionalized. The toxicity of the SH‐SSCNs is evaluated by choosing three typical cell lines (HUVEC, RAW264.7, and A549) as model cells, and no toxic effects are observed. It is also demonstrated that SH‐SSCNs can be used as a new class of magnetic resonance imaging (MRI) probes, having a remarkably high spin–spin (T₂) relaxivity (r₂* = 176.1 mM ^?1 S^?1). The combination of the sub‐100‐nm particle size, monodispersity in aqueous solution, superparamagnetism, and fluorescent properties of the SH‐SSCNs, as well as the non‐cytotoxicity in vitro, provides a novel and potential candidate for an earlier MRI diagnostic method of cancer.     

Fast Rate and Long Life Potassium‐Ion Based Dual‐Ion Battery through 3D Porous Organic Negative Electrode

Potassium‐based dual ion batteries (K‐DIBs) with potassium cation (K⁺) intercalation graphitic anodes have been investigated for their potential in large‐scale energy storage applications owing to their merits of low cost and environmental friendly. Nonetheless, graphite anodes are plagued by volume expansion from the large K⁺ ions and the co‐intercalation of solvent molecules during the charging. Accordingly, organic materials stand out for the flexible adjustable structures and abundant active sites, which can accommodate cations by multiple functional groups without structural collapse. However, K‐DIBs based on organic anodes have rarely been investigated. Herein, 3D porous dipotassium terephthalate nanosheets are synthesized via a freeze‐dry method as the K‐DIB anode, which can reversibly store K⁺ ions at a fast rate with a high specific capacity and robust stability due to the sufficient redox active sites and diffusion pathways of K⁺ ions in the 3D porous structure. Consequently, a novel K‐DIB configuration combining this fast kinetics organic anode and environmental friendly expanded graphite (EG) cathode is constructed (pK2TP//EG), which exhibits a high specific capacity (68 mAh g^‐1 at 2 C), good rate performance up to 20 C, and long cycling life with a capacity retention ~100% after 2000 cycles, which is the best performance observed among reported K‐DIBs.     

Multimodal Magnetic Nanoclusters for Gene Delivery,Directed Migration,and Tracking of Stem Cells

This study develops multimodal magnetic nanoclusters (M‐MNCs) for gene transfer, directed migration, and tracking of human mesenchymal stem cells (hMSCs). The M‐MNCs are designed with 5 nm iron oxide nanoparticles and a fluorescent dye (i.e., Rhodamine B) in the matrix of the Food and Drug Administration approved polymer poly(lactide‐co‐glycolide) using a nanoemulsion method. The synthesized M‐MNCs have a hydrodynamic diameter of ≈150 nm, are internalized by stem cells via endocytosis, and deliver genes with high efficiency. The cellular internalization and gene expression efficiency of the clustered nanoparticles are significantly higher than that of single nanoparticles. The M‐MNC‐labeled hMSCs migrate upon application of a magnetic force and can be visualized by both optical and magnetic resonance (MR) imaging. In animal models, the M‐MNC‐labeled hMSCs are also successfully tracked using optical and MR imaging. Thus, the M‐MNCs not only allow the efficient delivery of genes to stem cells but also the tracking of cells in animal models. Taken together, the results show that this new type of nanocomposite can be of great help in future stem cell research and in the development of cell‐based therapeutic agents.     

Achieving High Mid‐IR Bolometric Responsivity for Anisotropic Composite Materials from Carbon Nanotubes and Polymers

An anisotropic carbon nanotube (CNT)‐polymer composite for bolometric applications in the mid‐IR spectral range (2.5–20 μm) is studied. Composite alignment in conjunction with non‐uniform distribution of CNTs in the polymer matrix allows for a significant enhancement of the temperature coefficient of resistance (0.82% K^?1) with respect to uniform composite (0.24% K^?1). As a result a responsivity of ≈ 500 V W^?1 is reached, which is the highest for CNT‐based bolometers reported to date. Such remarkable optical and thermal characteristics are explained in terms of fluctuation tunneling theory taking into account the composite anisotropy and the gradient of the CNT concentration. Flatness of the photoresponse in the broad spectral mid‐IR range and enhanced responsivity provide a great potential for the use of such novel composite for applications in IR spectroscopy and thermal imaging.     

Redox reactions on TCNQ-modified self-assembled monomolecular films

Suitably modified mono- and bimolecular films, including bilayer lipid membranes (BLMs), offer exceptionally good opportunities for probing electric field effects on charge transfer and redox reactions in biosensor and molecular electronics research and development. This work presents the redox reactions of tetracyano-p-quinodimethane (TCNQ) molecules incorporated in a self-assembled octadecanethiol monolayer (SAM) on polycrystalline gold electrodes, depending upon the type of supporting electrolyte cations and their concentration. Our results show that TCNQ-modified Au–SAM electrodes exhibit selectivity versus alkali metal cations in aqueous supporting electrolyte (∽10 kJ mol⁻¹ difference between K⁺ and Li⁺ and between Cs⁺ and K⁺). The slope of the ‘calibration curves’ for Li⁺ and K⁺ is about 59 mV per decade of concentration of the analyte. The explanation of this behaviour is based on the Donnan potential model; however, an ion-pairing effect can also be involved. Our preliminary results show also that the TCNQ molecules within the octadecanethiol monolayer may act as a molecular redox device. © 1998 John Wiley & Sons, Ltd.     

Near‐Infrared Emitting and Pro‐Angiogenic Electrospun Conjugated Polymer Scaffold for Optical Biomaterial Tracking

Noninvasive tracking of biomaterials is vital for determining the fate and degradation of an implant in vivo, and to show its role in tissue regeneration. Current biomaterials have no inherent capacity to enable tracing but require labeling with, for example, fluorescent dyes, or nanoparticles. Here a novel biocompatible fully conjugated electrospun scaffold is described, based on a semiconducting luminescent polymer that can be visualized in situ after implantation using fluorescence imaging. The polymer, poly [2,3‐bis‐(3‐octyloxyphenyl)quinoxaline‐5,8‐diyl‐alt‐thiophene‐2,5‐diyl] (TQ1), is electrospun to form a fibrous mat. The fibers display fluorescence emission in the near‐infrared region with lifetimes in the sub‐nanosecond range, optimal for in situ imaging. The material shows no cytotoxic behaviors for embryonic chicken cardiomyocytes and mouse myoblasts, and cells migrate onto the TQ1 fibers even in the presence of a collagen substrate. Subcutaneous implantations of the material in rats show incorporation of the TQ1 fibers within the tissue, with limited inflammation and a preponderance of small capillaries around the fibers. The fluorescent properties of the TQ1 fibers are fully retained for up to 90 d following implantation and they can be clearly visualized in tissue using fluorescence and lifetime imaging, thus making it both a pro‐angiogenic and traceable biomaterial.