Ultrafast Self-Healing, Superstretchable, and Ultra-Strong Polymer Cluster-Based Adhesive Based on Aromatic Acid Cross-Linkers for Excellent Hydrogel Strain Sensors.

Synthetic hydrogel strain sensors rarely exhibit a comprehensive combination of mechanical properties such as ultra-stretchability, ultrafast self-healing, and high sensitivity. Herein, seven small molecule enhanced mechanical behaviors of polymer-cluster based hydrogels are demonstrated. The oxidized polyethyleneimine/polymeric acrylic acid (ohPEI/PAA) hydrogels with aromatic formic acids as supramolecular cross-linkers are prepared by simultaneous formation of ohPEI polymer clusters and PAA upon the addition of ammonium persulfate. The optimized hydrogel adhesive exhibits comprehensive excellent properties, such as high extensibility (up to 12 298%), real-time mechanical self-healing capability (<1 s, 93% efficiency), high uniformity, underwater adhesivity, and water-sealing ability. The proper binding strength of hydrogel and skin (47 kPa) allows the hydrogel to be utilized as highly sensitive (gauge factor:16.08), highly conductive (2.58 mS cm-1 ), and underwater strain sensors. Specially, the adhesive strength of the adhesive to wood after dehydration is extremely high, reaching up to 29.59 MPa. Additionally, when glycerol is introduced, the obtained gel maintains the physical properties even at harsh-temperature conditions (-40 to 80 °C). It presents that multiple and hierarchical non-covalent interactions including multiple hydrogen bonding interactions, π-π stacking, electrostatic interactions, and dipole-dipole interactions of polymer clusters, allow for the energy dissipation and contribute to the excellent performance of the hydrogel.

Dual Lewis Acid- and Base-Responsive Terpyridine-Based Hydrogel: Programmable and Spatiotemporal Regulation of Fluorescence for Chemical-Based Information Security.

A huge amount of data inundated in our daily life; there is an ever-increasing need to develop a new strategy of information encryption-decryption-erasing. Herein, a polymeric DCTpy/PAM hydrogel has been fabricated to store information via controllable Eu3+/Zn2+ ionoprinting for hierarchical and multidimensional information decryption. Eu3+ and Zn2+ have a competition and dynamic interaction toward DCTpy under NH3 stimuli in the polymeric DCTpy/PAM hydrogel network. The Eu(III)/Zn(II)@DCTpy/PAM hydrogel exhibits light red fluorescence of Eu3+ due to the antenna effect. Upon the addition of NH3, dissociation of the Eu3+-DCTpy complex takes place, and the Zn(II)/DCTpy/NH3 complex is formed with both ICT (intramolecular charge-transfer) and PET (photo-induced electron-transfer) process characteristics that exhibits yellow emission color. Subsequently, HCl can quench the fluorescence of the resulting hydrogel. By integrating transparency, adhesiveness, and programmable stimuli responsiveness of the hydrogel blocks in to one system, complex, multistage, and time-controlled information storage-encryption-decryption-erasing in sequence with multidimensions is illustrated via the molecule diffusion method. This work provides a novel and representative strategy in fabricating information encryption-decryption-erasing materials with high capacity and complexity by a simple terpyridine-based hydrogel.

Investigating the trans-membrane transport of HAIYPRH peptide-decorated nano-drugs.

Transferrin (Tf) has been effectively used to promote the cellular uptake of HAIYPRH (T7) peptide-conjugated nano-drugs. In this study, the enhancing effect of Tf on T7-decorated nano-drug transport was investigated using force tracing and nano-indentation techniques at a single-particle/cell level. Furthermore, the results were confirmed by ensemble fluorescence imaging.

Ultrasound-accelerated organogel: application for visual discrimination of Hg(2+) from Ag(+).

A new kind of naphthalimide-based organogelator, TN, was designed and synthesized. The intramolecular guanylation of TN promoted by Hg(2+) or Ag(+) in both solution and gel state was studied through several approaches including FL, UV-visible, NMR, FT-IR and SEM experiments. TN could selectively sense Hg(2+) and Ag(+) ions with obvious fluorescence quenching and color changes from yellow to colorless among test ions in the solution state. Interestingly, the S-gel of TN could be used to selectively discriminate Hg(2+) from Ag(+)via phase and morphology changes. Hg(2+) ions triggered the gel-to-gel transition with morphology changes of the TN S-gel from nanofibrils to porous sheet structure, together with fluorescence quenching. In contrast, the gel collapsed in the presence of Ag(+) ions, which was comprised of short and disordered fiber structure. To the best of the authors' knowledge, this is the first example of gels selectively sensing Hg(2+) or Ag(+)via a reaction approach.

Tunable multicolor emissions in a monocomponent gel system by varying the solvent, temperature and fluoride anion.

The facile tuning of the fluorescent properties of organogels is highly desirable for optical switches, light-emitting diodes, chemosensors and bioprobes. The design of organic molecules with multiple emission colors but only one molecular platform remains challenging. Herein, a new cholesterol-based organogelator N1 containing D-A pairs (salicylaldehyde and naphthalimide units) was designed. We successfully obtained multiple solvent-tuned emission colors in both the solution and gel states using a unimolecular platform. Moreover, the effects of the solvent on the gel morphology, rheology and anion-responsive properties were studied. Finally, we showed that the gel in benzene displayed reversible thermochromic properties with changes in emission color from yellow-green to red. Several experiments suggested that a short-distance and ordered array of the D-A pairs facilitated the efficient intermolecular electron transfer of the fluorophores.

Selective and visual Ca(2+) ion recognition in solution and in a self-assembly organogel of the terpyridine-based derivative triggered by ultrasound.

A new kind of terpyridine-based Ca(2+) sensor TS was designed and studied based on the internal charge transfer (ICT). In the diluted solution state, TS sensed Ca(2+) and Mg(2+) ions among test ions via an "off-on" approach as seen from fluorescence spectra of test ions. Moreover, TS was able to form stable fluorescent gels in organic solvents accelerated by ultrasound, indicating the ultrasound responsive properties of TS molecules. The S-gel of TS could be successfully used to selectively recognize Ca(2+) through fluorescent emission color and morphological changes, which was different from that of the solution state. It was predicated that the competition between the self-assembly of TS molecules and the host­guest interaction of TS with Ca(2+) or Mg(2+) was responsible for the sensing properties. To the best of our knowledge, this is the first example that organogels could selectively sense Ca2+ ions.

Evaluating the therapeutic efficacy of nano-drugs targeting epidermal growth factor receptor.

Epidermal growth factor receptor (EGFR) targeted nano-drugs facilitate effective diagnosis and treatment of cancer. Herein, the therapeutic efficacy of nano-drugs targeting EGFR was evaluated from the perspective of cell entry efficiency and induced cell mechanical properties using force tracing and nano-indentation techniques at the single particle/cell level in real time.

Spatiotemporal tracking of the transport of RNA nano-drugs: from transmembrane to intracellular delivery.

The popularity of RNA nanoparticles (RNPs) has risen rapidly during the past decade due to the development of RNA nanotechnology. Understanding the fast dynamic process of cell entry and intracellular delivery of RNPs is essential for the design of intelligent therapeutic RNA nano-drugs and mRNA vaccines.How the interaction between the membrane and target ligand of RNPs influences the cell entry, and how the dynamic mechanism of RNPs takes place in different organelles remain ill-defined. Herein, the cell entry of Antimir21-RNP-Apt is monitored using a force tracing technique with a high spatiotemporal resolution at the single particle level, the specific interaction of Apt and EGFR promotes the cell entry efficiency and achieves long-lasting curative effects. Furthermore, the intracellular delivery pathway through different organelles is discovered using fluorescence tracking, and the low motility in early endosomes and the high motility in late endosomes are analyzed. This report provides key strategies for engineering RNA nanomedicines and facilitating clinical translation.

Evaluating the single-molecule interactions between targeted peptides and the receptors on living cell membrane.

As potential ligands, targeted peptides have become an important part in the construction of intelligent drug delivery systems (DDSs). The targeting interaction of peptides with receptors is a key point affecting the efficacy of targeted nano-drugs. Herein, three common peptides (HAIYPRH (T7), YHWYGYTPQNVI (GE11), and RGD) that have been widely used in cancer targeted therapy and tumor diagnostics, targeting the corresponding receptors (transferrin receptor (TfR), epidermal growth factor receptor (EGFR), and ανß3 integrin receptor), were selected as examples to study the targeting interacton on living cell surface at the single-molecule level by using single-molecule force spectroscopy (SMFS) based on atomic force microscopy (AFM). The dissociation activation energy in the absence of an external force (ΔGß,0) of T7-TfR, GE11-EGFR, and RGD-ανß3 integrin is evaluated at single-molecule level. Among these three peptide-receptor pairs, the T7-TfR bond is the most stable with a smaller dissociation kinetic rate constant at zero force (Koff), larger kinetic on-rate constant (Kon), and shorter interaction time (τ). Furthermore, T7 can target TfR even more effectively on A549 cell membrane after treatment with drugs. Our methodology can also be applicable to the study of other ligand targeted DDSs.

A Zr-cluster based thermostable, self-healing and adaptive metallogel with chromogenic properties responds to multiple stimuli with reversible radical interaction.

A Zr-cluster based metallogel is synthesized via an unusual one-pot solvothermal method. The resulting metallogel is robust, adaptive, self-healing, highly thermostable and conductive. Moreover, the metallogel exhibits reversible stimuli-responsive properties. The gel could respond to at least four kinds of stimuli such as light, aliphatic amines, electricity and metals with color and fluorescence tunability. Importantly, the metallogel with electrochromic properties could be used as soft electrochromic devices for smart windows and electro display boards, and metalchromism provides a practical way for coating corrosion monitoring of metal materials.

Novel luminescent lanthanide(iii) hybrid materials: fluorescence sensing of fluoride ions and N,N-dimethylformamide.

Two novel luminescent organic-inorganic hybrid materials, Ln(L-SBA15)3phen (Ln = Eu, Tb), were designed and synthesized. The organic ligand phenylurea was modified by the silane coupling agent 3-(triethoxysilyl)propyl isocyanate (TESPIC) to form a precursor (L), which was covalently bonded onto a mesoporous SBA-15 backbone to form mesoporous L-SBA15 through co-hydrolysis and co-condensation reactions. 1,10-Phenanthroline monohydrate (phen) was selected as the second ligand to improve the luminescence of the final products, and the two mesoporous hybrid materials Ln(L-SBA15)3phen were obtained after the coordination reaction between the organic ligands (phen and L-SBA15) and Ln(iii) ions. Both the mesoporous hybrid materials were examined by Fourier transform infrared spectroscopy, transmission electron microscopy, small-angle X-ray diffraction, N2 adsorption-desorption curves, and photoluminescence spectroscopy. The results show that both the hybrid materials showed highly ordered mesoporous structures, high surface areas, and excellent photophysical properties (long luminescence lifetimes and high quantum efficiencies). Furthermore, the fluorescence sensing properties of the materials were investigated systematically, and the hybrid materials were revealed to be promising examples of dual functional materials with good ability to sense fluoride ions and a small organic molecule N,N-dimethylformamide.

Visual Recognition of Aliphatic and Aromatic Amines Using a Fluorescent Gel: Application of a Sonication-Triggered Organogel.

A naphthalimide-based fluorescent gelator (N1) containing an alkenyl group has been designed and characterized. This material is able to gelate alcohols via a precipitate-to-gel transformation when triggered with ultrasound for less than 2 min (S-gel). The gelation process in n-propanol was studied by means of absorption, fluorescence, and IR spectra, scanning electron microscopy (SEM) images, and X-ray diffraction patterns. The fluorescence intensity of N1 decreased during the gelation process in a linear relationship with the sonication time. The S-gel of N1 could be used to sense aliphatic and aromatic amines by measuring the change in the signal output. For example, the addition of propylamine to the S-gel of N1 resulted in a dramatic enhancement of the fluorescence intensity, accompanied by a gel-to-sol transition. On the contrary, when the S-gel of N1 was treated with aromatic amines such as aniline, fluorescence was quenched and there was no gel collapse. The sensing mechanisms were studied by (1)H NMR, small-angle X-ray scattering, SEM and spectroscopic experiments. It is proposed that isomerization of the alkenyl group of N1 from the trans to cis form occurs when the S-gel is treated with propylamine, resulting in a gel-sol transition. However, the aromatic aniline molecules prefer to insert into the gel networks of N1 via hydrogen-bonding and charge-transfer interactions, maintaining the gel state. As potential applications, testing strips of N1 were prepared to detect aniline.