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The implementation of two-dimensional (2D) hybrid organic-inorganic perovskites (HOIPs) in semiconductor device applications will have to accommodate the co-existence of strain and temperature stressors and requires a thorough understanding of the thermomechanical behavior of 2D HOIPs. This will mitigate thermomechanical stability issues and improve the durability of the devices, especially when one considers the high susceptibility of 2D HOIPs to temperature due to their soft nature. Here, we employ atomic force microscopy (AFM) stretching of suspended membranes to measure the temperature dependence of the in-plane Young's modulus ( E ∥ ) of model Ruddlesden-Popper 2D HOIPs with a general formula of (CH 3 (CH 2 ) 3 NH 3 ) 2 (CH 3 NH 3 ) n -1 Pb n I 3 n +1 (here, n = 1, 3, or 5). We find that E ∥ values of these 2D HOIPs exhibit a prominent non-monotonic dependence on temperature, particularly an abnormal thermal stiffening behavior (nearly 40% change in E ∥ ) starting around the order-disorder transition temperature of the butylammonium spacer molecules, which is significantly different from the thermomechanical behavior expected from their 3D counterpart (CH 3 NH 3 PbI 3 ) or other low-dimensional material systems. Further raising the temperature eventually reverses the trend to thermal softening. The magnitude of the thermally induced change in E ∥ is also much higher in 2D HOIPs than in their 3D analogs. Our results can shed light on the structural origin of the thermomechanical behavior and provide needed guidance to design 2D HOIPs with desired thermomechanical properties to meet the application needs.

Demands for high-performance electrical power transmission cables continue to rise, especially for offshore power transmission, electric vehicles, portable electronics, and deployable military applications. Carbon nanotubes (CNTs)-Copper (Cu) core-shell wire is regarded as one of the best candidate material systems for transmitting electricity and thermal energy. In this study, a facile and robust approach was developed to enhance the CNT-Cu interfacial interactions. This approach consists of a substrate-enhanced electroless deposition step for Cu pre-seeding and thiol functionalization. Benefiting from the thiol-activated CNT surface and Cu seed deposit, the CNTs-Cu core-shell wire forms a densely packed Cu shell with a void-free CNT-Cu interface. Consequently, the CNTs-Cu core-shell wire possesses (1) superior specific strength (eightfold stronger), (2) 30% higher specific conductivity, (3) 120% higher specific ampacity, and (4) an impressive 110% higher thermal conductivity compared with pure Cu wires. Moreover, this composite wire still maintains its structural integrity and electrical properties over 600 cycles of the fatigue bending test, rendering this system an excellent candidate for high-performance electrical cable and conductor applications.

In-plane strains are commonly found in two-dimensional (2D) metal halide organic-inorganic perovskites (HOIPs). The in-plane mechanical properties of 2D HOIPs are vital for mitigating the strain-induced stability issues of 2D HOIPs, yet their structure and mechanical property relationship largely remains unknown. Here, we employed atomic force microscope indentation to systematically investigate the in-plane Young's moduli E ∥ of 2D lead halide Ruddlesden-Popper HOIPs with a general formula of (R-NH 3 ) 2 PbX 4 , where the spacer molecules R-NH 3 + are linear alkylammonium cations (C m H 2 m +1 -NH 3 + , m = 4, 6, 8, or 12) and X = I, Br, or Cl. Fixing the spacer molecule to butylammonium, we discovered that the E ∥ of 2D HOIPs generally follows the trend of Pb-X bond strength, different from the tendency found in the out-of-plane moduli E ⊥ , showing more prominent effects of the metal halide inorganic framework on E ∥ than E ⊥ . E ∥ exhibits nonmonotonic dependence on the chain length of the linear alkyl spacer molecules, which would first decrease and plateau but then increase again. This is likely due to the competition of the bond strength and structural distortion in the inorganic layer, the relative fraction of the soft organic spacers, and the interfacial mechanical coupling associated with the interdigitation of the alkyl chains. The mechanical anisotropy of 2D HOIPs, marked by E ∥ / E ⊥ , shows wide tunability based on structural composition, particularly for iodide-based 2D HOIPs. Our results provide valuable insights into the structure-property relationships regarding the mechanical anisotropy and in-plane mechanical behaviors of 2D HOIPs, which can guide the materials design and device optimization to achieve required mechanical performance in 2D HOIP-based applications.

Mechanical stability of hybrid organic-inorganic perovskites (HOIPs) is essential to achieve long-term durable HOIP-based devices. While HOIPs in two-dimensional (2D) form offer numerous options in the structure and composition to tune their mechanical properties, little is known about the structure-mechanical-property relationship in this family of materials. Here, we investigated a series of 2D lead halide HOIPs by nanoindentation to explore the impact of critical factors controlling the properties of both the organic and inorganic layers on the materials' out-of-plane mechanical performance. We find that the lead-halide bond in the inorganic framework can significantly influence the mechanical properties of 2D Ruddlesden-Popper (RP) HOIPs with n = 1. Like 3D HOIPs, stronger lead-halide bond strength leads to a higher Young's modulus in these 2D HOIPs, i.e . , E ⊥ Cl ≳ E ⊥ Br > E ⊥ I . In contrast, the hardness of 2D RP HOIPs follows a trend of H Br 2D > H Cl 2D > H I 2D , which is different from that found in 3D HOIPs, probably due to the combined effects from the Pb-X bond strength and inorganic framework structural change ( e.g ., symmetry and distortion). We further show that the interface between the organic layers in 2D HOIPs can be an effective route to engineer the materials' mechanical properties. Replacing the weak CH 3 -CH 3 van der Waals forces by covalent bonds or phenyl-phenyl interactions in the interface can lead to a much stiffer and harder 2D HOIPs. Finally, we discover that the mechanical performance of 2D HOIPs with linear aliphatic diammonium spacer molecules is affected by the two basic structural parameters, i.e ., the thicknesses of the organic and inorganic layers, in a similar way compared to that of 2D RP HOIPs with linear aliphatic monoammonium spacer molecules. A thinner organic layer and a thicker inorganic layer can result in 2D HOIPs with larger elastic modulus and hardness values. Our results offer intriguing insights into the structure-property relationship of 2D HOIPs from a mechanical perspective, providing guidelines and inspirations to achieve material design with required mechanical properties for applications.

Two-dimensional (2D) layered hybrid organic-inorganic perovskites (HOIPs) have demonstrated improved stability and promising photovoltaic performance. The mechanical properties of such functional materials are both fundamentally and practically important to achieve both high performance and mechanically stable (flexible) devices. Here, we report the mechanical properties of a series of 2D layered lead iodide HOIPs and investigate the role of structural subunits (e.g., variation of the length of the organic spacer molecules, R and the number of inorganic layers, n) in the mechanical properties. Although 2D HOIPs have much lower nominal elastic modulus and hardness than 3D HOIPs, larger n number and shorter R lead to stiffer materials. Density functional theory simulations showed a trend similar to the experimental results. We compared these findings with other 2D layered crystals and shed light on routes to further tune the out-of-plane mechanical properties of 2D layered HOIPs.

Self-assembled monolayers (SAMs) have been widely used to engineer the electronic properties of substrate-supported graphene devices. However, little is known about how the surface chemistry of SAMs affects the interfacial mechanical properties of graphene supported on SAMs. Fluctuations and changes in these properties affect the stress transfer between substrate and the supported graphene and thus the performance of graphene-based devices. The changes in interfacial mechanical properties can be characterized by measuring the out-of-plane elastic properties. Combining contact resonance atomic force microcopy experiments with molecular dynamics simulations, we show that the head group chemistry of a SAM, which affects the interfacial interactions, can have a significant effect on the out-of-plane elastic modulus of the graphene-SAM heterostructure. Graphene supported on hydrophobic SAMs leads to heterostructures stiffer than those of graphene supported on hydrophilic SAMs, which is largely due to fewer water molecules present at the graphene-SAM interface. Our results provide an important, and often overlooked, insight into the mechanical properties of substrate-supported graphene electronics.

Heparin, an important polysaccharide, has been widely used for coatings of cardiovascular devices because of its multiple biological functions including anticoagulation and inhibition of intimal hyperplasia. In this study, surface heparinization of a commonly used 316L stainless steel (SS) was explored for preparation of a multifunctional vascular stent. Dip-coating of the stents in an aqueous solution of dopamine and hexamethylendiamine (HD) (PDAM/HD) was presented as a facile method to form an adhesive coating rich in primary amine groups, which was used for covalent heparin immobilization via active ester chemistry. A heparin grafting density of about 900 ng/cm(2) was achieved with this method. The retained bioactivity of the immobilized heparin was confirmed by a remarkable prolongation of the activated partial thromboplastin time (APTT) for about 15 s, suppression of platelet adhesion, and prevention of the denaturation of adsorbed fibrinogen. The Hep-PDAM/HD also presented a favorable microenvironment for selectively enhancing endothelial cell (EC) adhesion, proliferation, migration and release of nitric oxide (NO), and at the same time inhibiting smooth muscle cell (SMC) adhesion and proliferation. Upon subcutaneous implantation, the Hep-PDAM/HD exhibited mitigated tissue response, with thinner fibrous capsule and less granulation formation compared to the control 316L SS. This number of unique functions qualifies the heparinized coating as an attractive alternative for the design of a new generation of stents.

The creation of a platform for enhanced vascular endothelia cell (VEC) growth while suppressing vascular smooth muscle cell (VSMC) proliferation offers possibility for advanced coatings of vascular stents. Gallic acid (GA), a chemically unique phenolic acid with important biological functions, presents benefits to the cardiovascular disease therapy because of its superior antioxidant effect and a selectivity to support the growth of ECs more than SMCs. In this study, GA was explored to tailor such a multifunctional stent surface combined with plasma polymerization technique. On the basis of the chemical coupling reaction, GA was bound to an amine-group-rich plasma-polymerized allylamine (PPAam) coating. The GA-functionalized PPAam (GA-PPAam) surface created a favorable microenvironment to obtain high ECs and SMCs selectivity. The GA-PPAam coating showed remarkable enhancement in the adhesion, viability, proliferation, migration, and release of nitric oxide (NO) of human umbilical vein endothelial cells (HUVECs). The GA-PPAam coating also resulted in remarkable inhibition effect on human umbilical artery smooth muscle cell (HUASMC) adhesion and proliferation. These striking findings may provide a guide for designing the new generation of multifunctional vascular devices.

Neurodegenerative diseases or acute injuries of the nervous system always lead to neuron loss and neurite damage. Thus, the development of effective methods to repair these damaged neurons is necessary. The construction of biomimetic materials with specific physicochemical properties is a promising solution to induce neurite sprouting and guide the regenerating nerve. Herein, we present a simple method for constructing biomimetic graphene oxide (GO) composites by covalently bonding an acetylcholine-like unit (dimethylaminoethyl methacrylate, DMAEMA) or phosphorylcholine-like unit (2-methacryloyloxyethyl phosphorylcholine, MPC) onto GO surfaces to enhance neurite sprouting and outgrowth. The resulting GO composites were characterized by Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, UV-vis spectrometry, scanning electron microscopy, and contact angle analyses. Primary rat hippocampal neurons were used to investigate nerve cell adhesion, spreading, and proliferation on these biomimetic GO composites. GO-DMAEMA and GO-MPC composites provide the desired biomimetic properties for superior biocompatibility without affecting cell viability. At 2 to 7 days after cell seeding was performed, the number of neurites and average neurite length on GO-DMAEMA and GO-MPC composites were significantly enhanced compared with the control GO. In addition, analysis of growth-associate protein-43 (GAP-43) by Western blot showed that GAP-43 expression was greatly improved in biomimetic GO composite groups compared to GO groups, which might promote neurite sprouting and outgrowth. All the results demonstrate the potential of DMAEMA- and MPC-modified GO composites as biomimetic materials for neural interfacing and provide basic information for future biomedical applications of graphene oxide.

Designing a multifunctional surface based on the coimmobilization of two or more diverse biomolecules with synergic action is very important in certain cases. In this work, a facile method by two-step aimed to construct a polyfunctional coating containing -COOH, -NH2, and phenol/quinine groups was reported. The first-step was to introduce amine groups onto target modified-surface by coating with plasma polymerized allylamine (PPAam), followed by the second-step conjugation of gallic acid (3,4,5-trihydroxybenzoic acid) onto the PPAam surface. The density of -COOH, -NH2, and phenol/quinone groups could be regulated easily by adjusting the reaction time of GA conjugation, making it possible to coimmobilize two or three diverse molecules. This has been shown by the successful coimmobilization of anti-CD34 antibody and vascular endothelial growth factor (VEGF). The surface coimmobilized with the anti-CD34 antibody and VEGF presented significant enhancement in the capture of endothelial progenitor cells (EPCs) and the growth of human umbilical vein endothelial cells (HUVECs). These data suggest the huge potential of such polyfunctional coating for tailoring the desired interfacial properties of materials through selectively conjugating two or more diverse bioactive molecules with synergic action.

Recent investigations have demonstrated that polydopamine (PDA)-modified surfaces were beneficial to the proliferation of endothelial cells (ECs). In this work, PDA coated 316L stainless steels (316L SS) were thermally treated at 50, 100, and 150 °C respectively (hereafter designated as Th50, Th100, and Th150) and consequently produced diverse surface chemical components. In vitro hemocompatibility and vascular cell-material interactions with ECs and smooth muscle cells (SMCs) affected by surface characteristics have been investigated. The Th150, rich in quinone, showed the best hemocompatibility and could effectively inhibit platelet adhesion, activation, and fibrinogen conformation transition. The polydopamine-modified surfaces were found to induce dramatic cell-material interaction with enhanced ECs proliferation, viability and migration, release of nitric oxide (NO), and reduced SMCs proliferation. The inhibitory effect of SMCs proliferation might be associated with the surface catechol content. The coating on Th150 showed a good resistance to the deformation of compression and expansion of vascular stents. These results effectively suggested that the Th150 coating might be promising when served as a stent coating platform.