The negative regulation effect of tumor microenvironment (TME) greatly compromised the efficacy of various cancer treatments, especially cancer immunotherapy. As a result, it is generally recognized that remodeling of TME along with the treatment is a promising way to realize satisfactory cancer therapy. Here, in our study, a drug delivery system (DDS) composed cancer cell membrane (CCM) vehicle loaded mitoxantrone (Mit) and sorafenib (Sfn) was proposed with the aim to combine TME regulation and chemotherapy-induced immunotherapy in one platform. Our results confirmed that after treating with this DDS, the Mit induced immunogenic cell death (ICD) could be augmented by Sfn-based TME regulation to realize effective cancer immunotherapy. The Sfn was shown to downregulate of the regulatory T cells (Treg) level while activating the effector T cells of TME. The synergetic TME regulation along with cancer immunotherapy might be a promising way for advanced cancer treatment.

Iron oxide nanoparticles presenting colloidal stability in water were prepared through precipitation and then surface-functionalized with varying citric acid (CA) concentrations (0.10, 0.25, 0.50, and 0.70 g/mL). CA introduced functionality and minimized agglomeration. Iron oxide nanoparticles with colloidal stability in water at physiological pH were obtained after functionalization with 0.25–0.70 g/mL CA, whereas iron oxide nanoparticles without stability in water were obtained after functionalization with 0.10 g/mL CA. An electrode for glucose detection was fabricated by self-assembling colloidal-stable γ-Fe2O3 NP–CA in water on indium tin oxide (ITO) glass, followed by a glucose oxidase (GOx) and Nafion layer. The optimal functionalization of the γ-Fe2O3 NPs was obtained at a CA concentration of 0.25 g/mL. The electrochemical properties and electrocatalytic behavior of the modified electrode designated as Nafion/GOx/γ-Fe2O3 NP–0.25 CA/ITO were then evaluated. The electrode showed high sensitivity for glucose detection of 995.57 and 5.81 µA/(mM cm2) within the linear ranges of 0.1–5.0 µM and 5.0 µM–20.0 mM, respectively. The modified electrode also demonstrated a low limit of detection, good repeatability of 2.5% (n = 10), and sufficient reproducibility of 3.2% (n = 5).

RNA delivery into deep tissues with dense extracellular matrix (ECM) has been challenging. For example, cartilage is a major barrier for RNA and drug delivery due to its avascular structure, low cell density and strong negative surface charge. Cartilage ECM is comprised of collagens, proteoglycans, and various other noncollagneous proteins with a spacing of 20nm. Conventional nanoparticles are usually spherical with a diameter larger than 50-60nm (after cargo loading). Therefore, they presented limited success for RNA delivery into cartilage. Here, we developed Janus base nanotubes (JBNTs, self-assembled nanotubes inspired from DNA base pairs) to assemble with small RNAs to form nano-rod delivery vehicles (termed as “Nanopieces”). Nanopieces have a diameter of ∼20nm (smallest delivery vehicles after cargo loading) and a length of ∼100nm. They present a novel breakthrough in ECM penetration due to the reduced size and adjustable characteristics to encourage ECM and intracellular penetration.

Bioelectronics requires versatile, efficient, and low-cost interfaces between the biological entities and the conductive unit. Conductive polymers represent a valid choice to assemble such interfaces able to extract or impinge charges between the biological units and the conductive electronic systems. A drawback in the use of such systems is that the polymerization reaction often takes place in environments whose chemical and physical characteristics clash with the mild conditions required for living biological systems. In the present work, we successfully prove that the conductive polymer poly(gallic acid) can be synthesized in medium designed for bacterial growth, characterised by the presence of several adverse conditions including numerous chemicals, high ionic strength, and almost neutral pH. The gallic acid successfully polymerizes within few hours and with a 40% yield, by exploiting the catalytic activity of the enzyme laccase from the polypore mushroom Trametes versicolor. The resulting polymer is characterised by absorption and Nuclear Magnetic Resonance spectroscopies. The viability of Rhodobacter sphaeroides culture, assessed via the coffee-ring technique, shows an important, but not complete detrimental effect of the gallic acid on the bacterial growth.

Scaffolds based on two different geometries were constructed by additive manufacturing: one based on a triply periodic minimal surface, the Schwarz D surface, and the other based on a rectangular geometry with orthogonal through-holes. For construction of the scaffolds, two different materials were used: polylactic acid (PLA) in filament form and alumina in printable paste form. The structure of the resulting scaffolds was characterized via X-ray diffraction and scanning electron microscopy, and cell proliferation was assessed for each geometry and material, using fluorescence microscopy and DNA quantification via NanoDrop. Additive manufacturing allowed us to obtain scaffolds with the assessed materials while guaranteeing the interconnectivity of the pores in each one. The curved surfaces constructed with PLA were more favorable for cell attachment and proliferation of the CHO-K1 cell line.

Fibronectin (FN) is a mediator molecule, which can connect cell receptors to the extracellular matrix (ECM) in tissues. This function is highly desirable for biomaterial surfaces in order to support cell adhesion. Controlling the fibronectin adsorption profile on substrates is challenging because of possible conformational changes after deposition, or due to displacement by secondary proteins from the culture medium. Here, we aim to develop a method to realize self-stabilized ECM glycoprotein layers with preserved native secondary structure on substrates. Our concept is the assembly of FN layers at the air-water (A-W) interface by spreading FN solution as droplets on the interface and transfer of the layer by the Langmuir-Schäfer (LS) method onto a substrate. It is hypothesized that 2D confinement and high local concentration at A-W interface supports FN self-interlinking to form cohesive films. Rising surface pressure with time, plateauing at 10.5 mN·m-1 (after 10 hrs), indicated that FN was self-assembling at the A-W interface. In situ polarization-modulation infrared reflection absorption spectroscopy of the layer revealed that FN maintained its native anti-parallel β-sheet structure after adsorption at the A-W interface. FN self-interlinking and elasticity was shown by the increase in elastic modulus and loss modulus with time using interfacial rheology. A network-like structure of FN films formed at the A-W interface was confirmed by atomic force microscopy after LS transfer onto Si-wafer. FN films consisted of native, globular FN molecules self-stabilized by intermolecular interactions at the A-W interface. Therefore, the facile FN self-stabilized network-like films with native anti-parallel β-sheet structure produced here, could serve as stable ECM protein coatings to enhance cell attachment on in vitro cell culture substrates and planar implant materials.

In recent years, tissue engineering has helped to reduce hospital stays and deaths caused by skin wounds. Scaffolds are one of the main factors that influence the success of any tissue graft. Collagen is one of the main components of the extracellular matrix, and there has been much interest in new sources for application as a biomaterial. In this work, a tissue engineering scaffold was developed using the electrospinning technique. The chicken skin was used as an alternative source to obtain collagen. The combination of this collagen with elastin was successfully electrospun, and a distribution of diameters was obtained, less than 100 nm. In vitro tests showed the adhesion and proliferation of the cells, as well as an absence of cytotoxicity from non–cross-linked scaffolds and scaffolds that were cross-linked with carbonyldiimidazole. The structure and composition of the developed scaffolding provide a favorable environment for cell growth and generating a skin substitute.

A fundamental design rule that nature has developed for biological machines is the intimate correlation between motion and function. One class of biological machines is molecular motors in living cells, which directly convert chemical energy into mechanical work. They coexist in every eukaryotic cell, but differ in their types of motion, the filaments they bind to, the cargos they carry, as well as the work they perform. Such natural structures offer inspiration and blueprints for constructing DNA-assembled artificial systems, which mimic their functionality. In this article, we describe two groups of cytoskeletal motors, linear and rotary motors. We discuss how their artificial analogues can be built using DNA nanotechnology. Finally, we summarize ongoing research directions and conclude that DNA origami has a bright future ahead.

Obtention of titanium (Ti)- and titanium dioxide (TiO2)–based nanocomposites is of great interest for biological nanomaterial applications, including for dental implants. Their mechanical properties can be improved by use of hydroxyapatite (HA) and chitosan through their biological anchorage with osseointegration and antibacterial activity. Electrochemical methods were chosen to obtain these composites in a quick and controllable way. In this work, electrochemical synthesis in one (alternated potential) or two steps (alternated or constant potential) was successfully applied. The single step (SS) obtained TiO2 + HA sample had different optical properties, as shown using ultraviolet–visible spectrometry, and the HA phase formation was proved using Raman spectroscopy. Thereby, SS_TiO2 + HA increased the corrosion resistance of titanium in artificial saliva medium, as shown by linear polarization and electrochemical impedance spectroscopy results. When using chitosan, the samples showed two corrosion interfaces, indicating its dissolution in human medium. These results indicate that the samples are excellent materials for dental implants.

This article addresses why biomaterials are a growing part of materials science. We consider two areas at two different scales. At the nanometer scale, enzymes are heterogeneous nanoparticles of extraordinary deformability; this property allows us to view biomolecules informed by concepts of materials science and nonlinear physics. A degree of universality in the mechanical behavior of the molecules appears in the ubiquitous softening transitions; some results obtained dynamically by nanorheology, and others obtained in equilibrium experiments through the method of the DNA springs are summarized. These soft molecules represent an opportunity for studies of dissipation at the atomic scale. At the mesoscopic scale, composite functional materials with biological components hold promise for applications such as low power, chemically driven, biodegradable devices. A concrete example, and a program for the future, is the artificial axon. It is a synthetic structure that supports action potentials based on the same physical mechanism as the voltage spikes in nerve cells. A network of such axons, which is yet to come, would constitute an artificial brain. Beyond device applications, the focus here is on the basic science, namely, a constructivist approach to cybernetics, algorithmic mathematics, and the brain.

Biological entities are capable of amazing material feats, such as self-organization, self-repair, self-replication, and self-immolation. Indeed, the most intriguing feature of living biomaterials, whether they are tissues, cells, or intracellular structures, is their ability to autonomously sense, decide, and perform work without the need of a project manager. The effect is multiscale—from enzymes to full organisms, each level is capable of such autonomous activities. Further, each scale has similar energy-using units that work together to compose the larger-scale material. For instance, autonomous cells work together to create tissues. In this article, we will discuss some of the outstanding and desirable properties of active biological materials that we might consider mimicking in future materials. We will discuss how such active materials are powered and explore some fundamental lessons we can learn to direct future fundamental scientific inquiries to begin to understand and use these properties to make synthetic, autonomous materials of the future.

Natural structural materials (NSMs) such as nacre, teeth, bones and crustacean exoskeleton are usually made of weak biomaterials arranged in specific structural design imparting them remarkable mechanical characteristics. Such hierarchical structural layouts found in nature encourage designing of mechanically desirable synthetic structural materials (SSMs). Among variety of natural hierarchical layouts, this paper specifically focuses on helicoidal architectural design found in the tough dactyl club of mantis shrimp. We first decode the mechanics behind helicoidal microstructural design and document the development of impact resistant macroscale helicoidal architectured synthetic structural materials (HA-SSMs). Next, near-field electrospinning technique (NFES)- both melt (polycaprolactone) and solution (polyvinylidene fluoride) type has been discussed in detail, as a novel method for developing lab scale 3D biomimetic HA-SSMs in micro-nanoscale. Further, the effect of the helical arrangement, size of substructures and surface treatment on strength and toughness of NFES fabricated HA-SSMs samples is analysed.

Particular attention has been recently devoted to the development of biohybrid photoconverters based on the bacterial Reaction Center (RC) of Rhodobacter sphaeroides. This highly efficient photoenzyme has a conversion yield close to unit that makes it extremely appealing in the field of artificial photosynthesis. Isolated RCs suffer of a limited absorption cross-section in the visible spectral region that limits their applicative employment. Here we report the synthesis of two heptamethine cyanine molecules, whose photophysical properties make them potentially suitable as light harvesting antennas for the RC.

While initial interest in nanocomposites was to explore size effects in mechanical behavior, current research is focused around the new paradigm of interface-dominated/enabled mechanical behavior. The use of advanced computational tools to accelerate the discovery, design, and fundamental understanding of behavior is highlighted along with novel synthesis and in situ nanomechanical characterization tools. Designed interfaces can be used as building blocks to create new forms of hierarchical composites with unprecedented mechanical and physical behavior. New frontiers in the field of mechanical behavior of nanocomposites involving metallic, nanocarbon, bioinspired, and biomaterials are reviewed.

The photosynthetic Reaction Center from the carotenoidless mutant strain of the purple non sulphur bacterium Rhodobacter (R.) sphaeroides was reconstituted in artificial phospholipid vesicles (liposomes) to mimic the physiological membrane environment. The pH dependence in the interval 5 – 10 of the rate of the charge-recombination reactions from the final electron acceptors QA and QB to the primary electron donor (namely kAD and kBD) have been investigated. The liposomes were constituted of either the zwitterionic phosphatidylcholine (PC) or the negatively charged phosphatidylglycerol (PG), two of the main phospholipids found in the photosynthetic membrane of the bacterium. In both cases, the kAD has no pH dependence similarly to the detergent case. The kBD also has a pH dependence similar to the detergent case, having two distinct regions below pH 7 and above pH 9. Fitting of the titration curve to a function involving two protonation sites results in a marked shift of the pKAs between the different solubilizing environments. These differences are discussed in the frame of possible physiological implications.

Despite lower hardness, stiffness, and resistance to harsh environments, heavy metallic parts and soft polymer-based composites are often preferred to ceramics because they offer higher resilience. By contrast, highly mineralized biomaterials combine these properties through hierarchical and heterogeneous architecture. Reproducing these internal designs into synthetic highly mineralized materials would therefore widen their range of application. To this aim, external fields have been used to control the orientation and position of microparticles and build complex architectures. This approach is compatible with most manufacturing processes and provides large flexibility in design. Here, I present an overview of these processes and describe how they can augment the properties of the materials produced. Theoretical and experimental descriptions are detailed to determine the strengths and limitations of each technique. With this knowledge, potential areas of improvement and future research directions will lead to the creation of highly mineralized materials with unprecedented functionalities.

The effect of ions on the structure and dynamics of aggracan solutions was investigated using a variety of scattering techniques (neutron spin echo, small angle neutron scattering, static and dynamic light scattering). The results show that aggrecan forms microgel-like assemblies which remain stable in the presence of counter-ions. As opposed to many synthetic polyelectrolytes which exhibit a great sensitivity to ion concentration and charge valency, it was found that aggrecan solutions are remarkable insensitive to charge valence. This property of aggrecan is consistent with its biological role as an ion reservoir mediating calcium metabolism and maintaining dimensional stability in cartilage and bone.

Biogenic minerals are widely studied materials for their particular properties derived from their hierarchical structure, using building blocks with sizes spanning several orders of magnitude. These special features can be assessed with different analytical tools, and it is important to know their capabilities and limitations. In order to determine the hierarchical structure of the shells, the nacre and prismatic layers of two marine animals were characterized by infrared spectroscopy, X-ray diffraction, and scanning electron microscopy. Based on these assessments, we found that the combination of these three techniques is useful to describe each structure level, and to explain some of the unique properties observed in these natural materials.

Electroactive conducting polymers are suitable for soft actuators (artificial muscles). The actuation is induced by electrochemical oxidation of conducting polymer (film) in an electrolyte solution, due to insertion of bulky counter ions (dopant ions). The magnitude of deformation (strain) depends on the size of dopant ions and the degree of oxidation. It is worthwhile to know the relationship between the magnitudes of deformation and ion size. An electrodeposited Polypyrrole film was electrochemically cycled in aqueous electrolytes of NaCl, NaBr, NaNO3, NaBF4 and NaClO4. The strain of film during electrochemical oxidation and reduction was precisely measured using a laser displacement meter and a handmade apparatus. From the strain and electrical charges inserted in the film during oxidation, the volumes and radii of dopant ions were estimated, assuming the isotropic expansion of the film. The estimated anion radii of Cl-, Br-, NO3-, BF4- and ClO4- were 235, 246, 250, 270 and 290, respectively. The results were discussed taking the crystallographic and hydrated ion radii in literatures into consideration.

The photosynthetic reaction center (RC) is an integral membrane protein that, upon absorption of photons, generates a hole-electron couple with a yield close to one. This energetic state has numerous possible applications in several biotechnological fields given that its lifetime is long enough to allow non-metabolic ancillary redox chemistry to take place. Here we focus on RCs reconstituted in liposomes, formed with sole phospholipids or in blends with other lipids, and show that the electrical charge sitting on the polar head of such hydrophobic molecules does play an important role on the stability of the hole-electron couple. More specifically this study shows that the presence of negative charges in the surrounding of the protein stabilizes the charge-separated state while positive charges have a strong opposite effect.