Reexamination of Damping in Sliding Friction.

Friction is responsible for about one-third of the primary energy consumption in the world. So far, a thorough atomistic understanding of the frictional energy dissipation mechanisms is still lacking. The Amontons' law states that kinetic friction is independent of the sliding velocity while the Prandtl-Tomlinson model suggests that damping is proportional to the relative sliding velocity between two contacting objects. Through careful analysis of the energy dissipation process in atomic force microscopy measurements, here we propose that damping force is proportional to the tip oscillation speed induced by friction. It is shown that a physically well-founded damping term can better reproduce the multiple peaks in the velocity-dependent friction force observed in both experiments and molecular dynamics simulations. Importantly, the analysis gives a clear physical picture of the dynamics of energy dissipation in different friction phases, which provides insight into long-standing puzzles in sliding friction, such as velocity weakening and spring-stiffness-dependent friction.

Resonance in Atomic-Scale Sliding Friction.

Friction represents a major energy dissipation mode, yet the atomistic mechanism of how friction converts mechanical motion into heat remains elusive. It has been suggested that excess phonons are mainly excited at the washboard frequency, the fundamental frequency at which relative motion excites the interface atoms, and the subsequent thermalization of these nonequilibrium phonons completes the energy dissipation process. Through combined atomic force microscopy measurements and atomistic modeling, here we show that the nonlinear interactions between a sliding tip and the substrate can generate excess phonons at not only the washboard frequency but also its harmonics. These nonequilibrium phonons can induce resonant vibration of the tip and lead to multiple peaks in the friction force as the tip sliding velocity ramps up. These observations disclose previously unrecognized energy dissipation channels associated with tip vibration and provide insights into engineering friction force through adjusting the resonant frequency of the tip-substrate system.

Concentration effects on capture rate and translocation configuration of nanopore-based DNA detection.

Nanopore is a kind of powerful tool to detect single molecules and investigate fundamental biological processes. In biological cells or real detection systems, concentration of DNA molecules is various. Here, we report an experimental study of the effects of DNA concentration on capture rate and translocation configuration with different sized nanopores and applied voltages. Three classes of DNA translocation configurations have been observed including linear translocation, folded translocation, and cotranslocation. In the case of relatively large sized nanopore or high applied voltage, considerable cotranslocation events have been detected. The percentage of cotranslocation events also increases with DNA concentration, which leads to the relationship between capture rate and DNA concentration deviates from linearity. Therefore, in order to reflect the number of translocation molecules accurately, the capture rate should be corrected by double-counting cotranslocation events. These results will provide a valuable reference for the design of nanopore sensors.

Diminishing Cohesion of Chitosan Films in Acidic Solution by Multivalent Metal Cations.

Chitosan is a natural polymer with good biocompatibility, biodegradability, and bioactivity that has great potential for biomedical and industrial applications. Like other natural sugar-based polymers, chitosan molecules own versatile adhesion abilities to bind with various surfaces, owing to multiple functional moieties contained in the chain. To develop the promising biomaterials based on the chitosan chemistry, it is fundamentally important to figure out its adhesion mechanism under a certain condition, which leaves us numbers of open questions. In this work, we characterized the chitosan films adsorbed on a mica substrate in acidic solution and investigated the effects of multivalent salts on the cohesive behaviors of the films by means of the surface forces apparatus. The results showed that the cohesion capacities of chitosan films were reduced to around 30% of their original states after the addition of 10-7 M LaCl3 into 150 mM acetic acid, which could be partially recovered by holding the films at the contact position for a longer time. Surprisingly, the cohesion loss in the films exhibited the dependence on the properties of the metal cations including valance and concentration. The topography of the chitosan-coated surface also showed obvious aggregation in the presence of submicromolar of the salts. Here, we attributed these phenomena regarding cohesion loss to the mechanisms involved in the absorption of metal cations by the chitosan chains, which not only consumed the binding sites but also induced conformation change in the polymer network. Our findings may offer a suggestion for the production of chitosan-based materials to notice the potential impacts of ultralow concentrated salts that are usually neglected even under acidic conditions.

Discrimination of Protein Amino Acid or Its Protonated State at Single-Residue Resolution by Graphene Nanopores.

The function of a protein is determined by the composition of amino acids and is essential to proteomics. However, protein sequencing remains challenging due to the protein's irregular charge state and its high-order structure. Here, a proof of principle study on the capability of protein sequencing by graphene nanopores integrated with atomic force microscopy is performed using molecular dynamics simulations. It is found that nanopores can discriminate a protein sequence and even its protonation state at single-residue resolution. Both the pulling forces and current blockades induced by the permeation of protein residues are found to be highly correlated with the type of amino acids, which makes the residues identifiable. It is also found that aside from the dimension, both the conformation and charge state of the residue can significantly influence the force and current signal during its permeation through the nanopore. In particular, due to the electro-osmotic flow effect, the blockade current for the double-protonated histidine is slightly smaller than that for single-protonated histidine, which makes it possible for discrimination of different protonation states of amino acids. The results reported here present a novel protein sequencing scheme using graphene nanopores combined with nanomanipulation technology.

Adaptive hydrophobic and hydrophilic interactions of mussel foot proteins with organic thin films.

The adhesion of mussel foot proteins (Mfps) to a variety of specially engineered mineral and metal oxide surfaces has previously been investigated extensively, but the relevance of these studies to adhesion in biological environments remains unknown. Most solid surfaces exposed to seawater or physiological fluids become fouled by organic conditioning films and biofilms within minutes. Understanding the binding mechanisms of Mfps to organic films with known chemical and physical properties therefore is of considerable theoretical and practical interest. Using self-assembled monolayers (SAMs) on atomically smooth gold substrates and the surface forces apparatus, we explored the force-distance profiles and adhesion energies of three different Mfps, Mfp-1, Mfp-3, and Mfp-5, on (i) hydrophobic methyl (CH3)- and (ii) hydrophilic alcohol (OH)-terminated SAM surfaces between pH 3 and pH 7.5. At acidic pH, all three Mfps adhered strongly to the CH3-terminated SAM surfaces via hydrophobic interactions (range of adhesive interaction energy = -4 to -9 mJ/m(2)) but only weakly to the OH-terminated SAM surfaces through H- bonding (adhesive interaction energy ≤ -0.5 mJ/m(2)). 3, 4-Dihydroxyphenylalanine (Dopa) residues in Mfps mediate binding to both SAM surface types but do so through different interactions: typical bidentate H-bonding by Dopa is frustrated by the longer spacing of OH-SAMs; in contrast, on CH3-SAMs, Dopa in synergy with other nonpolar residues partitions to the hydrophobic surface. Asymmetry in the distribution of hydrophobic residues in intrinsically unstructured proteins, the distortion of bond geometry between H-bonding surfaces, and the manipulation of physisorbed binding lifetimes represent important concepts for the design of adhesive and nonfouling surfaces.

Experimental observation of the ion-ion correlation effects on charge inversion and strong adhesion between mica surfaces in aqueous electrolyte solutions.

Direct force measurements between two mica surfaces in aqueous electrolyte solutions over broad ranges of LaCl3 concentrations and pH values were carried out with a surface forces apparatus. Charge inversion on mica surfaces is detected once the LaCl3 concentration reaches a critical value. With the continual increase of LaCl3 concentrations, the mica surface will be overscreened by the counterions. It is demonstrated that the two mica surfaces may experience the jump-in contact even at high LaCl3 concentrations, which is seldom seen in monovalent salt solutions. The strong adhesion cannot be attributed to the van der Waals force alone, but should include the ion-ion correlation forces. Through adjusting the pH values in LaCl3 solutions, the ion-ion correlation force can be evaluated quantitatively. These results provide important insight into the fundamental understanding in the role of ion-ion correlations in ion screening mechanism and interactions between charged objects.

Tuning interfacial molecular asymmetry to engineer protective coatings with superior surface anchoring, antifouling and antibacterial properties.

Multifunctional robust protective coatings that combine biocompatibility, antifouling and antimicrobial properties play an essential role in reducing host reactions and infection on invasive medical devices. However, developing these protective coatings generally faces a paradox: coating materials capable of achieving robust adhesion to substrates via spontaneous deposition inevitably initiate continuous biofoulant adsorption, while those employing strong hydration capability to resist biofoulant attachment have limited substrate binding ability and durability under wear. Herein, we designed a multifunctional terpolymer of poly(dopamine methyacrylamide-co-2-methacryloyloxyethyl phoasphorylcholine-co-2-(dimethylamino)-ethyl methacrylate) (P(DMA-co-MPC-co-DMAEMA)), which integrates desired yet traditionally incompatible functions (i.e., robust adhesion, antifouling, lubrication, and antimicrobial properties). Direct normal and lateral force measurements, dynamic adsorption tests, surface ion conductance mapping were applied to comprehensively investigate the nanomechanics of coating-biofloulant interactions. Catechol groups of DMA act as basal anchors for robust substrate deposition, while the highly hydrated zwitterion of MPC provides apical protection to resist biofouling and wear. Moreover, the antimicrobial property is conferred through the protonation of tertiary amine groups on DMAEMA, inhibiting infection under physiological conditions. This work provides an effective strategy for harmonizing demanded yet incompatible properties in one coating material, with significant implications for the development of multifunctional surfaces towards the advancement of invasive biomedical devices. STATEMENT OF SIGNIFICANCE: Multifunctional robust protective coatings have been widely utilized in invasive medical devices to mitigate host responses and infection. However, modified surface coatings often encounter a trade-off between robust adhesion to substrates and strong hydration capability for antifouling and antimicrobial properties. We propose a universal strategy for surface modification by dopamine-assisted co-deposition with a multifunctional terpolymer of P(DMA-co-MPC-co-DMAEMA) that simultaneously achieves robust adhesion, antifouling, and antimicrobial properties. Through elucidating the nanomechanics with fundamentally understanding the interactions between the coating and biomacromolecules, we highlight the role of DMA for substrate adhesion, MPC for biofouling resistance, and DMAEMA for antimicrobial activity. This approach presents a promising strategy for constructing multifunctional coatings on minimally invasive medical devices by tuning interfacial molecular asymmetricity to reconcile incompatible properties within one coating.

The quality of life in nasopharyngeal carcinoma radiotherapy: A longitudinal study.

Objective: This article aims to longitudinally compare nasopharyngeal carcinoma (NPC) patients' quality of life (QoL) during radiotherapy (RT) and identify QoL correlates. Methods: This study included 98 patients, with 85 completing full follow-up. Data were collected at baseline (T1), midpoint of RT (T2), and RT completion (T3), between October 2021 and November 2022. QoL was assessed using the European Organization for Research and Treatment of Cancer Quality of Life Questionnaire-Core 30 (EORTC QLQ-C30). RIOM severity was evaluated by the toxicity criteria of Radiation Therapy Oncology Group (RTOG). The nutritional status was evaluated using the Nutritional Risk Screening 2002 (NRS 2002), body mass index (BMI), and the Patient-Generated Subjective Global Assessment (PG-SGA). The generalized estimating equation described the QoL evolution and correlated it with RIOM, nutritional status, and other influential factors. Results: Significant deterioration was observed in various subscales of EORTC QLQ-C30 during RT, including global health status (GHS), physical function, role function, emotional function, fatigue, nausea/vomiting, pain, insomnia, appetite loss, and constipation (all P â€‹< â€‹0.05). Substantial deterioration was also observed in RIOM, nutritional status, and part of hematological indexes (all P â€‹< â€‹0.05). The decline of QoL was associated with gender, age, education level, chemotherapy regimen, Karnofsky performance status (KPS) score, RIOM severity, NRS 2002 score, PG-SGA score, and lymphocyte level (all P â€‹< â€‹0.05). Conclusions: QoL declined during RT and were associated with certain factors. Healthcare professionals should focus on alleviating treatment-related complications and identifying individuals at high risk of malnutrition early to improve outcomes for patients with NPC.

Modulating Friction by the Phase of the Vertical Vibrational Excitation at Washboard Frequency.

Applying external vibrations at the resonant frequencies of the frictional system has been a highly effective approach to suppress friction but usually requires additional energy consumption. In this study, we find that in addition to exerting the vibration at the resonant frequency of the frictional system, the friction force on the atomically flat silicon surface can also present a local minimum when the oscillation frequency of the vertical vibrational excitation equals the washboard frequency with respect to the sliding velocity. Moreover, compared with the additional energy consumption at the resonant frequency, applying vertical vibrational excitation at the washboard frequency requires much less energy consumption. The study further shows that the friction force under the washboard frequency can be effectively mediated depending on how the initial phase angle of the vertical vibrational excitation affects the effective substrate potential barrier at the slip moment of the tip. We have also extended the proposed friction modulation technique on atomically flat surfaces to periodic textured surfaces and confirmed its practicality and great potential for controlling friction.

Adhesion of mussel foot protein Mefp-5 to mica: an underwater superglue.

Mussels have a remarkable ability to attach their holdfast, or byssus, opportunistically to a variety of substrata that are wet, saline, corroded, and/or fouled by biofilms. Mytilus edulis foot protein-5 (Mefp-5) is one of several proteins in the byssal adhesive plaque of the mussel M. edulis. The high content of 3,4-dihydroxyphenylalanine (Dopa) (~30 mol %) and its localization near the plaque-substrate interface have often prompted speculation that Mefp-5 plays a key role in adhesion. Using the surface forces apparatus, we show that on mica surfaces Mefp-5 achieves an adhesion energy approaching E(ad) = ~-14 mJ/m(2). This exceeds the adhesion energy of another interfacial protein, Mefp-3, by a factor of 4-5 and is greater than the adhesion between highly oriented monolayers of biotin and streptavidin. The adhesion to mica is notable for its dependence on Dopa, which is most stable under reducing conditions and acidic pH. Mefp-5 also exhibits strong protein-protein interactions with itself as well as with Mefp-3 from M. edulis.

Nutrition management for patients with head and neck cancer during peri-radiotherapy: A systematic review and quality appraisal of clinical practice guidelines using the AGREE II instrument.

Objective: To evaluate the quality of clinical practice guidelines (CPGs) for nutrition management of patients with head and neck cancer (HNC) during peri-radiotherapy, as well as to summarize the nutrition recommendations fitting the subject. Methods: CPGs published in English, Chinese and German were identified from databases, guideline networks, and websites of nutritional associations from the databases' inception to March 8, 2022. Three independent appraisers used the Appraisal of Guidelines for Research and Evaluation II (AGREE II) Instrument to assess the quality of CPGs. The intraclass correlation coefficient (ICC) was used to calculate appraiser agreement. Results: 769 records were identified. After removing duplicates, 470 articles were screened. 12 CPGs were identified with nutrition-specific recommendations. 67% of CPGs were rated as high quality, and 33% as low quality. Recommendations were categorized into nutritional risk screening, nutrition assessment, nutrition counseling, nutrition interventions, nutrition intake, swallowing function management, weight management, exercise, multidisciplinary team, post-discharge care, nutrients, and pharmacologic interventions. Conclusion: We found discrepant recommendations in existing CPGs, including nutrition screening, nutrition assessment, nutrition intake, and nutrients. We also reported the absence of essential parts of CPGs, including the views of its target users, the statement of external review, the method to formulate the recommendations, strategies to improve uptake, and resource implications of applying the CPGs. CPGs with low quality should be improved in future updates based on currently available guideline development tools. Specialized CPGs on nutrition management for HNC patients during peri-radiotherapy should be developed. Systematic review registration: https://www.crd.york.ac.uk/PROSPERO/index.php, identifier CRD42022320322.

Navigated Delivery of Peptide to the Nanopore Using In-Plane Heterostructures of MoS2 and SnS2 for Protein Sequencing.

The impressive success of DNA sequencing using nanopores makes it possible to realize nanopore based protein sequencing. Well-controlled capture and linear movement of the protein are essential for accurate nanopore protein sequencing. Here, by taking advantage of different binding affinities of protein to two isomorphic materials, we theoretically designed a heterostructual platform for delivering the unfolded peptide to the nanopore sensing region. Due to the stronger binding between the peptide and SnS2 compared to MoS2, the peptide would adsorb to the SnS2 nanostripe and keep its threadlike conformation in the MoS2/SnS2/MoS2 heterostructure. Through switching the direction of the applied electric field in real time, the peptide was strategically driven to move along the designed path to the target nanopore. The ionic current blockades were also found to be different as the compositions of the peptide were changed, indicating the possibility for differentiating different peptides using this platform.

Sequence-Specific Detection of DNA Strands Using a Solid-State Nanopore Assisted by Microbeads.

Simple, rapid, and low-cost detection of DNA with specific sequence is crucial for molecular diagnosis and therapy applications. In this research, the target DNA molecules are bonded to the streptavidin-coated microbeads, after hybridizing with biotinylated probes. A nanopore with a diameter significantly smaller than the microbeads is used to detect DNA molecules through the ionic pulse signals. Because the DNA molecules attached on the microbead should dissociate from the beads before completely passing through the pore, the signal duration time for the target DNA is two orders of magnitude longer than free DNA. Moreover, the high local concentration of target DNA molecules on the surface of microbeads leads to multiple DNA molecules translocating through the pore simultaneously, which generates pulse signals with amplitude much larger than single free DNA translocation events. Therefore, the DNA molecules with specific sequence can be easily identified by a nanopore sensor assisted by microbeads according to the ionic pulse signals.

Study of DNA adsorption on mica surfaces using a surface force apparatus.

We report our studies on the adsorption properties of double-stranded DNA molecules on mica surfaces in a confined environment using a surface force apparatus. Specifically, we studied the influence of cation species and concentrations on DNA adsorption properties. Our results indicated that divalent cations (Mg(2+) and Co(2+)) preferred to form uniform and moderately dense DNA layers on a mica substrate. By measuring the interactions between DNA-coated mica and bare mica in an aqueous solution, obvious adhesion was observed in a cobalt chloride solution, possibly due to the ion-correlation attraction between negatively charged DNA and the mica surface. Furthermore, the interaction differences that were observed with MgCl2 and CoCl2 solutions reveal that the specific adsorption behaviors of DNA molecules on a mica substrate were mediated by these two salts. Our results are helpful to elucidate the dynamics of DNA binding on a solid substrate.

Boronate complex formation with Dopa containing mussel adhesive protein retards ph-induced oxidation and enables adhesion to mica.

The biochemistry of mussel adhesion has inspired the design of surface primers, adhesives, coatings and gels for technological applications. These mussel-inspired systems often focus on incorporating the amino acid 3,4-dihydroxyphenyl-L-alanine (Dopa) or a catecholic analog into a polymer. Unfortunately, effective use of Dopa is compromised by its susceptibility to auto-oxidation at neutral pH. Oxidation can lead to loss of adhesive function and undesired covalent cross-linking. Mussel foot protein 5 (Mfp-5), which contains ∼ 30 mole % Dopa, is a superb adhesive under reducing conditions but becomes nonadhesive after pH-induced oxidation. Here we report that the bidentate complexation of borate by Dopa to form a catecholato-boronate can be exploited to retard oxidation. Although exposure of Mfp-5 to neutral pH typically oxidizes Dopa, resulting in a>95% decrease in adhesion, inclusion of borate retards oxidation at the same pH. Remarkably, this Dopa-boronate complex dissociates upon contact with mica to allow for a reversible Dopa-mediated adhesion. The borate protection strategy allows for Dopa redox stability and maintained adhesive function in an otherwise oxidizing environment.