Metastable Supramolecular Assembly of Simple Monomers Enabled by Confinement: Towards Aqueous Phase Room Temperature Phosphorescence.

The application of supramolecular assembly (SA) with room temperature phosphorescence (RTP) in aqueous phase has the potential to revolutionize numerous fields. However, using simple molecules with crystalline RTP to construct SA with aqueous phase RTP is hardly possible from the standpoint of forces. The reason lies in that the transition from crystal to SA involves a structure transformation from highly stable to more dynamic state, leading to increased non-radiative deactivation pathways and silent RTP signal. Here, with the benefit of the confinement from the layered double hydroxide (LDH), various simple molecules (benzene derivatives) can successfully form metastable SA with aqueous phase RTP. The maximum of RTP lifetime and efficiency can reach 654.87 ms and 5.02%, respectively. Mechanistic studies reveal the LDH energy trap can strengthen the intermolecular interaction, providing the prerequisite for the existence of metastable SA and appearance of aqueous phase RTP. The universality of this strategy will usher exploration into other multifunctional monomer, facilitating the development of SAs with aqueous phase RTP.

Dynamic Control over Hierarchically Dendritic Architectures of Simple Heterogenous Monomers by Living Supramolecular Assembly.

The successful preparation of supramolecular block copolymers (SBCPs) by living supramolecular assembly technology requires two kinetic systems in which both the seed (nucleus) and heterogenous monomer providers are in non-equilibrium. However, employing simple monomers to construct the SBCPs via this technology is almost impossible because the low spontaneous nucleation barrier of simple molecules prevents the formation of kinetic states. Here, with the help of confinement from layered double hydroxide (LDH), various simple monomers successfully form living supramolecular co-assemblies (LSCA). LDH overcomes a considerable energy barrier to obtain living seeds to support the growth of the inactivated second monomer. The ordered LDH topology is sequentially mapped to the seed, second monomer, and binding sites. Thus, the multidirectional binding sites are endowed with the ability to branch, making the branch length of dendritic LSCA reach its maximum value of 3.5 cm so far. The strategy of universality will guide exploration into the development of multi-function and multi-topology advanced supramolecular co-assemblies.

Biased Symmetry Breaking in the Formation of Intercalated Layered Double Hydroxides: toward Control of Homochiral Supramolecular Assembly.

Homochiral supramolecular assembly (HSA) based on achiral molecules has provided important clues to understand the origin of biological homochirality from the aspect of symmetry breaking. However, planar achiral molecules still face the challenge of forming HSA due to the lack of driving force for twisted stacking, which is a prerequisite for homochirality. Here, with the benefit of the formation of 2D intercalated layered double hydroxide (LDH, host-guest nanomaterials) in vortex motion, planar achiral guest molecules can form the chiral units with spatially asymmetrical structure in the confinement space of LDH. Once the LDH is removed, these chiral units are in a thermodynamic non-equilibrium state, which can be amplified to HSA by self-replicating. Especially, the homochiral bias can be predicted in advance by controlling the vortex direction. Therefore, this study breaks the bottleneck of complicated molecular design and provides a new technology to achieve HSA made of planar achiral molecules with definite handedness.

TRPC6 promotes daunorubicin-induced mitochondrial fission and cell death in rat cardiomyocytes with the involvement of ERK1/2-DRP1 activation.

Daunorubicin (DNR-) induced cardiotoxicity seriously restricts its clinical application. Transient receptor potential cation channel subfamily C member 6 (TRPC6) is involved in multiple cardiovascular physiological and pathophysiological processes. However, the role of TRPC6 anthracycline-induced cardiotoxicity (AIC) remains unclear. Mitochondrial fragmentation greatly promotes AIC. TRPC6-mediated ERK1/2 activation has been shown to favor mitochondrial fission in dentate granule cells. The aim of the present study was to elucidate the effects of TRPC6 on daunorubicin- induced cardiotoxicity and identify the mechanisms associated with mitochondrial dynamics. The sparkling results showed that TRPC6 was upregulated in models in vitro and in vivo. TRPC6 knockdown protected cardiomyocytes from DNR-induced cell apoptosis and death. DNR largely facilitated mitochondrial fission, boosted mitochondrial membrane potential collapse and damaged debilitated mitochondrial respiratory function in H9c2 cells，these effects were accompanied by TRPC6 upregulation. siTRPC6 effectively inhibited these mitochondrial adverse aspects showing a positive unexposed effect on mitochondrial morphology and function. Concomitantly, ERK1/2-DRP1 which is related to mitochondrial fission was significantly activated with amplified phosphorylated forms in DNR-treated H9c2 cells. siTRPC6 effectively suppressed ERK1/2-DPR1 over activation, hinting at a potential correlation between TRPC6 and ERK1/2-DRP1 by which mitochondrial dynamics are possibly modulated in AIC. TRPC6 knockdown also raised the Bcl-2/Bax ratio, which may help to block mitochondrial fragmentation-related functional impairment and apoptotic signaling. These findings suggested an essential role of TRPC6 in AIC by intensifying mitochondrial fission and cell death via ERK1/2-DPR1, which could be a potential therapeutic target for AIC.

Time-dependent Phosphorescence Color of Carbon Dots in Binary Salt Matrices through Activations by Structural Confinement and Defects for Dynamic Information Encryption.

The emergence of time-dependent phosphorescence color (TDPC) materials has taken information encryption to high-security levels. However, due to the only path of exciton transfer, it is almost impossible to obtain TDPC for chromophores with a single emission center. Theoretically, in inorganic-organic composites, the exciton transfer of organic chromophores depends on the inorganic structure. Here, we assign two structural effects to inorganic NaCl by metal (Mg2+ or Ca2+ or Ba2+ ) doping, which triggers the TDPC performance of carbon dots (CDs) with a single emission center. The resulting material is used for multi-level dynamic phosphorescence color 3D coding to achieve information encryption. The structural confinement activates the green phosphorescence of CDs; while the structural defect activates tunneling-related yellow phosphorescence. Such simply doped inorganic matrices can be synthesized using the periodic table of metal cations, endowing chromophores with tremendous control over TDPC properties. This demonstration extends the design view of dynamic luminescent materials.

Instantaneous Ablation Behavior of Laminated CFRP by High-Power Continuous-Wave Laser Irradiation in Supersonic Wind Tunnel.

Experimental and numerical investigations of the instantaneous ablation behavior of laminated carbon fiber-reinforced polymer (CFRP) exposed to an intense continuous-wave (CW) laser in a supersonic wind tunnel are reported. We establish an in situ observation measurement in the experiments to examine the instantaneous ablation behavior. The surface recession depth is calculated by using the Particle Image Velocimetry (PIV) method, taking the ply angle of laminated CFRP as a reference. A coupled thermal-fluid-ablation numerical model incorporating mechanisms of oxidation, sublimation, and thermomechanical erosion is developed to solve the ablation-through problem of multilayer materials. The results show that the laser ablation depth is related to the laser power density, airflow velocity and airflow mode. Thermomechanical erosion is the primary ablation mechanism when the surface temperature is relatively low and the cavity flow mode is a closed cavity flow. When the surface temperature reaches the sublimation of carbon and the airflow mode is transformed to open cavity flow, sublimation plays a dominant role and the ablation rate of thermomechanical erosion gradually decreases.

Photoluminescence Mechanism of Carbon Dots: Triggering Multiple Color Emissions through Controlling the Degree of Protonation.

Carbon dots (CDs) have excellent optical properties, low toxicity and easy preparation, which have led to them being widely used in biomedicine, sensing and optical devices. However, although great progress has been made in the preparation of CDs, the detailed exploration of their photoluminescence (PL) mechanism is still under debate due to their complex structures and surface functionalities. Here, we proposed a single change in the pH of the synthesis condition, which had no effect on the CDs intrinsic core states and avoided the mutual influence of multiple PL origins. The m-phenylenediamine (m-PD) served as a carbon source, whose protonation degree determined the surface state of the resulting CDs and the accompanying fluorescence characteristics. The as-obtained CDs materials can be applied in the chemical sensor and anti-counterfeiting fields in a targeted manner. Therefore, our work not only contributes to the explanation of the CDs PL mechanism, but also obtains a series of CDs materials with controllable PL properties.

Dielectric dispersion characteristics of the phospholipid bilayer with subnanometer resolution from terahertz to mid-infrared.

There is growing interest in whether the myelinated nerve fiber acts as a dielectric waveguide to propagate terahertz to mid-infrared electromagnetic waves, which are presumed stable signal carrier for neurotransmission. The myelin sheath is formed as a multilamellar biomembrane structure, hence insights into the dielectric properties of the phospholipid bilayer is essential for a complete understanding of the myelinated fiber functioning. In this work, by means of atomistic molecular dynamics simulations of the dimyristoylphosphatidylcholine (DMPC) bilayer in water and numerical calculations of carefully layered molecules along with calibration of optical dielectric constants, we for the first time demonstrate the spatially resolved (in sub-nm) dielectric spectrum of the phospholipid bilayer in a remarkably wide range from terahertz to mid-infrared. More specifically, the membrane head regions exhibit both larger real and imaginary permittivities than that of the tail counterparts in the majority of the 1-100 THz band. In addition, the spatial variation of dielectric properties suggests advantageous propagation characteristics of the phospholipid bilayer in a relatively wide band of 55-85 THz, where the electromagnetic waves are well confined within the head regions.

Long non-coding RNA LINC00511 facilitates colon cancer development through regulating microRNA-625-5p to target WEE1.

The altered part of long non-coding RNA LINC00511 (LINC00511) is extensively discussed in malignancies. Finitely, the mechanism of LINC00511 in colon cancer (CC) development lacks thorough explorations. Hence, this work is started from the LINC00511-mediated microRNA (miR)-625-5p/WEE1 axis in the CC process. LINC00511, miR-625-5p, and WEE1 levels were tested in CC tissues and cells. Subcellular localization of LINC00511 was clarified. CC cells were transfected with oligonucleotides that altered LINC00511, and miR-625-5p expression to define their performance in CC cell progression. The tumorigenic ability of cells was verified in xenografted tumors. CC tissues and cells highly expressed LINC00511 and WEE1 and lowly expressed miR-625-5p. LINC00511 was mainly localized in the cytoplasm. Deleted LINC00511 or restored miR-625-5p delayed cellular growth in CC. LINC00511 sponged miR-625-5p to target WEE1. Silenced miR-625-5p mitigated the role of depleted LINC00511, while inhibited WEE1 rescued the effect of silenced miR-625-5p on the biological functions of CC cells. It is summarized that down-regulated LINC00511 obstructs tumorigenesis of CC through restoring miR-625-5p and silencing WEE1, consolidating a basal reference for CC-oriented therapy.

Application of Bacillus mucilaginosus in the carbonation of steel slag.

The stacking of steel slag has detrimental effects mainly for the waste of resources and the pollution of environment. In this study, a novel method based on microbially induced calcium precipitation (MICP) was proposed by utilizing a type of microorganism named Bacillus mucilaginosus, which could secrete carbonic anhydrase (CA) through the metabolism process, accelerating the hydration of carbon dioxide (CO2) and thus facilitating the formation of carbonate ions (CO32-). First, comparing the biologically deposited calcium carbonate with the chemically deposited one, it was found that the crystallinity and crystal size of the biological deposition was lower, leading to its cementitious properties. Under the condition of 1 wt. (weight) % dosage, the carbonation degree increased from 66.34 to 86.25% and the compressive strength improved greatly from 7.4 to 11.2 MPa as well. The weight gain rate of biologically carbonated specimens was also twice as much as the directly carbonated ones. This work strongly demonstrated that biological carbonation technology could not only improve the CO2 sequestration potential of steel slag but also enhance the mechanical properties and durability of steel slag products. KEY POINTS: • Bacillus mucilaginosus could resuscitate and proliferate in the steel slag environment. • B. mucilaginosus secreted carbon anhydrase, which could accelerate the hydration of CO2 and facilitate the precipitation of calcium carbonate. • Biologically carbonated steel slag had greater mechanical performance than directly carbonated one.

Mid-infrared multispectral confocal microscope using off-axis parabolic mirrors to study epiretinal membranes.

Mid-infrared (mid-IR) multispectral microscopy, especially operating at the wavelength of 5-11 µm, is an effective tool for detecting, identifying, and quantifying the structure and composition of biological tissues. Compared with that based on the optical lens, the mid-infrared microscope composed of off-axis parabolic (OAP) mirrors is low cost, simple, and suitable for longer range of wavelength without chromatic aberrations, while keeping the optical transmission efficiency. Here we report a compact and versatile mid-infrared multispectral confocal microscope based on off-axis parabolic mirrors. We also perform numerical calculations based on the vectorial diffraction theory on OAP mirrors and analyze the typical aberrations and misalignment of the OAP-based optical system. Finally, we perform multispectral imaging of the epiretinal membrane of the human eyes with the spectrum selected according to its resonance absorption peak. The system is designed to perform multispectral or even hyperspectral imaging to identify and predict potential disease.

Location and Conformational Ensemble of Menaquinone and Menaquinol, and Protein-Lipid Modulations in Archaeal Membranes.

Halobacteria, a type of archaea in high salt environments, have phytanyl ether phospholipid membranes containing up to 50% menaquinone. It is not understood why a high concentration of menaquinone is required and how it influences membrane properties. In this study, menaquinone-8 headgroup and torsion parameters of isoprenoid tail are optimized in the CHARMM36 force field. Molecular dynamics simulations of archaeal bilayers containing 0 to 50% menaquinone characterize the distribution of menaquinone-8 and menaquinol-8, as well as their effects on mechanical properties and permeability. Menaquinone-8 segregates to the membrane midplane above concentrations of 10%, favoring an extended conformation in a fluid state. Menaquinone-8 increases the bilayer thickness but does not significantly alter the area compressibility modulus and lipid chain ordering. Counterintuitively, menaquinone-8 increases water permeability because it lowers the free energy barrier in the midplane. The thickness increase due to menaquinone-8 may help halobacteria ameliorate hyper-osmotic pressure by increasing the membrane bending constant. Simulations of the archaeal membranes with archaerhodopsin-3 show that the local membrane surface adjusts to accommodate the thick membranes. Overall, this study delineates the biophysical landscape of 50% menaquinone in the archaeal bilayer, demonstrates the mixing of menaquinone and menaquinol, and provides atomistic details about menaquinone configurations.

Preventive treatment with ginsenoside Rb1 ameliorates monocrotaline-induced pulmonary arterial hypertension in rats and involves store-operated calcium entry inhibition.

CONTEXT: Ginsenoside Rb1, the main active ingredient of ginseng, exhibits ex vivo depression of store-operated calcium entry (SOCE) and related vasoconstriction in pulmonary arteries derived from pulmonary hypertension (PH) rats. However, the in vivo effects of ginsenoside Rb1 on PH remain unclear. OBJECTIVE: This study explored the possibility of using ginsenoside Rb1 as an in vivo preventive medication for type I PH, i.e., pulmonary arterial hypertension (PAH), and potential mechanisms involving SOCE. MATERIALS AND METHODS: Male Sprague-Dawley rats (170-180 g) were randomly divided into Control, MCT, and MCT + Rb1 groups (n = 20). Control rats received only saline injection. Rats in the MCT + Rb1 and MCT groups were intraperitoneally administered single doses of 50 mg/kg monocrotaline (MCT) combined with 30 mg/kg/day ginsenoside Rb1 or equivalent volumes of saline for 21 consecutive days. Subsequently, comprehensive parameters related to SOCE, vascular tone, histological changes and hemodynamics were measured. RESULTS: Ginsenoside Rb1 reduced MCT-induced STIM1, TRPC1, and TRPC4 expression by 35.00, 31.96, and 32.24%, respectively, at the protein level. SOCE-related calcium entry and pulmonary artery contraction decreased by 162.6 nM and 71.72%. The mean pulmonary artery pressure, right ventricle systolic pressure, and right ventricular mass index decreased by 19.5 mmHg, 21.6 mmHg, and 39.50%. The wall thickness/radius ratios decreased by 14.67 and 17.65%, and the lumen area/total area ratios increased by 18.55 and 15.60% in intrapulmonary vessels with 51-100 and 101-150 µm o.d. CONCLUSION: Ginsenoside Rb1, a promising candidate for PH prevention, inhibited SOCE and related pulmonary vasoconstriction, and relieved MCT-induced PAH in rats.

Catechol-functionalized hydrogels: biomimetic design, adhesion mechanism, and biomedical applications.

Hydrogels are a unique class of polymeric materials that possess an interconnected porous network across various length scales from nano- to macroscopic dimensions and exhibit remarkable structure-derived properties, including high surface area, an accommodating matrix, inherent flexibility, controllable mechanical strength, and excellent biocompatibility. Strong and robust adhesion between hydrogels and substrates is highly desirable for their integration into and subsequent performance in biomedical devices and systems. However, the adhesive behavior of hydrogels is severely weakened by the large amount of water that interacts with the adhesive groups reducing the interfacial interactions. The challenges of developing tough hydrogel-solid interfaces and robust bonding in wet conditions are analogous to the adhesion problems solved by marine organisms. Inspired by mussel adhesion, a variety of catechol-functionalized adhesive hydrogels have been developed, opening a door for the design of multi-functional platforms. This review is structured to give a comprehensive overview of adhesive hydrogels starting with the fundamental challenges of underwater adhesion, followed by synthetic approaches and fabrication techniques, as well as characterization methods, and finally their practical applications in tissue repair and regeneration, antifouling and antimicrobial applications, drug delivery, and cell encapsulation and delivery. Insights on these topics will provide rational guidelines for using nature's blueprints to develop hydrogel materials with advanced functionalities and uncompromised adhesive properties.

R5 HIV-1 gp120 Activates p38 MAPK to Induce Rat Cardiomyocyte Injury by the CCR5 Coreceptor.

BACKGROUND: Effective antiretroviral therapy extends the survival of patients with human immunodeficiency virus (HIV)/acquired immune deficiency syndrome, but these patients remain at higher risk for heart diseases compared with the general population. Previous studies have suggested that HIV-1 glycoprotein 120 (gp120) may be associated with heart disease. However, the underlying mechanisms by which HIV-1 gp120-mediated myocardial injury occurs remain unknown. OBJECTIVE: The current study aimed to uncover the mechanism of C-C chemokine receptor 5 (CCR5) coreceptor (R5) HIV-1 gp120-induced myocardial injury. METHODS: Morphology analysis, determination of the percentage of cell apoptosis, as well as lactate dehydrogenase (LDH) and creatine kinase (CK) assays were used to analyze whether R5 HIV-1 gp120 induced myocardial cell injury. We analyzed the phosphorylation of p38 mitogen-activated protein kinase (MAPK) with the CCR5 antagonist D-Ala-peptide T-amide (DAPTA) and NMDA receptor antagonist MK801, detected LDH and CK assays with p38 MAPK antagonist SB203580 (SB), and detected the percentage of cell apoptosis and death with DAPTA to investigate the mechanism of R5 HIV-1 gp120-induced myocardial cell injury. RESULTS: R5 HIV-1 gp120 damaged myocardial cells and induced p38 MAPK phosphorylation. SB blocked R5 HIV-1 gp120-induced myocardial cell injury. DAPTA blocked R5 HIV-1 gp120-mediated p38 MAPK phosphorylation, while MK801 did not. DAPTA inhibited R5 HIV-1 gp120-induced myocardial cell injury. CONCLUSION: Our data indicate that R5 HIV-1 gp120 activated p38 MAPK to trigger myocardial cell injury by the CCR5 coreceptor.

Calcineurin/NFAT Signaling Modulates Pulmonary Artery Smooth Muscle Cell Proliferation, Migration and Apoptosis in Monocrotaline-Induced Pulmonary Arterial Hypertension Rats.

BACKGROUND/AIMS: Pulmonary arterial hypertension (PAH) is a severe and debilitating disease characterized by remodeling of the pulmonary vessels, which is driven by excessive proliferation and migration and apoptosis resistance in pulmonary artery smooth muscle cells (PASMCs). The calcineurin (CaN)/nuclear factor of activated T-cells (NFAT) signaling pathway is the most important downstream signaling pathway of store-operated Ca2+ entry (SOCE), which is increased in PAH. CaN/NFAT has been reported to contribute to abnormal proliferation in chronic hypoxia (CH)-induced PAH. However, the effect of CaN/NFAT signaling on PASMC proliferation, migration and apoptosis in monocrotaline (MCT)-induced PAH remains unclear. METHODS: PAH rats were established by a single intraperitoneal injection of MCT for 21 days. PASMCs were isolated and cultured in normal and MCT-induced PAH Sprague-Dawley rat. PASMCs were treated with CsA targeting CaN and siRNA targeting NFATc2-4 gene respectively by liposome. We investigated the expression of calcineurin/NFAT signaling by immunofluorescence, qRT-PCR and Western blotting methods. Cell proliferation was monitored using MTS reagent or by assessing proliferating cell nuclear antigen (PCNA) expression. Cell apoptosis was evaluated with an Annexin V - FITC/propidium iodide (PI) apoptosis kit by flow cytometry. PASMC migration was assessed with a Transwell chamber. RESULTS: MCT successfully induced PAH and pulmonary vascular remodeling in rats. CaN phosphatase activity and nuclear translocation of NFATc2-4 were increased in PASMCs derived from MCT-treated rats. In addition, CaNBß/NFATc2-4 expression was amplified at the mRNA and protein levels. PASMC proliferation and migration were markedly inhibited in a dosedependent manner by cyclosporin A (CsA). Furthermore, siRNA targeting NFATc2 and NFATc4 attenuated the excessive proliferation and migration and apoptosis resistance in PASMCs derived from both CON and MCT-treated rats, while NFATc3 knockdown specifically affected MCT-PASMCs. CONCLUSION: Our results demonstrate that CaN/NFAT signaling is activated and involved in the modulation of PASMC proliferation, migration and apoptosis in MCT-induced PAH.

A Universal Organic Cathode for Ultrafast Lithium and Multivalent Metal Batteries.

Low-cost multivalent battery chemistries (Mg2+ , Al3+ ) have been extensively investigated for large-scale energy storage applications. However, their commercialization is plagued by the poor power density and cycle life of cathodes. A universal polyimides@CNT (PI@CNT) cathode is now presented that can reversibly store various cations with different valences (Li+ , Mg2+ , Al3+ ) at an extremely fast rate. The ion-coordination charge storage mechanism of PI@CNT is systemically investigated. Full cells using PI@CNT cathodes and corresponding metal anodes exhibit long cycle life (>10000 cycles), fast kinetics (>20 C), and wide operating temperature range (-40 to 50 °C), making the low-cost industrial polyimides universal cathodes for different multivalent metal batteries. The stable ion-coordinated mechanism opens a new foundation for the development of high-energy and high-power multivalent batteries.

Azo compounds as a family of organic electrode materials for alkali-ion batteries.

Organic compounds are desirable for sustainable Li-ion batteries (LIBs), but the poor cycle stability and low power density limit their large-scale application. Here we report a family of organic compounds containing azo group (N=N) for reversible lithiation/delithiation. Azobenzene-4,4'-dicarboxylic acid lithium salt (ADALS) with an azo group in the center of the conjugated structure is used as a model azo compound to investigate the electrochemical behaviors and reaction mechanism of azo compounds. In LIBs, ADALS can provide a capacity of 190 mAh g-1 at 0.5 C (corresponding to current density of 95 mA g-1) and still retain 90%, 71%, and 56% of the capacity when the current density is increased to 2 C, 10 C, and 20 C, respectively. Moreover, ADALS retains 89% of initial capacity after 5,000 cycles at 20 C with a slow capacity decay rate of 0.0023% per cycle, representing one of the best performances in all organic compounds. Superior electrochemical behavior of ADALS is also observed in Na-ion batteries, demonstrating that azo compounds are universal electrode materials for alkali-ion batteries. The highly reversible redox chemistry of azo compounds to alkali ions was confirmed by density-functional theory (DFT) calculations. It provides opportunities for developing sustainable batteries.

A straightforward STED-background corrected fitting model for unbiased STED-FCS analyses.

Combining stimulated emission depletion and fluorescence correlation spectroscopy (STED-FCS) provides a powerful and sensitive tool for studying the molecular dynamics in live cells with high spatio-temporal resolution. STED-FCS gives access to molecular diffusion characteristic at the nanoscale occurring within short period of times. However due to the incomplete suppression of fluorescence in the STED process, the STED-FCS point spread function (PSF) deviates from a Gaussian shape and challenges the analysis of the auto-correlation curves obtained by FCS. Here, we model the effect of the incomplete fluorescence suppression in STED-FCS experiments and propose a new fitting model improving the accuracy of the diffusion times and average molecule numbers measurements. The implementation of a STED module with pulsed laser source on a commercial confocal/FCS microscope allowed us to apply the STED-background corrected model to fit the STED-FCS measurements. The experimental results are in good accordance with the theoretical analysis both for the number of molecules and the diffusion time which decrease accordingly with the STED power.

Analytical hessian fitting schemes for efficient determination of force-constant parameters in molecular mechanics.

Building upon our recently developed partial Hessian fitting (PHF) method (Wang et al., J. Comput. Chem. 2016, 37, 2349), we formulated and implemented two other rapid force-field parameterization schemes called full Hessian fitting (FHF) and internal Hessian fitting (IHF), and comparisons were made among these three parameterization schemes to assess their performance. FHF minimizes deviation between the Hessian matrices in Cartesian coordinates computed by quantum mechanics (QM) and molecular mechanics (MM), to determine the best possible MM force-constant parameters. While PHF requires step-by-step fittings of 3 × 3 partial Hessian matrices, FHF compares the lower triangular part of the QM and MM Hessian matrices, which allows simultaneous determination of all force-constant parameters. In addition to this simple FHF scheme, IHF was developed such that it considers the Hessian matrices in redundant internal coordinates, where all possible internal coordinates that arise from the user-defined interatomic connectivity are utilized. The results show that IHF performs best overall, followed by PHF and then FHF. Python-based programing codes were developed to automate various tedious steps involved in the parameterization processes. © 2017 Wiley Periodicals, Inc.