Monophenylboryl aza-BODIPY with free rotation of the B-phenyl group for enhanced photothermal conversion.

Owing to the efficient non-radiative relaxation by the free rotation of the B-phenyl moiety, monophenyl substituted aza-BODIPY on the boron centre with near-infrared absorption has high photothermal conversion efficiency, which is highly desirable for a photothermal therapy agent.

Aza-BODIPY with two efficacious fragments for NIR light-driven photothermal therapy by triggering cancer cell apoptosis.

The reasonable structure of aza-BODIPY renders it as an efficient photothermal reagent for photothermal therapy. Herein, we describe the design and synthesis of aza-BODIPY NMeBu with the free rotating tert-butyl group and the dimethylamino-substituted segment to promote the photothermal conversion via the excited state non-radiative transition. NMeBu was found to be the π-π stacking form in the unit cell based on X-ray analysis. NMeBu-NPs by self-assembly possessed a near-infrared absorption (λabs = 772 nm), and once activated by near-infrared light, the photothermal efficiency in aqueous solution can reach 49.3%. NMeBu-NPs can penetrate the cell and trigger cell death via the apoptosis pathway under low concentration and low light power irradiation, thereby avoiding dark toxicity. Aza-BODIPY created using this procedure has excellent photothermal efficiency and could serve as a potential candidate for the treatment of cancer cells and tumors.

Photoinduced Phase Transition in Infinite-Layer Nickelates.

The quantum phase transition caused by regulating the electronic correlation in strongly correlated quantum materials has been a research hotspot in condensed matter science. Herein, a photon-induced quantum phase transition from the Kondo-Mott insulating state to the low temperature metallic one accompanying with the magnetoresistance changing from negative to positive in the infinite-layer NdNiO2 films is reported, where the antiferromagnetic coupling among the Ni1+ localized spins and the Kondo effect are effectively suppressed by manipulating the correlation of Ni-3d and Nd-5d electrons under the photoirradiation. Moreover, the critical temperature Tc of the superconducting-like transition exhibits a dome-shaped evolution with the maximum up to ≈42 K, and the electrons dominate the transport process proved by the Hall effect measurements. These findings not only make the photoinduction a promising way to control the quantum phase transition by manipulating the electronic correlation in Mott-like insulators, but also shed some light on the possibility of the superconducting in electron-doped nickelates.

Preparation of ß-cyclodextrin covalent organic framework-immobilized poly(glycidyl methacrylate) nanoparticle-coated open tubular capillary electrochromatography column for chiral separation.

A new enantioselective open-tubular capillary electrochromatography was developed employing poly(glycidyl methacrylate) nanoparticles/ß-cyclodextrin covalent organic frameworks chemically immobilized on the inner wall of the capillary as a stationary phase. A pretreated silica-fused capillary reacted with 3-aminopropyl-trimethoxysilane followed by poly(glycidyl methacrylate) nanoparticles and ß-cyclodextrin covalent organic frameworks through a ring-opening reaction. The resulting coating layer on the capillary was characterized by scanning electron microscopy and Fourier transform infrared spectroscopy. The electroosmotic flow was studied to evaluate the variation of the immobilized columns. The chiral separation performance of the fabricated capillary columns was validated by the analysis of the four racemic proton pump inhibitors including lansoprazole, pantoprazole, tenatoprazole, and omeprazole. The influences of bonding concentration, bonding time, bonding temperature, buffer type and concentration, buffer pH, and applied voltage on the enantioseparation of four proton pump inhibitors were investigated. Good enantioseparation efficiencies were achieved for all enantiomers. In the optimum conditions, the enantiomers of four proton pump inhibitors were fully resolved within 10 min with high resolutions of 9.5-13.9. The column-to-column and inter- to intra-day repeatability of the fabricated capillary columns through relative standard deviation were found better than 9.54%, exhibiting satisfactory stability and repeatability of the fabricated capillary columns.

Biomechanical Evaluation of Rigid Interspinous Process Fixation Combined With Lumbar Interbody Fusion Using Hybrid Testing Protocol.

Rigid interspinous process fixation (RIPF) has been recently discussed as an alternative to pedicle screw fixation (PSF) for reducing trauma in lumbar interbody fusion (LIF) surgery. This study aimed to investigate biomechanics of the lumbar spine with RIPF, and also to compare biomechanical differences between two postoperative stages (before and after bony fusion). Based on an intact finite-element model of lumbosacral spine, the models of single-level LIF with RIPF or conventional PSF were developed and were computed for biomechanical responses to the moments of four physiological motions using hybrid testing protocol. It was found that compared with PSF, range of motion (ROM), intradiscal pressure (IDP), and facet joint forces (FJF) at adjacent segments of the surgical level for RIPF were decreased by up to 8.4%, 2.3%, and 16.8%, respectively, but ROM and endplate stress at the surgical segment were increased by up to 285.3% and 174.3%, respectively. The results of comparison between lumbar spine with RIPF before and after bony fusion showed that ROM and endplate stress at the surgical segment were decreased by up to 62.6% and 40.4%, respectively, when achieved to bony fusion. These findings suggest that lumbar spine with RIPF as compared to PSF has potential to decrease the risk of adjacent segment degeneration but might have lower stability of surgical segment and an increased risk of cage subsidence; When achieved bony fusion, it might be helpful for the lumbar spine with RIPF in increasing stability of surgical segment and reducing failure of bone contact with cage.

Biomechanical responses of the human lumbar spine to vertical whole-body vibration in normal and osteoporotic conditions.

BACKGROUND: The prevalence of osteoporosis is continuing to escalate with an aging population. However, it remains unclear how biomechanical behavior of the lumbar spine is affected by osteoporosis under whole-body vibration, which is considered a significant risk factor for degenerative spinal disease and is typically present when driving a car. Accordingly, the objective of this study was to compare the spine biomechanical responses to vertical whole-body vibration between normal and osteoporotic conditions. METHODS: A three-dimensional finite-element model of the normal human lumbar spine-pelvis segment was developed using computed tomographic scans and was validated against experimental data. Osteoporotic condition was simulated by modifying material properties of bone tissues in the normal model. Transient dynamic analyses were conducted on the normal and osteoporotic models to compute deformation and stress in all lumbar motion segments. FINDINGS: When osteoporosis occurred, vibration amplitudes of the vertebral axial displacement, disc bulge, and disc stress were increased by 32.1-45.4%, 25.7-47.1% and 23.0-42.7%, respectively. In addition, it was found that for both the normal and osteoporotic models, the response values (disc bugle and disc stress) were higher in L4-L5 and L5-S1 intervertebral discs than in other discs. INTERPRETATION: Osteoporosis deteriorates the effect of whole-body vibration on lumbar spine, and the lower lumbar segments might have a higher likelihood of disc degeneration under whole-body vibration.

Identification of potent antimicrobial peptides via a machine-learning pipeline that mines the entire space of peptide sequences.

Systematically identifying functional peptides is difficult owing to the vast combinatorial space of peptide sequences. Here we report a machine-learning pipeline that mines the hundreds of billions of sequences in the entire virtual library of peptides made of 6-9 amino acids to identify potent antimicrobial peptides. The pipeline consists of trainable machine-learning modules (for performing empirical selection, classification, ranking and regression tasks) assembled sequentially following a coarse-to-fine design principle to gradually narrow down the search space. The leading three antimicrobial hexapeptides identified by the pipeline showed strong activities against a wide range of clinical isolates of multidrug-resistant pathogens. In mice with bacterial pneumonia, aerosolized formulations of the identified peptides showed therapeutic efficacy comparable to penicillin, negligible toxicity and a low propensity to induce drug resistance. The machine-learning pipeline may accelerate the discovery of new functional peptides.

Effect of different fixation methods on biomechanical property of cervical vertebral body replacement and fusion.

BACKGROUND: The main purpose of this study was to examine the effect of different fixation methods (anterior fixation, self-stabilizing fixation and anterior-posterior fixation) on biomechanical property of vertebral body replacement and fusion. METHODS: Three finite element models of cervical vertebral body replacement and fusion were established. The implanted models included artificial vertebral body and fixation system, and the loads imposed on the models included 75 N compression load and 1 Nm moment load. FINDINGS: For anterior-posterior fixation, the cervical load was mainly transmitted by the posterior pedicle screw and rod (more than 50%), and the stress shielding problem was the most significant than the self-stabilizing and anterior fixation. Self-stabilizing fixation was more helpful to the fusion of implant and vertebrae, but the higher risk of vertebral body collapse was worthy of attention if the cervical spine with osteoporosis. The stress of bone was mainly concentrated around the screw hole. The maximum stress (20.03 MPa) was lower than the yield stress of cortical bone and the possibility of fracture around the fixation device of cervical spine was low. The anterior fixation could meet the requirement of vertebral body replacement and fusion, and the addition of posterior pedicle screws and rods might obtain better treatment in cases of severe spine injury or osteoporosis. INTERPRETATION: The findings of this study may provide guidance on clinical treatments for choosing more appropriate fixation methods for different patients.

Attachment of -tBu groups to aza-BODIPY core at 3,5-sites with ultra-large Stokes shift to enhance photothermal therapy through apoptosis mechanism.

By the introduction of the -tBu groups into aza-BODIPY core, di-tert-butyl-substituted aza-BODIPYs at 3,5-sites (tBuazaBDPs) were prepared for the first time. Based on the X-ray analysis of CN-tBuazaBDP, this molecular structure is twisted. Near-infrared dye SMe-tBuazaBDP has the ultra-large Stokes shift (152 â€‹nm) in aza-BODIPY system, combining with the twisted intramolecular charge transfer and the free rotation of the -tBu groups at 3,5-sites. Although the barrier-free rotors of the distal -tBu groups in SMe-tBuazaBDP result in low fluorescence quantum yield, the photothermal conversion efficiency is markedly enhanced. SMe-tBuazaBDP nanoparticles with low power laser irradiation were proven to block cancer cell cycle, inhibit cancer cell proliferation, and induce cancer cell apoptosis in photothermal therapy (PTT). The strategy of "direct attachment of -tBu groups to aza-BODIPY core" gives a new design platform for a photothermal therapy agent.

Synthesis of aza-BODIPYs with barrier-free rotation of the -tBu group at 3-site and enhancement of photothermal therapy by triggering cancer cell apoptosis.

Breaking through the traditional 1,7,3,5-aryl substituted aza-BODIPY structure, asymmetric aza-BODIPYs, tBu-azaBDPs, containing non-aryl group at 3-site were prepared for the first time. tBu-azaBDP exhibited a severely twisted configuration. tBu-azaBDPs had a near-infrared fluorescence emission and high molar extinction coefficients. Although the barrier-free rotation of the distal -tBu group in tBu-azaBDP resulted in low fluorescence quantum yield, the photothermal conversion efficiency was markedly enhanced. tBu-azaBDP nanoparticles with laser irradiation were revealed to induce cell apoptosis in photothermal therapy. We consider that development of aza-BODIPYs with the barrier-free rotation of the -tBu group at 3-site provides a strong platform for design of phototherapy agents for cancer treatment in photothermal therapy by apoptosis.

Molecular reaction and dynamic mechanism of iodate reduction to molecular iodine by nitrogen(III) in aqueous solution.

This work studies the molecular reaction and dynamic mechanism of iodate reduction by nitrogen(III) in aqueous solution using the ab initio molecular dynamics (AIMD) method based on density functional theory (DFT). Two possible reaction pathways (without and with H+) are proposed. The thermodynamic parameters of the proposed reaction pathways are calculated. The theoretical calculation aspects of iodate reduction, including the atomic dipole moment corrected Hirshfeld population (ADCH) atomic charge values, the intrinsic reaction coordinate (IRC) curves, the calculated interaction regional indicator (IRI) isosurfaces with the corresponding sign(λ2)ρ scatter plots, electrostatic potential (ESP) analysis and molecular reaction dynamics are discussed in-depth. The results show that the reaction pathway with H+ is confirmed based on the Gibbs free energy analysis. The transition state proved that the iodate reduction with nitrous acid undergoes four steps according to oxygen-atom deprivation. The IRC curves describe the energy change of the chemical bonds of the reactant conformations in the four steps, with an energy reduction of 71.95, 69.35, 130.15, and 125.87 kJ mol-1, respectively. The ESP interpenetration diagram and IRI isosurfaces provide detailed information on the nucleophilicity and electrophilicity of the reactant conformations. By decreasing the O atom number in HIOx (x = 1, 2, 3), the maximum positive charge decreases, and the positive charge coverage area increases, thus resulting in energy reduction and consequently a more stable conformation. Molecular reaction dynamics analytical results indicated that a relatively stable status of the reactants of the four steps was achieved after around 200 fs, and that the HIO3-HNO2 reaction released the highest energy.

Biomechanical analysis of lumbar nonfusion dynamic stabilization using a pedicle screw-based dynamic stabilizer or an interspinous process spacer.

This study aimed to investigate and compare the effects of two widely used nonfusion posterior dynamic stabilization (NPDS) devices, pedicle screw-based dynamic stabilizer (PSDS) and interspinous process spacer (IPS), on biomechanics of the implanted lumbar spine under static and vibration loadings. The finite element model of healthy human lumbosacral segment was modified to incorporate NPDS device insertion at L4-L5 segment. Bioflex and DIAM were used as PSDS-based and IPS-based NPDS devices, respectively. As a comparison, lumbar interbody fusion with rigid stabilization was also simulated at L4-L5. For static loading, segmental range of motion (ROM) of the models under moments of four physiological motions was computed using hybrid testing protocol. For vibration loading, resonant modes and dynamic stress of the models under vertical excitation were extracted through random response analysis. The results showed that compared with the rigid fusion model, ROM of the nonfusion models was higher at L4-L5 level but lower at adjacent levels (L1- L2, L2-L3, L3-L4, L5-S1). Compared with the Bioflex model, the DIAM model produced higher ROM at L4-L5 level but lower ROM at adjacent levels, especially under lateral bending and axial rotation; resonant frequency of the DIAM model was slightly lower; dynamic response of nucleus stress at L4-L5 level was slightly higher for the DIAM model, and the dynamic stress at adjacent levels was no obvious difference between the nonfusion models. This study reveals biomechanical differences between the Bioflex and DIAM systems, which may provide references for selecting surgical approaches in clinical practice.

Near-infrared upper phenyl-fused BODIPY as a photosensitizer for photothermal-photodynamic therapy.

The introduction of a ring-fused segment into a BODIPY scaffold promoted a spectral bathochromic-shift and enhanced the intersystem crossing capability by a twisted structure. In this work, we designed and synthesized an upper ring-fused BODIPY with 4-dimethylaminostyryl groups (BBDP), which had excellent optical performance for photothermal-photodynamic therapy.

ß-Cyclodextrin covalent organic framework supported by polydopamine as stationary phases for electrochromatographic enantioseparation.

In this work, a new open-tubular capillary electrochromatography (OT-CEC) column was prepared using ß-cyclodextrin covalent organic framework (ß-CD COF) as a stationary phase. Polydopamine was used to assist fabrication of ß-CD COF on an inner wall of a fused-silica capillary. The coating layer on the capillary was characterized by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). Electroosmotic flow (EOF) was also studied to evaluate the variation of the inner wall of immobilized columns. Furthermore, the chiral separation effectiveness of the fabricated capillary column was evaluated by CEC using enantiomers of several related proton pump inhibitors as model analytes, including omeprazole, lansoprazole, pantoprazole and tenatoprazole. The effects of bonding time and concentration of ß-CD COF, the type, concentration and pH of buffer, applied voltage were investigated to obtain satisfactory enantioselectivity. In the optimum conditions, the enantiomers of four analytes were resolved within 15 min with resolutions of 1.63-2.62. The relative standard deviation values for migration times and resolutions of the analytes representing intraday and interday were less than 6.75% and 4.24%, respectively. The results reveal that ß-CD COF has great potential as chiral-stationary phases for enantioseparation in CEC.

Authentic Intelligent Machine for Scaling Driven Discovery: A Case for Chiral Quantum Dots.

The scaling laws have long been used as evidence of science where many fundamental physics laws emerge. As emerging nanomaterials, quantum dots are also sensitive to scaling because of their strong size effect. In this work, we developed the chiral dielectric theory based on the exciton absorption mechanism to explain the increment of the dielectric constant from chirality via its dimensionality. To help researchers discover and develop scaling relevant theories, the Authentic Intelligent Machine (AIM) protocol was developed to generate and interpret experimental data in an analytical and scaling-oriented manner. We show how the AIM protocol interprets spectra such as transient absorption data of chiral quantum dots with theories, where discrepancies concerning the dielectric constant were discovered. Examples for applying the AIM protocol on other spectra, such as absorption spectra and photoluminescence spectra, are also given.

1,7-Di-tert-butyl-Substituted aza-BODIPYs by Low-Barrier Rotation to Enhance a Photothermal-Photodynamic Effect.

1,7-Di-tert-butyl-substituted aza-BODIPYs (tBu-azaBDP) were successfully obtained for the first time. The structures of tBu-azaBDP and Ph-azaBDP were confirmed by X-ray crystal analysis, and tBu-azaBDP 2 is more twisted than Ph-azaBDP 5. tBu-azaBDPs have significant photo-stability and enhanced water solubility. tBu-azaBDPs possess excellent optical properties, such as high molar extinction coefficients, broad full width half maxima, and large Stokes shifts, which is comparable to those of the parent dye Ph-azaBDP. Although the low-barrier rotation of the distal -tBu groups in tBu-azaBDPs results in low quantum yield, photothermal conversion efficiency and singlet oxygen generation ability of tBu-azaBDPs are more effective than those of Ph-azaBDP, which is highly desirable for a photothermal-photodynamic therapy agent.

[Biomechanical study of different approach for lumbar interbody fusion surgeries under vibration load].

The human spine injury and various lumbar spine diseases caused by vibration have attracted extensive attention at home and abroad. To explore the biomechanical characteristics of different approaches for lumbar interbody fusion surgery combined with an interspinous internal fixator, device for intervertebral assisted motion (DIAM), finite element models of anterior lumbar interbody fusion (ALIF), transforaminal lumbar interbody fusion (TLIF) and lateral lumbar interbody fusion (LLIF) are created by simulating clinical operation based on a three-dimensional finite element model of normal human whole lumbar spine. The fusion level is at L4-L5, and the DIAM is implanted between spinous process of L4 and L5. Transient dynamic analysis is conducted on the ALIF, TLIF and LLIF models, respectively, to compute and compare their stress responses to an axial cyclic load. The results show that compared with those in ALIF and TILF models, contact forces between endplate and cage are higher in LLIF model, where the von-Mises stress in endplate and DIAM is lower. This implies that the LLIF have a better biomechanical performance under vibration. After bony fusion between vertebrae, the endplate and DIAM stresses for all the three surgical models are decreased. It is expected that this study can provide references for selection of surgical approaches in the fusion surgery and vibration protection for the postsurgical lumbar spine.

Barbituric and thiobarbituric acid-based UiO-66-NH2 adsorbents for iodine gas capture: Characterization, efficiency and mechanisms.

Efficient iodine gas capture is necessitated in many industries like spent nuclear fuel off-gas treatment in view of environmental protection and resource recycling. However, the adsorption efficiency and stability of the current adsorbents are limited. In the present work, efficient and stable barbituric and thiobarbituric acid-based UiO-66-NH2 adsorbents (i.e., UiO-66-NH-B.D and UiO-66-NH-T.D, respectively) have been synthesized by post-synthetic covalent modification. Characterization approaches, including SEM-EDS, TEM, XRD, FTIR, XPS, 1H NMR, TGA and BET, are used to obtain information on the properties and adsorption mechanisms of these metal-organic framework (MOF) adsorbents. The kinetics and mechanisms involved are studied in detail. The treatment efficiency and recyclability of the adsorbents are checked and compared with the adsorbents reported in previous works. The results show that the current adsorbents are potentially suitable for efficient iodine gas capture. High maximum iodine adsorption amount by UiO-66-NH-B.D and UiO-66-NH-T.D (1.17 and 1.33 g/g) was achieved under 75 °C. These new adsorbents are thermally stable for iodine adsorption and regenerated and reused with good performance. The adsorption mechanisms were revealed based on experimental results, indicating that iodine is adsorbed by both physisorption and chemisorption.

Numerical Simulation of Continuous Extraction of Li+ from High Mg2+/Li+ Ratio Brines Based on Free Flow Ion Concentration Polarization Microfluidic System.

Ion concentration polarization (ICP) is a promising mechanism for concentrating and/or separating charged molecules. This work simulates the extraction of Li+ ions in a diluted high Mg2+/Li+ ratio salt lake brines based on free flow ICP focusing (FF-ICPF). The model solution of diluted brine continuously flows through the system with Li+ slightly concentrated and Mg2+ significantly removed by ICP driven by external pressure and perpendicular electric field. In a typical case, our results showed that this system could focus Li+ concentration by ~1.28 times while decreasing the Mg2+/Li+ ratio by about 85% (from 40 to 5.85). Although Li+ and Mg2+ ions are not separated as an end product, which is preferably required by the lithium industry, this method is capable of decreasing the Mg2+/Li+ ratio significantly and has great potential as a preprocessing technology for lithium extraction from salt lake brines.

Preparation of a polydopamine/ß-cyclodextrin coated open tubular capillary electrochromatography column and application for enantioseparation of five proton pump inhibitors.

An open tubular capillary electrochromatography column was prepared by immobilizing ß-cyclodextrin on the inner wall of pretreated capillary via noncovalent adsorption of polydopamine. The resulting coating layer on the capillary was characterized by scanning electron microscopy and Fourier transform infrared spectroscopy. Electroosmotic flow was studied to evaluate the variation of the immobilized columns. The prepared columns showed good chiral separation performance toward five proton pump inhibitors including lansoprazole, pantoprazole, tenatoprazole, rabeprazole, and omeprazole. The influences of ß-cyclodextrin concentration, coating time, buffer pH, buffer concentration, and applied voltage on separation were investigated. In the optimum conditions, the enantiomers of five analytes were fully resolved within 15 min with high resolutions of 4.57 to 8.13. The method was extensively validated in terms of accuracy, precision, and linearity and proved to be robust. The relative standard deviation values for migration times and peak areas of the analytes representing intraday and interday were less than 1.9 and 3.6%, respectively. Further, the polydopamine/ß-cyclodextrin coated capillary column could be successively used over 100 runs without showing significant decrease in the separation efficiency.