Non-covalently Functionalized Graphene Oxide-Based Coating to Enhance Thermal Stability and Flame Retardancy of PVA Film

The synergistic effect of conventional flame-retardant elements and graphene has received extensive attention in the development of a new class of flame retardants. Compared to covalent modification, the noncovalent strategy is simpler and expeditious and entirely preserves the original quality of graphene. Thus, non-covalently functionalized graphene oxide(FGO) with a phosphorus–nitrogen compound was successfully prepared via a one-pot process in this study. Polyethyleneimine and FGO were alternatively deposited on the surface of a poly(vinyl alcohol)(PVA) film via layer-by-layer assembly driven by electrostatic interaction, imparting excellent flame retardancy to the coated PVA film. The multilayer FGO-based coating formed a protective shield encapsulating the PVA matrix, effectively blocking the transfer of heat and mass during combustion. The coated PVA has a higher initial decomposition temperature of about 260 °C and a nearly 60% reduction in total heat release than neat PVA does. Our results may have a promising prospect for flame-retardant polymers.

Non-covalent interaction between almond protein and sinapic acid: impact on protein structure and antioxidant activity

Plant phenolic acids are good sources of antioxidants and sinapic acid(SA)is one of them that can be applied in protein-based food system.However,little research is available regarding interactions between almond protein(AP)and SA.In this study,structure-affinity interaction between SA and AP,structure and antioxidant activity of proteins were investigated.Different mathematical models showed that Ka of binding SA and AP were 3.27×10^4 L/mol and 3.08×10^4 L/mol.CD(Circular dichroism)spectroscopy and FT-IR(Fourier transform infrared)spectroscopy showed that the amount of random coil andα-helix decreased whileβ-sheet increased in AP-SA complex.In combination,the interaction model of AP-SA complex was static quenching and attributed to hydrophobic interaction.Further,AP-SA complex exerted better DPPH radical scavenging ability(36.97±0.78%),ABTS+radical scavenging ability(47.26±0.45%),and higher ORAC value(2.41±0.23 M trolox/g)compared to AP.In the further,SA can be applied in protein matrix to improve film stability,gel strength and restraining fat oxidation degradation.

Modulating vectored non-covalent interactions for layered assembly with engineerable properties

Vectored non-covalent interactions—mainly hydrogen bonding and aromatic interactions—extensively contribute to(bio)-organic self-assembling processes and significantly impact the physicochemical properties of the associated superstructures.However,vectored non-covalent interaction-driven assembly occursmainly along one-dimensional(1D)or three-dimensional(3D)directions,and a two-dimensional(2D)orientation,especially that of multilayered,graphene-like assembly,has been reported less.In this present research,by introducing amino,hydroxyl,and phenyl moieties to the triazine skeleton,supramolecular layered assembly is achieved by vectored non-covalent interactions.The planar hydrogen bonding network results in high stability,with a thermal sustainability of up to about 330°C and a Young’s modulus of up to about 40 GPa.Upon introducing wrinkles by biased hydrogen bonding or aromatic interactions to disturb the planar organization,the stability attenuates.However,the intertwined aromatic interactions prompt a red edge excitation shift effect inside the assemblies,inducing broad-spectrum fluorescence covering nearly the entire visible light region(400–650 nm).We show that bionic,superhydrophobic,pillar-like arrays with contact angles of up to about 170°can be engineered by aromatic interactions using a physical vapor deposition approach,which cannot be realized through hydrogen bonding.Our findings show the feasibility of 2D assembly with engineerable properties by modulating vectored non-covalent interactions.

Medicinal chemistry strategies towards the development of non-covalent SARS-CoV-2 Mpro inhibitors

The main protease(M^(pro))of SARS-CoV-2 is an attractive target in anti-COVID-19 therapy for its high conservation and major role in the virus life cycle.The covalent M^(pro)inhibitor nirmatrelvir(in combination with ritonavir,a pharmacokinetic enhancer)and the non-covalent inhibitor ensitrelvir have shown efficacy in clinical trials and have been approved for therapeutic use.Effective antiviral drugs are needed to fight the pandemic,while non-covalent M^(pro)inhibitors could be promising alternatives due to their high selectivity and favorable druggability.Numerous non-covalent M^(pro)inhibitors with desirable properties have been developed based on available crystal structures of M^(pro).In this article,we describe medicinal chemistry strategies applied for the discovery and optimization of non-covalent M^(pro)inhibitors,followed by a general overview and critical analysis of the available information.Prospective viewpoints and insights into current strategies for the development of non-covalent M^(pro)inhibitors are also discussed.

Non-covalent interaction-based molecular electronics with graphene electrodes

Recent years have witnessed the fabrication of various non-covalent interaction-based molecular electronic devices.In the noncovalent interaction-based molecular devices,the strength of the interfacial coupling between molecule and electrode is weakened compared to that of the covalent interaction-based molecular devices,which provides wide applications in fabricating versatile molecular devices.In this review,we start with the methods capable of fabricating graphene-based nanogaps,and the following routes to construct non-covalent interaction-based molecular junctions with graphene electrodes.Then we give an introduction to the reported non-covalent interaction-based molecular devices with graphene electrodes equipped with different electrical functions.Moreover,we summarize the recent progress in the design and fabrication of new-type molecular devices based on graphene and graphene-like two-dimensional(2D)materials.The review ends with a prospect on the challenges and opportunities of non-covalent interaction-based molecular electronics in the near future.

Self-adaptive non-covalent albumin-binding near-infrared probe conjugates enabling precise sentinel lymph node metastasis illumination and primary tumor imaging

Tumor sentinel lymph node(SLN)metastasis plays a vital role in tumor staging and therapeutic decision-making process.However,precise diagnosis of primary tumors and lymphatic metastases is still hindered by low imaging resolution and poor photostability of fluorescent probes.Herein,we report three novel IR820-fatty acid(FA)conjugates(IR-OA,IR-LA,and IR-PA)for precise lymphatic metastasis illumination and primary tumor diagnosis.The IR-FA conjugates are able to non-covalently bound to albumin in vivo,and the fluorescence quantum yield is significantly enhanced after incubation with bovine serum albumin(BSA)in vitro.Moreover,the BSA-IR-FA conjugates display large Stokes shift(>120 nm),dramatically improving in vivo imaging resolution.Among them,IR-PA demonstrates distinct advantage over IR-OA,IR-LA,and IR-maleimide(MAL)(fluorescent probe previously reported by our group)in terms of fluorescence quantum yield,photostability,and imaging resolution.As a result,IR-PA exhibits satisfactory imaging results with high fluorescence intensity and imaging resolution in sentinel lymph node metastasis illumination and primary tumor location.Our findings provide a self-adaptive albumin-binding near-infrared probe conjugate for accurate diagnosis of primary tumors and lymphatic metastases.

Regulating the melting point by non-covalent interaction toward a promising insensitive melt-castable energetic material:1,2-Difluoro-4,5-dinitrobenzene

Searching for insensitive melt-castable energetic materials is still facing great challenges.In this work,we developed a promising strategy that is regulating the ratio of non-covalent interaction by fluorine atoms to regulate the melting point to develop new melt-castable energetic materials.Using this method,a highly sym-metric 1,2-difluoro-4,5-dinitrobenzene(DFDNB)was synthesized in one step and fully characterized.DFDNB has a desirable melting point(83.2℃),high decomposition temperature(>400℃),acceptable detonation properties(6786 m s^(-1),21.5 GPa)but superior safety performance(>40 J,>360 N),and excellent chemical compatibility with 1,3,5-trinitro-1,3,5-triazine(RDX)that make it a promising insensitive melt-castable energetic material.A detailed study based on crystal stacking,electrostatic potential,and intermolecular weak interactions in DFDNB and its isomers or analogs demonstrates that non-covalent interactions including the C-F…H,N-O…H hydrogen bonding,and C-F…O halogen-like bonding play an important role in regulating the melting point.

Improved Non-Covalent Biofunctionalization of Multi-Walled Carbon Nanotubes Using Carbohydrate Amphiphiles with a Butterfly-Like Polyaromatic Tail

We have developed an efficient strategy for the non-covalent functionalization of multi-walled carbon nanotubes(MWCNTs)which allows a biomimetic presentation of carbohydrates on their surface byπ-πstacking interactions.The strategy is based on the use of sugar-based amphiphiles functionalized with tetrabenzo[a,c,g,i]fluorene(Tbf),a polyaromatic compound with a topology that resembles a butterfly with open wings.The new carbohydrate-tethered Tbf amphiphiles have been synthesized in a straightforward manner using click chemistry.The reported method has been developed in order to improve the rather low ability of pyrene-based systems to exfoliate MWCNTs in water.By means of thermogravimetric analysis(TGA),ultraviolet(UV),infrared(IR),and fluorescence spectroscopies the interaction between MWCNTs and the Tbf group has been found to be stronger than those involving pyrene-based amphiphilic carbohydrates.The resulting aggregates with a multivalent sugar exposition on their surface are able to engage in specific ligand-lectin interactions similar to glycoconjugates on a cell membrane.

Evaluation of non-covalent interaction between Seryl-Histidine dipeptide and cyclophilin A using NMR and molecular modeling

Seryl-Histidine dipeptide(Ser-His) has been previously reported to be capable of cleaving DNAs and carboxyl esters,as well as proteins.The protein cleavage mechanism has not been addressed yet.As an initial step of protein cleavage activity,the non-covalent binding affinity of Ser-His for proteins is a crucial prerequisite.In this work,we took cyclophilin A(CyPA) as a substrate protein,and evaluated the non-covalent interaction between CyPA and Ser-His using a combination of NMR spectroscopy and molecular modeling approach.Two independent Ser-His binding sites on CyPA were detected using 15N-1H heteronuclear single-quantum coherence(HSQC) spectra.Each binding site binds one Ser-His molecule.Dissociation constants,Kd1 and Kd2,were estimated to be 2.07 and 6.66 mmol/L,respectively,indicative of the weak non-covalent interaction between Ser-His and CyPA.Based on molecular modeling results,we suggest that both the α-amino and the side chain hydroxyl group of Ser-His are crucial for the non-covalent interaction between Ser-His and CyPA.This work sheds light on the molecular mechanism of Ser-His and its analogues cleaving proteins.

Non-covalent glycosylated gold nanoparticles/peptides nanovaccine as potential cancer vaccines

Herein,we firstly developed a non-covalent glycosylated gold nanoparticles/peptides nanovaccine which is assembled byβ-cyclodextrin(β-CD)based host-guest recognitions.This nanovaccine can generate significant titers of antibodies and improve the therapeutic effect against melanoma,suggesting the immunogenicity of peptide antigens can be improved by loading with this carrier.The novel vaccine carrier provides a platform for the transport of various antigens especially T cell-independent antigens.

ESI-MS study on non-covalent bond complex of rhFKBP12 and new neurogrowth promoter

An ESI-MS method for studying the non-covalent bond complex of rhFKBP12 with its nonimmunosuppressive ligands was developed. The method was used to screen out three com-pounds capable of binding to rhFKBP12 non-covalently from 52 compounds. By competing binding experiment, the binding site and the relative binding strength of these three compounds 000107, 000308 and A2B12 with rhFKBP12 were measured. All of them have the same binding site as FK506 does. X-ray crystalline diffraction experiment of non-covalent bond complex of 000107, 000308 with rhFKBP12 by Tsinghua University showed the same results. Among them 000308 has good effect on stimulating neurite to grow in chicken sensory neuronal cultures.

Synthesis, Crystal Structure and Non-covalent Interactions Analysis of Novel N-Substituted Thiosemicarbazone

()*￡-1 -(4-Fluorobenzylidene)^l-(4-ethylphenyl)thiosemicarbazone was synthesized via the reaction of 4-(4-ethylphenyl)thiosemicarbazide and 4-fluorobenzaldehyde. The title compound was characterized by FTIR, and 13C NMR, mass spectrometry and elemental analysis techniques. Structural property of the title compound was displayed by the X-ray single crystal diffraction. The title compound crystallized in triclinic space group Pl witli a=0.6494(4) nm,a=0.7971(5) nm, c=1.5492( 10) nm,a=83.690( 11)°,β=84.185(10)。γ=84.348(11)。molecular formula Ci6H16FN3S,Mr=301.39,V=0.7868(9) nm^3, Z=2, Dc=1.272 g/cm……3,^000)=316,“=0.213 mm-1, 5=1.02, 7?=O.O513, and cw7[Z>2o(Z)]=0.1662. The intennolecular interactions in the crystal structure were explained using the Hirshfeld surface and their associated two-dimensional fingerprint plots. The title compound showed C-H-S(l-x,-y,-z) and NH(1-y,-z) intermolecular interactions, and formed the supramolecular self-assemblies through R2^2(12) and R2^2(8) ring motifs. Shape index and curvediiess were performed to further understand some unique weak interactions, for instance, the weakπ…π stacking contacts in molecular structure witli difierent characteristic regions. Besides, the reduced density gradient(RDG) function provided a real-space function for discussing non-covalent interactions within molecule, such as hydrogen bonds, weak van der Waals interactions and attractive or repulsive effects.

Aggregate Engineering in Supramolecular Polymers via Extensive Non-covalent Networks

Aggregate engineering of non-covalent networks endows supramolecular polymers with thermo-mechanical versatility,stimuli-responsive phase transitions and intrinsic damage-healing capabilities.However,most non-covalent networks are vulnerable at elevated temperatures,which suppresses the robustness of supramolecular polymers.Herein,ureidocytosine(UCy)motifs,which are capable of forming extensive non-covalent networks and thus robust molecular aggregates via multivalent hydrogen bonds and aromatic stackings,are proposed to enable precise programming of the thermo-mechanical versatility.Molecular simulations reveal that the enthalpic contributions from the UCy aggregates play dominant roles to compensate the entropic loss from the redistributions of polymeric spacers and stabilize the non-covalent networks over wide temperature windows.Such aggregate-level strategy offers prospects for applications which require thermo-mechanical versatility of supramolecular polymers,such as 3D printing,microfabrication and damage-healing coating.

Non-Covalent Functionalization of Graphene with Bisphenol A for High-Performance Supercapacitors

The reduced graphene oxide(RGO)/bisphenol A(BPA)composites were prepared by an adsorption-reduction method.The composites are characterized by X-ray diffraction(XRD),UV-vis,thermogravimetric(TG)analysis,field emission scanning electron microscopy(FESEM),transmission electron microscopy(TEM).The results confirm that BPA is adsorbed on the basal plane of RGO byπ-πstacking interaction.Furthermore,the electrochemical behaviors were evaluated by cyclic voltammetry,galvanostatic charge/discharge techniques and electrochemical impedance spectroscopy(EIS).The results show that the RGO/BPA nanocomposites exhibit ultrahigh specific capacitance of 466 F•g^(−1) at a current density of 1 A•g^(−1),excellent rate capability(more than 81%retention at 10 A•g^(−1) relative to 1 A•g^(−1))and superior cycling stability(90%capacitance decay after 4000 cycles).Consequently,the RGO/BPA nanocomposites can be regarded as promising electrode materials for supercapacitor applications.

Extra contribution to the crystal stability of insensitive explosive TATB: The cooperativity of intermolecular interactions

An in-depth analysis on the cooperativity of intermolecular interactions including hydrogen bonding andπ-π stacking in 1,3,5-triamino-2,4,6-trinitrobenzene(TATB) crystal was studied. Two quantities, cooperativity rate and energy, were defined to evaluate the nature and strength of cooperativity in a series of clusters diverging from 1D to 3D prototypes. The origin and mechanism of the cooperative effect were settled to demonstrate that the nature of cooperativity is determined by whether the non-covalent interactions compete or promote with each other, which is manifested by the changing trend of electron transfer. There exists obvious cooperative effect in intra-layer and inter-layer structures as they own the equivalent non-covalent interactions, while anti-cooperative effect is also observed if two interactions correlate with each other. On the whole, in the process of crystal formation, the apparent cooperativity is the check and balance of the two effects, which is capable to support a global interaction among all of molecules and contribute to the stabilization of system. Based on the results, one may get a new insight to understand the relationship between non-covalent interactions and low impact sensitivity.

Preparation and characterization of supramolecular gel suitable for fractured formations

The excellent mechanical properties of supramolecular gel could adapt to the complex reservoir environment and had broad application prospects in the field of oil and gas drilling and production engineering.In this paper,a supramolecular gel based on hydrophobic association and hydrogen bonding was prepared by micellar copolymerization,which could be used to plug fractures and pores in formations.Supramolecular gel was a gel network system with high performance characteristics formed by self-assembly of non-covalent bond interaction.The rheological properties,mechanical mechanics,temperature resistance and swelling ability of supramolecular gel were studied.The results showed that the supramolecular gel had a dense three-dimensional network structure with open and interconnected pore structures,which could exhibit good rheological properties and strong viscoelastic recovery ability.The mechanical properties of the supramolecular gel were excellent,it had a tensile stress of 0.703 MPa and an elongation at break of 1803%.When the compressive strain was 96%,the compressive stress could reach 14.5 MPa.Supramolecular gel also showed good temperature resistance and swelling properties.At the aging temperature of 135℃,supramolecular gels still maintained good gel strength,and it only took 12 h to reach the equilibrium swelling ratio of 35.87 in 1%NaCl solution.It was also found that supramolecular gel in low concentration saline(1%NaCl solution)showed relatively faster swelling than high concentration saline(25%NaCl solution).The swelling process of the supramolecular gel was non-Fick diffusion(typeⅡ).This indicated that the organic/inorganic permeability network was well formed.Therefore,the diffusion rate of small molecules could be guaranteed to be equal to the relaxation rate of large molecules before and after the phase transition temperature.In addition to the diffusion of water molecules,the swelling process of the supramolecular gel was also affected by the relaxation of gel network and polymer chain segment,the interaction between water molecules and polymer network and the groups of polymer network and other factors.Supramolecular gel particles could be used as plugging materials for drilling fluids,which had excellent ability to plug formation fractures and pores.The plugging ability of the supramolecular gel was up to 6.7 MPa for 0.5 mm fracture width,and 9.6 MPa for porous media with 5 mD permeability.Compared with HT-PPG gel particles commonly used in oil fields,supramolecular gel particles had better plugging ability on fractures and porous media.The development and application of supramolecular gel had far-reaching significance for promoting the functional application of polymer materials in drilling and production engineering.

Functionality of Covalent Organic Framework (COF) in Gas Storage Application: First Principal Study

Industrial growth in recent years led to air pollution and an increase in concentration of hazardous gases such as O3 and NO. Developing new materials is important to detect and reduce air pollutants. While catalytic decomposition and zeolites are traditional ways used to reduce the amount of these gases. We need to develop and explore new promising materials. Covalent organic framework (COF) has become an attractive platform for researcher due to its extended robust covalent bonds, porosity, and crystallinity. In this study, first principal calculations were performed for gases adsorption using COFs containing nitrogen and π-bonds. Different building blocks (BBs) and linkers (LINKs/LINK1 & LINK2) were investigated by means of density functional theory (DFT) calculations with B3LYP and 3-21G basis sets to calculate the binding energies of gases @COF systems. Electrostatic potential maps (ESPM), Mulliken charges and non-covalent interaction (NCI) are used to understand the type of interactions between gas and COFs fragments. O3 was found to bind strongly with COF system in comparison with NO which could make COF a useful selective material for mixed gases environment for sensing and removal application.

Functionalized graphene oxide-reinforced electrospun carbon nanofibers as ultrathin supercapacitor electrode

Graphene oxide has been used widely as a starting precursor for applications that cater to the needs of tunable graphene. However, the hydrophilic characteristic limits their application, especially in a hydrophobic condition. Herein, a novel non-covalent surface modification approach towards graphene oxide was conducted via a UV-induced photo-polymerization technique that involves two major routes; a UV-sensitive initiator embedded via pi-pi interactions on the graphene planar rings, and the polymerization of hydrophobic polymeric chains along the surface. The functionalized graphene oxide successfully achieved the desired hydrophobicity as it displayed the characteristic of being readily dissolved in organic solvent. Upon its addition into a polymeric solution and subjected to an electrospinning process,non-woven random nanofibers embedded with graphene oxide sheets were obtained. The prepared polymeric nanofibers were subjected to two-step thermal treatments that eventually converted the polymeric chains into a carbon-rich conductive structure. A unique morphology was observed upon the addition of the functionalized graphene oxide, whereby the sheets were embedded and intercalated within the carbon nanofibers and formed a continuous structure. This reinforcement effectively enhanced the electrochemical performance of the carbon nanofibers by recording a specific capacitance of up to 140.10 F/g at the current density of 1 A/g, which was approximately three folds more than that of pristine nanofibers.It also retained the capacitance up to 96.2% after 1000 vigorous charge/discharge cycles. This functionalization technique opens up a new pathway in tuning the solubility nature of graphene oxide towards the synthesis of a graphene oxide-reinforced polymeric structure.

Non-fused medium bandgap electron acceptors for efficient organic photovoltaics

The cost-effective organic semiconductors are strongly needed in organic photovoltaics(OPVs). Herein,two medium bandgap(MBG) electron acceptors, TPT4F and TPT4Cl are developed via the new design of multi-noncovalent interaction assisted unfused core, flanked with two electron withdrawing end groups. These fullly non-fused MBG acceptors adapt the planar and rigid conformation in solid, therefore exhibiting the ordered face-on stacking and strong photoluminescence in films. As results, TPT4Cl^(-)based OPVs, upon blending with the PBDB-TF polymer donor, have achieved a power conversion efficiency of 10.16% with a low non-radiative loss of 0.27 e V, representing one of the best fullly non-fused medium bandgap acceptors with desirable cost-efficiency balance.

有机卤素键晶体及其在光电子学中的应用

有机卤素共晶是由两个或者更多不同组分通过碳卤键构成的.因其多样化的化学物理特性,及在有机光电子学领域的潜在应用价值,有机卤素共晶引起了研究者的广泛关注.本综述文章中,我们简单总结了有机卤键共晶的制备方法和在光电子器件领域应用的最新进展.此外,我们还讨论了目前有机卤键共晶的研究方向及面临的技术挑战,同时对有机卤键共晶的进一步研究和应用前景进行了展望.