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Most 2D nonlinear optical (NLO) materials do not have an ultrawide bandgap, therefore, they are unsuitable for working in the deep-ultraviolet spectral range (< 200 nm). Herein, the theoretical prediction of an excellent monolayer BeP2O4H4 (ML-BPOH) is reported. DFT analyses suggest a low cleavage energy (≈45 meV per atom) from a naturally existed bulk-BPOH material, indicating feasible exfoliation. This novel 2D material exhibits excellent properties including an ultrawide bandgap (Eg) of 7.84 eV, and a strong second-order nonlinear susceptibility ( d b u l k e f f $d_{bulk}^{eff}$ = 0.43 pm V-1), which is comparable to that of benchmark bulk-KBBF crystal (d16 = 0.45 pm V-1). The wide bandgap and large SHG effect of ML-BPOH are mainly derived from the (PO2H2)- tetrahedron. Notably, ML-BPOH exhibits an outstanding 50% variation in dsheet under minor stress stimuli (±3%) due to rotation of structurally rigid (PO2H2)- tetrahedron. This indicates significant potential for application in material deformation monitoring.
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Birefringent crystals are the key components of functional optics, contributing significantly to scientific and technological advancements. To enhance birefringence, the presence of stereochemically active lone pairs offers a unique opportunity. In fact, strengthening the stereochemical activity and aligning uniformly lone pairs face tough challenges. Herein, an anisotropic layered crystal, Sb4O5I2, is discovered to exhibit enhanced birefringence. The influence of crystal symmetry on the birefringence of Sb4O5X2 (X = Cl, Br, or I) is found to be minor. Instead, the asymmetric nature of ABUCBs (i.e., cis-X3[SbO3]6- and cis-X3[SbO4]8-) plays a crucial role in enhancing the optical anisotropy. And the orientation of these ABUCBs is equally important. We demonstrate that by adjusting the Sb/I ratio from 5:1 to 2:1, all of the intralayer Sb atoms in Sb5O7I-P63 are forced onto the surface position. This structural adjustment leads to strengthened ionic bonding interactions, enhanced activity of the lone pairs, and uniform alignments of the ABUCBs in Sb4O5I2. Consequently, this results in a 6-fold increase in birefringence.
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We define the anisotropic structure building unit that encompasses diverse chemical bonds (ABUCB). The ABUCB is highly likely to cause anisotropy in both crystallographic structure and spatial electron distribution, ultimately resulting in enhanced macroscopic optical anisotropy. Accordingly, the (PO3F)2- or (SO3F)- tetrahedron involving the unique P-F or S-F bond serves as such an ABUCB. The distinct chemical bond effectively alters the microscopic nature of the structure building unit, such as polarizability anisotropy, hyperpolarizability, and geometry distortion; this consequently changes the macroscopic second-order nonlinear optical (2nd-NLO) properties of the materials. In this review, we summarize both typical and newly emerged compounds containing ABUCBs. These compounds encompass approximately 90 examples representing six distinct categories, including phosphates, borates, sulfates, silicates, chalcogenides and oxyhalides. Furthermore, we demonstrate that the presence of ABUCBs in DUV/UV NLO compounds contributes to an increase in birefringence and retention of a large band gap, facilitating phase matching in high-energy short-wavelength spectral ranges. On the other hand, the inclusion of ABUCBs in IR NLO compounds offers a feasible method for increasing the band gap and consequently enhancing the larger laser-induced damage threshold. This review consolidates various trial-and-error explorations and presents a novel strategy for designing 2nd-NLO compounds, potentially offering an opportunity for the development of high-performance 2nd-NLO materials.
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Heat-activated second harmonic generation (SHG) switching materials are gaining interest for their ability to switch between SHG on and off states, offering potential in optoelectronic applications. The novel nonlinear optical (NLO) switch, (C5H6NO)+(CH3SO3)- (4-hydroxypyridinium methylsulfonate, 4HPMS), is a near-room-temperature thermal driven material with a strong SHG response (3.3 × KDP), making it one of the most potent heat-stimulated NLO switches. It offers excellent contrast of 13 and a high laser-induced damage threshold (2.5 × KDP), with reversibility > 5â cycles. At 73 °C, 4HPMS transitions from the noncentrosymmetric Pna21 room temperature phase (RTP) to the centrosymmetric P21/c phase, caused by the rotation of the (C5H6NO)+ and (CH3SO3)- due to partially thermal breaking of intermolecular hydrogen bonds. The reverse phase change exhibits a large 50 °C thermal hysteresis. Density functional theory (DFT) calculations show that (C5H6NO)+ primarily dictates both the SHG coefficient (dij) and birefringence (âµn(Zeiss) = 0.216 vs âµn(cal.) = 0.202 at 546â nm; Δn(Immersion) = 0.210 vs âµn(cal.) = 0.198 at 589.3â nm), while the band gap (Eg) is influenced synergistically by (C5H6NO)+ and (CH3SO3)-. Additionally, 4HPMS-RTP also exhibits mechanochromism upon grinding as well as an aggregation-enhanced emission in a mixture of acetone and water.
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Thermoelectric copper selenides are highly attractive owing to not only their constituent nontoxic, abundant elements but also their ultralow liquid-like lattice thermal conductivity (κlat). For the first time, the promising thermoelectric properties of the new KCu5Se3 are reported herein, showing a high power factor (PF = 9.0 µWcm-1 K-2) and an intrinsically ultralow κlat = 0.48 Wm-1 K-1. The doped K1-xBaxCu5Se3 (x = 0.03) realizes a figure-of-merit ZT = 1.3 at 950 K. The crystallographic structure of KCu5Se3 allows complex lattice dynamics that obey a rare dual-phonon transport model well describing a high scattering rate and an extremely short phonon lifetime that are attributed to interband phonon tunneling, confinement of the transverse acoustic branches, and temperature-dependent anharmonic renormalization, all of which generate an unprecedently high contribution of the diffusive phonons (70% at 300 K). The overall weak chemical bonding feature of KCu5Se3 gives K+ cations a quiescence behavior that further blocks the heat flux transfer. In addition, the valence band edge energy dispersion of KCu5Se3 is quasilinear that allows a large Seebeck coefficient even at high hole concentrations. These in-depth understandings of the ultralow lattice thermal conductivity provide new insights into the property-oriented design and synthesis of advanced complex chalcogenide materials.
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AIM: To explore the mechanism of the healing of tendon tissue and anti-adhesion, and to discuss the role of the transforming growth factor-ß3 (TGF-ß3)/cAMP response element binding protein-1 (CREB-1) signaling pathway in the healing process of tendons. METHOD: All mice were divided into four groups of 1, 2, 4, and 8 weeks respectively. Each time group was divided into four treatment groups: the amplification group, the inhibition group, the negative group, and the control group. When the tendon injury model was established, the CREB-1 virus was injected into the tendon injury parts. A series of methods such as gait behaviourism, anatomy, histological examination, immunohistochemical examination and collagen staining were employed to assess the tendon healing and the protein expression of TGF-ß3, CREB-1, Smad3/7 and type I/III collagen (COL-I/III). CREB-1 virus was sent to tendon stem cells to assess the protein expression of TGF-ß1, TGF-ß3, CREB-1, COL-I/III by methods such as immunohistochemistry and Western blot. RESULTS: The amplification group showed better gait behaviourism than the inhibition group in the healing process. The amplification group also had less adhesion than the negative group. Hematoxylin-eosin (HE) staining of tendon tissue sections showed that the number of fibroblasts in the amplification group was less than the inhibition group, and the immunohistochemical results indicated that the expression of TGF-ß3, CREB-1, and Smad7 at each time point was higher than the inhibition group. The expression of COL-I/III and Smad3 in the amplification group was lower than the inhibition group at all time points. The collagen staining indicated that the ratio of type I/III collagen in the amplification group was higher than the negative group at 2,4,8 week. The CREB-1 amplification virus could promote the protein expression of TGF-ß3, CREB-1 and inhibit the protein expression of TGF-ß1 and COL-I/III in the tendon stem cells. CONCLUSION: In the process of tendon injury healing, CREB-1 could promote the secretion of TGF-ß3, so as to promote the tendon healing and have the effect of anti-adhesion in tendons. It might provide new intervention targets for anti-adhesion treatment of tendon injuries.
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Proteína de Ligação ao Elemento de Resposta ao AMP Cíclico , Traumatismos dos Tendões , Fator de Crescimento Transformador beta3 , Cicatrização , Animais , Camundongos , Tendões , Traumatismos dos Tendões/metabolismo , Proteína de Ligação ao Elemento de Resposta ao AMP Cíclico/metabolismo , Transdução de Sinais , Fator de Crescimento Transformador beta3/metabolismo , Camundongos Endogâmicos C57BL , Masculino , Células-Tronco , Análise da Marcha , Aderências Teciduais/prevenção & controleRESUMO
Nonlinear optical (NLO) switch materials that turn on/off second-harmonic generation (SHG) at a phase transition temperature (Tc ) are promising for applications in the fields of photoswitching and optical computing. However, precise control of Tc remains challenging, mainly because a linearly tunable Tc has not been reported to date. Herein, we report a unique selenate, tetragonal P 4 â¾ ${\bar{4}}$ 21 c [Ag(NH3 )2 ]2 SeO4 with a=b=8.5569(2)â Å and c=6.5208(2)â Å that exhibits a strong SHG intensity (1.3×KDP) and a large birefringence (Δnobv. =0.08). This compound forms a series of isostructural solid-solution crystals [Ag(NH3 )2 ]2 Sx Se1-x O4 (x=0-1.00) that exhibit excellent NLO switching performance and an unprecedented linearly tunable T c , x , e x p . = T 0 - k x ${{T}_{\left(c,{\rm \ }x\right),{\rm \ }\left({\rm e}{\rm x}{\rm p}.\right)}{\rm \ }={T}_{0}-kx}$ spanning 430 to 356â K. The breaking of localized hydrogen bonds between SeO4 2- and the cation triggers a phase transition accompanied by hydrogen bond length changes with increasing x and a linear change in the enthalpy Δ H x = Δ U 1 - Δ U 2 x + Δ U 2 ${{{\rm { \Delta{}}}H}_{x}=\left({\rm { \Delta{}}}{U}_{1}-{\rm { \Delta{}}}{U}_{2}\right)x+{\rm { \Delta{}}}{U}_{2}}$ .
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The discovery of compounds with low thermal conductivity and the understanding of their microscopic mechanisms are of great challenges and scientific significance. Herein, we report a unique ternary sulfide compound, Cu3 BiS3 , in which all Cu atoms are coordinated within a two-dimensional [CuS3 ] triangle plane. This local coordination leads to efficient out-of-plane phonon scattering and an ultralow thermal conductivity. Through DFT phonon spectrum calculations and analyses, we reveal that the lowest vibration frequency decreases from 2 THz for high-dimensional [CuS4 ] tetrahedral coordinated Cu atoms in CuBiS2 (CN=4, with an average Cu-S bond length of 2.328â Å) to 1.5 THz for low-dimensional [CuS3 ] triangular coordinated Cu atoms in Cu3 BiS3 (CN=3, with a shorter Cu-S bond length of 2.285â Å). This is due to the out-of-plane thermal vibration of the Cu atoms in the latter. Consequently,Cu3 BiS3 exhibits one of the lowest values of κlat (0.32â W/m K) among its peer, with a 36 % reduction compared to CuBiS2 (0.50â W/m K). This groundbreaking discovery highlights the significant role of 2D local coordination in reducing thermal conductivity through characteristic out-of-plane phonon scattering, while also contributing to a large Grüneisen parameter (2.06) in Cu3 BiS3 .
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The fictive temperature (Tf ) is widely applied to understand the relaxation thermodynamics of a glass; however, its atomic structural origin is still unclear. Here, we report two novel AZnP3 O9 glasses obtained by melting the composition identical single crystals. These glasses exhibit structural inheritance within 5â Å from the single crystal counterparts that is quantified by δ=nglass /ncry (0≤δ≤1, n is the number of pair correlation functions). Among the available glass-formers, glass KZnP3 O9 exhibits the highest structural inheritance (δ=1, nglass =8). More insightfully, a reverse correlation between δ and the relaxation thermodynamic parameters is observed in glass AZnP3 O9 , revealing for the first time the atomic structural origin of fictive temperature.
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Room-temperature thermoelectric materials are the key to miniaturizing refrigeration equipment and have great scientific and social implications, yet their application is hindered by their extreme scarcity. BiTe exhibiting strong spin-orbit coupling peaks ZT at 600â K. Herein, we discover the synergy effect of Sb doping in BiTe that eliminates the detrimental band inversion and leads to an overlap of conduction band (CB) and valence band that significantly increases the S from 33 to 124â µV K-1 . In addition, this effect enhances the µ from 58 to 92â cm2 â V-1 s-1 owing to the sharp increase in the CB slope along the Γ-A in the first Brillouin zone. Furthermore, Sb doping increases the anharmonicity, shortens the phonon lifetime and lowers κlat . Finally, Se/Sb codoping further optimizes the ZT to 0.6 at 300â K, suggesting that Bi0.6 Sb0.4 Te1-y Sey is a potential room-temperature TE material.
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The strong mutual coupling of and even the opposite change in the key parameters, such as the band gap (Eg ) and second-order harmonic generation (SHG), leads to the extreme scarcity in high-performance IR nonlinear optical (NLO) chalcogenides. Herein, we report 8 new sulfides, Na2 Ba[(Agx Na1-x )2 Sn2 S7 ] (1, x=0; 1â series, x=0.1-0.6; Na2 Ba[(Li0.58 Na0.42 )2 Sn2 S7 ], 1-0.6Li); Na2 Sr[Cu2 Sn2 S7 ] (2); and Na2 Ba[Cu2 Sn2 S7 ] (3). We use the structural tolerance factor ( t I e x p ${{t}_{I}^{exp}}$ ) to connect the chemical composition, crystal structure, and NLO properties. Guided by these correlations, a better balance between Eg and SHG is realized in 1, which exhibits a large Eg of 3.42â eV and excellent NLO properties (SHG: 1.5×AGS; laser-induced damage threshold: 12×AGS), representing the best performance among the known Hg- or As-free sulfides to date.
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BACKGROUND: Non-small cell lung carcinoma (NSCLC) is one of the most common human cancers, comprising approximately 80-85% of all lung carcinomas. An estimated incidence of NSCLC is approximately 2 million new cases per year worldwide. RESULTS: In recent decade, the treatment of NSCLC has made breakthrough progress owing to a large number of targeted therapies which were approved for clinical use. Epidemiology, genetic susceptibility, and molecular profiles in patients are likely to play an important factor in response rates and survival benefits to these targeted treatments and thus warrant further investigation on ethnic differences in NSCLC. In this study, a total number of 1500 Chinese patient samples,1000 formalin fixed paraffin-embedded (FFPE) and 500 blood samples, from patients with NSCLC were analyzed by targeted sequencing to explore mutational landscape in ethnic groups associated with China. CONCLUSIONS: Overall, the data presented here provide a comprehensive analysis of NSCLC mutational landscape in Chinese patients and findings are discussed in the context of similar studies on different ethnic groups.
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Carcinoma Pulmonar de Células não Pequenas/genética , Sequenciamento do Exoma , Exoma/genética , Idoso , Carcinoma Pulmonar de Células não Pequenas/epidemiologia , Carcinoma Pulmonar de Células não Pequenas/patologia , China/epidemiologia , Estudos de Coortes , Feminino , Sequenciamento de Nucleotídeos em Larga Escala , Humanos , Masculino , Pessoa de Meia-Idade , Mutação/genéticaRESUMO
OBJECTIVES: To investigate the genetic polymorphism of InDel loci in SifalnDel 45plex system in the Han population in Jiangsu Province and the Mongolian population in Inner Mongolia, and to evaluate the effectiveness of the system in forensic medicine. METHODS: SifaInDel 45plex system was used for genotyping in blood samples of 398 unrelated individuals from the above two populations, and allele frequencies and population genetic parameters of the two populations were calculated respectively. Eight intercontinental populations in the gnomAD database were used as reference populations. The genetic distances between the two studied populations and eight reference populations were calculated based on the allele frequencies of 27 autosomal-InDels (A-InDels). The phylogenetic trees and multidimensional scaling (MDS) analysis diagrams were constructed accordingly. RESULTS: Among two studied populations, the 27 A-InDels and 16 X-InDels showed no linkage disequilibrium between each other and the allele frequency distributions were in Hardy-Weinberg equilibrium. The CDP of the 27 A-InDels in two studied populations were all higher than 0.999 999 999 9, and the CPEtrio were all less than 0.999 9. The CDP of the 16 X-InDels in Han in Jiangsu and Mongolian in Inner Mongolia female and male samples were 0.999 997 962, 0.999 998 389, and 0.999 818 940, 0.999 856 063, respectively. The CMECtrio were all less than 0.999 9. The results of population genetics showed that the Jiangsu Han nationality, Inner Mongolia Mongolian nationality and East Asian population clustered into one branch, showing closer genetic relationship. The other 7 intercontinental populations clustered into another group. And the above 3 populations displayed distant genetic relationships with the other 7 intercontinental populations. CONCLUSIONS: The InDels in the SifaInDel 45plex system have good genetic polymorphism in the two studied populations, which can be used for forensic individual identification or as an effective complement for paternity identification, and to distinguish different intercontinental populations.
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Genética Populacional , Polimorfismo Genético , Humanos , Filogenia , Frequência do Gene , Povo Asiático/genética , China , Mutação INDELRESUMO
We report a Zintl phase thermoelectric material, coarse grain-In0.99 Ga0.01 Te, achieving a ZT peak of 1.2 at 648â K and an average ZT=0.8 in 300-650â K, which outperforms all the known InTe-based materials to date. The synergistic optimization of electronic property and phonon transport are achieved by the purification of grain boundary scattering, together with the Ga-doping-induced weak phonon-electron coupling, which enhances the carrier mobility and carrier concentration simultaneously and consequently gives a remarkably increased power factor of 8.9â µW cm-1 K-2 . The DFT phonon calculations indicate the dopant reduces the deformation potential coefficient and induces the lattice shrink, which reduces significantly the acoustic cutoff frequency, and enhances the scattering phase space. Moreover, the bonding hierarchy leads to the dense intragranular dislocation arrays, which suppresses the lattice thermal conductivity further and induces an ultralow lattice thermal conductivity (0.21â Wm-1 K-1 ).
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Non-linear optical chalcogenides with a wide band gap (Eg ) and excellent NLO properties are key materials for highly desirable multiwaveband tunable optical parametric oscillators (OPOs). We exploit the "electronic structure engineer bucket effect" to develop a novel dual-waveband SrZnGeS4 with an ultrawide transparency window. It exhibits an asymmetric Fdd2 structure that consists of layers formed by corner-sharing [ZnGeS6 ] dimers. SrZnGeS4 is transparent from 0.30 to 23.6â µm, spanning the UV-, vis-, mid- and far-IR spectral regions and has the widest Eg (3.63â eV) in the AeMII MIV Q4 family to date. It exhibits phase matching, high SHG intensities (e.g., 11.0×KDP and 17.5×AGS under λinc =1450 and 950â nm, respectively), and a very high laser-induced damage threshold (35×AGS). These results not only suggest bright prospects for high-power laser applications but may also enable applications of the multiwaveband OPO system from the UV-visible to far-IR regions.
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Crystalline solids that exhibit inherently low lattice thermal conductivity (κlat) have attracted a great deal of attention because they offer the only independent control for pursuing a high thermoelectric figure of merit (ZT). Herein, we report the successful preparation of CsCu4Q3 (Q = S (compound 1), Se (compound 2)) with the aid of a safe and facile boron-chalcogen method. The single-crystal diffraction data confirm the P4/mmm hierarchical structures built up by the mixed-valence [(Cu+)4(Q2-)2](Q-) double anti-CaF2 layer and the NaCl-type Cs+ sublattice involving multiple bonding interactions. The electron-poor compound CsCu4Q3 features Cu-Q antibonding states around EF that facilitates a high σ value of 3100 S/cm in 2 at 323 K. Significantly, the ultralow κlat value of 2, 0.20 W/m/K at 650 K (70% lower than that of Cu2Se), is mainly driven by the vibrational coupling of the rigid double anti-CaF2 layer and the soft NaCl-type sublattice. The hierarchical structure increases the bond multiplicity, which eventually leads to a large phonon anharmonicity, as evidenced by the effective scattering of the low-lying optical phonons to the heat-carrying acoustic phonons. Consequently, the acoustic phonon frequency in 2 drops sharply from 118 cm-1 (of Cu2Se) to 48 cm-1. In addition, the elastic properties indicate that the hierarchical structure largely inhibits the transverse phonon modes, leading to a sound velocity (1571 m/s) and a Debye temperature (189 K) lower than those of Cu2Se (2320 m/s; 292 K).
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We herein report a novel semiorganic NLO material, (C5H6ON)+(H2PO4)-, 4HPP, showing promising excellent properties in the important solar-blind UV region where LAP and its deuterated form DLAP are the only commercialized semiorganic materials. For the first time, the 4-hydroxypyridine (4HP+, (C5H6ON)+) cation is identified as NLO active and how to eliminate the dipole-dipole interaction to avoid the unwanted center-symmetry-trap caused by the polar-induced susceptibility is well demonstrated. Remarkably, 4HPP exhibits competitive and even better properties compared with LAP that include better thermal stability (decomposition at 166 vs 112 °C of LAP); wider transparency range (0.26-1.50 µm); very strong SHG response (3 × KDP); a suitable large birefringence (Δncal = 0.25 vs 0.075 of LAP); and a high laser-induced damage threshold (2.2 × KDP). First-principles calculations show that the π-conjugated organic (4HP)+ cation governs the optical anisotropy, whereas the synergy of the organic and inorganic moieties dominates the SHG process. Our discovery points out a new path for the rational design of high performance semiorganic materials that require an acentric structure.
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PURPOSE: To observe the changes of gait behavior and the expression of wound healing factors of transforming growth factor-ß1 (TGF-ß1), TGF-ß3 and cAMP response element binding protein-1 (CREB-1) during the healing of Achilles tendon in a rat model, and to investigate whether gait analysis can be used to evaluate the tendon healing. METHODS: Achilles tendon of 40 healthy male Sprague-Dawley rats were transected and sutured to establish the Achilles tendon injury (ATI) model. They were randomly divided into 4 groups based on the observational time point at 1, 2, 4 and 6 weeks after injury (n = 10 for each group). Before modeling, 9 rats were randomly selected for CatWalk gait analysis, which contained step cycle, single stance time and average speed. Data were recorded as the normal controls. After then, ATI models were established in the left hind limbs of the all 40 rats (ATI group), while the right hind limbs were only cut and sutured without injury of the Achilles tendon (sham operation group). At 1, 2, 4 and 6 weeks after injury, the gait behavior of the corresponding group of rats (n = 9) as observed and recorded by CatWalk platform. After then, the rats were sacrificed and Achilles tendon of both limbs was harvested. The tendon healing was observed by gross anatomy and histological examination, and the protein and mRNA expression of TGF-ß1, TGF-ß3, CREB-1 were observed by immunohistochemistry and qPCR. The results of tendon gross grading were analyzed by Wilcoxon rank sum test, and other data were analyzed by one-way analysis of variance among multiple groups. RESULTS: Compared with normal controls, all gait indexes (step cycle, single stance time and average speed) were greatly affected following ATI, which however improved with time. The step cycle was significantly lower at 1, 2 and 4 weeks after ATI (compared with normal controls, all p < 0.05), but almost returned to the normal level at 6 weeks ((0.694 ± 0.102) vs. (0.503 ± 0.094) s, p > 0.05). The single stance time of the ATI group was significantly shorter at 1 and 2 weeks after operation ((0.078 ± 0.010) s at 1 week, (0.078 ± 0.020) s at 2 weeks, all p < 0.001) and revealed no significant difference at 4 weeks (p = 0.120). The average speed of ATI group at 1, 2, 4, 6 weeks was significantly lower than that in the normal control group (all p < 0.001). Gross observation showed that the grade of local scar adhesion in ATI group increased significantly at 2, 4 and 6 weeks, compared with the sham operation group (all p < 0.001). Extensive adhesion was formed at 6 weeks after ATI. The results of HE staining showed that the number of fibroblast increased gradually and arranged more orderly in ATI group at 1, 2 and 4 weeks (all p < 0.001), and decreased at 6 weeks, but it was still significantly higher than that of the sham operation group (p < 0.001). Immunohistochemistry showed that the positive expression of TGF-ß1, TGF-ß3, CREB-1 in ATI group was higher than that in the sham operation group at 4 time points (all p < 0.05), which reached the peak at 2 weeks after operation and decreased at 4 weeks (p = 0.002, p < 0.001, p = 0.041, respectively). The results of qPCR suggested that the mRNA expression of TGF-ß1, TGF-ß3, CREB-1 in ATI group was higher than that in the sham operation group at all-time points (all p < 0.05), which reached the peak at 2 weeks after operation, decreased at 4 weeks, and significantly decreased at 6 weeks (all p < 0.001). CONCLUSION: Gait behavior indexes are associated with Achilles tendon healing. The study gives an insight of TGF-ß1, TGF-ß3, CREB-1 changes in the coursing of Achilles tendon healing and these cytokines may be able to be used to regulate the Achilles tendon healing.
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Tendão do Calcâneo , Animais , Proteína de Ligação a CREB , Análise da Marcha , Masculino , Ratos , Ratos Sprague-Dawley , Fator de Crescimento Transformador beta1/genética , Fator de Crescimento Transformador beta3 , CicatrizaçãoRESUMO
Current nonlinear optical materials face a conventional limitation in the trade-off between the band gap and birefringence, especially in the deep UV spectral region. To circumvent this dilemma, we propose a general principle, π-conjugated confinement, to partially decouple the interunit π-conjugated interactions by the separation of non-π-conjugated units. The goal is to further enlarge the band gap to a value larger than that of the singular π-conjugated counterpart and to maintain a suitable density of π-conjugated units to gain a large optical anisotropy. We reveal that π-conjugated confinement is a shared structural feature for all DUV NLO materials known to date, and thus, it provides a novel and essential design criterion for future design synthesis. Guided by this principle, the carbonophosphates are predicted to be a new promising DUV candidate system. Sr3 Y[PO4 ][CO3 ]3 (1) and Na3 X[PO4 ][CO3 ] (X=Ba, Sr, Ca, Mg, 2-5) exhibit not only greatly enhanced birefringence that is 3-24 times larger than that of singular phosphates but also enhanced band gaps that are 0.2-1.7â eV wider than those of singular carbonates.
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Over recent decades, guided by the anionic group theory of nonlinear optical (NLO) materials, rational design strategies have been primarily focused on anionic moieties; consequently, structural modification and design of cationic moieties have long been neglected. Herein, we report a strategy for the coordination of cationic moieties that substantially enhances the optical properties of NLO materials. For an example with well-known crystal structure, [Ag(NH3 )2 ]2 SO4 , we demonstrate that the coordination of the Ag+ cation by the neutral ligand drives the formation of a noncentrosymmetric tetragonal P 4 â¾ 21 c structure as a positive uniaxial crystal. The bending of the [Ag(NH3 )2 ]+ cationic moiety parallel to the z-axis generates an anisotropic arrangement of the dipoles, i.e., a dipole of 0.12â D along the z-direction, yet zero dipole in the xy-plane, which interacts anisotropically with the incident light oscillating electromagnetic wave, leading to optical anisotropy with a large birefringence. The incident beam of 589.3â nm normal to the (110) crystal plane measures Δnobv. =0.08, and [Ag(NH3 )2 ]2 SO4 also exhibits a phase-matching NLO response 1.4 times that of KH2 PO4 (KDP) (obv. 1.4×KDP @1064â nm; cal. d36 =1.50â pm V-1 ).