Progress in Modern Marine Biomaterials Research.

The growing demand for new, sophisticated, multifunctional materials has brought natural structural composites into focus, since they underwent a substantial optimization during long evolutionary selection pressure and adaptation processes. Marine biological materials are the most important sources of both inspiration for biomimetics and of raw materials for practical applications in technology and biomedicine. The use of marine natural products as multifunctional biomaterials is currently undergoing a renaissance in the modern materials science. The diversity of marine biomaterials, their forms and fields of application are highlighted in this review. We will discuss the challenges, solutions, and future directions of modern marine biomaterialogy using a thorough analysis of scientific sources over the past ten years.

Spectroscopic Methods Used in Implant Material Studies.

It is recognized that interactions between most materials are governed by their surface properties and manifest themselves at the interface formed between them. To gain more insight into this thin layer, several methods have been deployed. Among them, spectroscopic methods have been thoroughly evaluated. Due to their exceptional sensitivity, data acquisition speed, and broad material tolerance they have been proven to be invaluable tools for surface analysis, used by scientists in many fields, for example, implant studies. Today, in modern medicine the use of implants is considered standard practice. The past two decades of constant development has established the importance of implants in dentistry, orthopedics, as well as extended their applications to other areas such as aesthetic medicine. Fundamental to the success of implants is the knowledge of the biological processes involved in interactions between an implant and its host tissue, which are directly connected to the type of implant material and its surface properties. This review aims to demonstrate the broad applications of spectroscopic methods in implant material studies, particularly discussing hard implants, surface composition studies, and surface-cell interactions.

Tactic, reactive, and functional droplets outside of equilibrium.

Under non-equilibrium conditions, liquid droplets coupled to their environment by sustained flows of matter and/or energy can become "active" systems capable of various life-like functions. When "fueled" by even simple chemical reactions, such droplets can become tactic and can perform "intelligent" tasks such as maze solving. With more complex chemistries, droplets can support basic forms of metabolism, grow, self-replicate, and exhibit evolutionary changes akin to biological cells. There are also first exciting examples of active droplets connected into larger, tissue-like systems supporting droplet-to-droplet communication, and giving rise to collective material properties. As practical applications of droplets also begin to appear (e.g., in single-cell diagnostics, new methods of electricity generation, optofluidics, or sensors), it appears timely to review and systematize progress in this highly interdisciplinary area of chemical research, and also think about the avenues (and the roadblocks) for future work.

Light-Driven, Dynamic Assembly of Micron-To-Centimeter Parts, Micromachines and Microbot Swarms.

This work describes light-driven assembly of dynamic formations and functional particle swarms controlled by appropriately programmed light patterns. The system capitalizes on the use of a fluidic bed whose low thermal conductivity assures that light-generated heat remains "localized" and sets strong convective flows in the immediate vicinity of the particles being irradiated. In this way, even low-power laser light or light from a desktop slide projector can be used to organize dynamic formations of objects spanning four orders of magnitude in size (from microns to centimeters) and over nine orders of magnitude in terms of mass. These dynamic assemblies include open-lattice structures with individual particles performing intricate translational and/or rotational motions, density-gradient particle arrays, nested architectures of mechanical components (e.g., planetary gears), or swarms of light-actuated microbots controlling assembly of other objects.

An integrated self-optimizing programmable chemical synthesis and reaction engine.

Robotic platforms for chemistry are developing rapidly but most systems are not currently able to adapt to changing circumstances in real-time. We present a dynamically programmable system capable of making, optimizing, and discovering new molecules which utilizes seven sensors that continuously monitor the reaction. By developing a dynamic programming language, we demonstrate the 10-fold scale-up of a highly exothermic oxidation reaction, end point detection, as well as detecting critical hardware failures. We also show how the use of in-line spectroscopy such as HPLC, Raman, and NMR can be used for closed-loop optimization of reactions, exemplified using Van Leusen oxazole synthesis, a four-component Ugi condensation and manganese-catalysed epoxidation reactions, as well as two previously unreported reactions, discovered from a selected chemical space, providing up to 50% yield improvement over 25-50 iterations. Finally, we demonstrate an experimental pipeline to explore a trifluoromethylations reaction space, that discovers new molecules.

Delocalized, asynchronous, closed-loop discovery of organic laser emitters.

Contemporary materials discovery requires intricate sequences of synthesis, formulation, and characterization that often span multiple locations with specialized expertise or instrumentation. To accelerate these workflows, we present a cloud-based strategy that enabled delocalized and asynchronous design-make-test-analyze cycles. We showcased this approach through the exploration of molecular gain materials for organic solid-state lasers as a frontier application in molecular optoelectronics. Distributed robotic synthesis and in-line property characterization, orchestrated by a cloud-based artificial intelligence experiment planner, resulted in the discovery of 21 new state-of-the-art materials. Gram-scale synthesis ultimately allowed for the verification of best-in-class stimulated emission in a thin-film device. Demonstrating the asynchronous integration of five laboratories across the globe, this workflow provides a blueprint for delocalizing-and democratizing-scientific discovery.

Hydrogels as Scaffolds in Bone-Related Tissue Engineering and Regeneration.

Several years have passed since the medical and scientific communities leaned toward tissue engineering as the most promising field to aid bone diseases and defects resulting from degenerative conditions or trauma. Owing to their histocompatibility and non-immunogenicity, bone grafts, precisely autografts, have long been the gold standard in bone tissue therapies. However, due to issues associated with grafting, especially the surgical risks and soaring prices of the procedures, alternatives are being extensively sought and researched. Fibrous and non-fibrous materials, synthetic substitutes, or cell-based products are just a few examples of research directions explored as potential solutions. A very promising subgroup of these replacements involves hydrogels. Biomaterials resembling the bone extracellular matrix and therefore acting as 3D scaffolds, providing the appropriate mechanical support and basis for cell growth and tissue regeneration. Additional possibility of using various stimuli in the form of growth factors, cells, etc., within the hydrogel structure, extends their use as bioactive agent delivery platforms and acts in favor of their further directed development. The aim of this review is to bring the reader closer to the fascinating subject of hydrogel scaffolds and present the potential of these materials, applied in bone and cartilage tissue engineering and regeneration.

Proteins, peptides and peptidomimetics as active agents in implant surface functionalization.

The recent impact of implants on improving the human life quality has been enormous. During the past two decades we witnessed major advancements in both material and structural development of implants. They were driven mainly by the increasing patients' demand and the need to address the major issues that come along with the initially underestimated complexity of the bone-implant interface. While both, the materials and design of implants reached a certain, balanced state, recent years brought a shift in focus towards the bone-implant interface as the weakest link in the increasing implant long-term usability. As a result, several approaches were developed. They aimed at influencing and enhancing the implant osseointegration and its proper behavior when under load and stress. With this review, we would like to discuss the recent advancements in the field of implant surface modifications, emphasizing the importance of chemical methods, focusing on proteins, peptides and peptidomimetics as promising agents for titanium surface coatings.

Additive Contact Polarization of Nonferroelectric Polymers for Patterning of Multilevel Memory Elements.

When a thin polymer film supported by a conductive substrate is contacted by and then separated from a micropatterned polymeric stamp, the so-called contact electrification creates electrical charges over the stamped regions. Simultaneously, image charges are induced in the conductive substrate. Together, the surface and image charges establish large fields within the film, in effect polarizing it. Upon consecutive stampings, the magnitudes of polarization add up, enabling imprinting of multilevel polarization patterns. Because the electric field is high only within the film but low across the Gaussian surface surrounding the film/substrate system, the discharge of surface charges is slow and the polarization patterns are relatively long-lived. These findings are significant since multilevel polarization states have, to date, been achieved only in ferroelectrics or some specialized polymers-the current method extends them to common polymers such as poly(methyl methacrylate), poly(vinyl pyrrolidone), or poly(vinyl acetate).

DMPC Phospholipid Bilayer as a Potential Interface for Human Cystatin C Oligomerization: Analysis of Protein-Liposome Interactions Using NMR Spectroscopy.

Studies revolving around mechanisms responsible for the development of amyloid-based diseases lay the foundations for the recognition of molecular targets of future to-be-developed treatments. However, the vast number of peptides and proteins known to be responsible for fibril formation, combined with their complexity and complexity of their interactions with various cellular components, renders this task extremely difficult and time-consuming. One of these proteins, human cystatin C (hCC), is a well-known and studied cysteine-protease inhibitor. While being a monomer in physiological conditions, under the necessary stimulus-usually a mutation, it tends to form fibrils, which later participate in the disease development. This process can potentially be regulated (in several ways) by many cellular components and it is being hypothesized that the cell membrane might play a key role in the oligomerization pathway. Studies involving cell membranes pose several difficulties; therefore, an alternative in the form of membrane mimetics is a very attractive solution. Here, we would like to present the first study on hCC oligomerization under the influence of phospholipid liposomes, acting as a membrane mimetic. The protein-mimetic interactions are studied utilizing circular dichroism, nuclear magnetic resonance, and size exclusion chromatography.

Targeted crystallization of mixed-charge nanoparticles in lysosomes induces selective death of cancer cells.

Lysosomes have become an important target for anticancer therapeutics because lysosomal cell death bypasses the classical caspase-dependent apoptosis pathway, enabling the targeting of apoptosis- and drug-resistant cancers. However, only a few small molecules-mostly repurposed drugs-have been tested so far, and these typically exhibit low cancer selectivity, making them suitable only for combination therapies. Here, we show that mixed-charge nanoparticles covered with certain ratios of positively and negatively charged ligands can selectively target lysosomes in cancerous cells while exhibiting only marginal cytotoxicity towards normal cells. This selectivity results from distinct pH-dependent aggregation events, starting from the formation of small, endocytosis-prone clusters at cell surfaces and ending with the formation of large and well-ordered nanoparticle assemblies and crystals inside cancer lysosomes. These assemblies cannot be cleared by exocytosis and cause lysosome swelling, which gradually disrupts the integrity of lysosomal membranes, ultimately impairing lysosomal functions and triggering cell death.

Heterogeneous Catalysis "On Demand": Mechanically Controlled Catalytic Activity of a Metal Surface.

A metal surface passivated with a tightly packed self-assembled monolayer (SAM) can be made catalytically active upon the metal's mechanical deformation. This deformation renders the SAM sparser and exposes additional catalytic sites on the metal's surface. If the deformation is elastic, return of the metal to the original shape "heals" the SAM and nearly extinguishes the catalytic activity. Kelvin probe force microscopy and theoretical considerations both indicate that the catalytic domains "opening up" in the deformed SAM are of nanoscopic dimensions.

Metal-Organic Framework "Swimmers" with Energy-Efficient Autonomous Motility.

Placed at a water/air interface, particles of porphyrin-based MOFs (metal-organic frameworks) cut from large-area films display efficient, multiple-use autonomous motility powered by release of solvents incorporated in the MOF matrix and directionality dictated by their shapes. The particles can be refueled multiple times and can achieve speeds of ca. 200 mm·s-1 with high kinetic energy per unit of chemical "fuel" expended (>50 µJ·g-1). Efficiency of motion depends on the nature of the fuel used as well as the microstructure and surface wettability of the MOF surface. When multiple movers are present at the interface, they organize into "open" structures that exhibit collective, time-periodic motions.

Design of short peptides to block BTLA/HVEM interactions for promoting anticancer T-cell responses.

Antibody based immune-checkpoint blockade therapy is a major breakthrough in oncology, leading to clinical benefit for cancer patients. Among the growing family of inhibitory receptors, the B and T lymphocyte attenuator (BTLA), which interacts with herpes virus entry mediator (HVEM), is a promising target for immunotherapy. Indeed, BTLA inhibits T-cell proliferation and cytokine production. The crystal structure of the BTLA/HVEM complex has shown that the HVEM(26-38) fragment is directly involved in protein binding. We designed and analyzed the capacity of several analogs of this fragment to block the ligation between BTLA and HVEM, using competitive ELISA and cellular assay. We found that the HVEM(23-39) peptide can block BTLA/HVEM ligation. However, the blocking ability was due to the Cys encompassed in this peptide and that even free cysteine targeted the BTLA protein and blocked its interaction with HVEM. These data highlight a Cys-related artefact in vitro, which should be taken in consideration for future development of BTLA/HVEM blocking compounds.