71 research outputs found
Torsional Entropy at the Origin of the Reversible Temperature-Induced Phase Transition of Cellulose
The temperature-induced phase transition of native cellulose
was
studied by X-ray diffraction and molecular dynamics (MD) simulation.
Upon heating, this transition is characterized by an important expansion
of the distance between the planes of glucopyranose rings, which is
observed both experimentally and in MD. Computed trajectories suggest
that this expansion is caused by a rotation of the exocyclic hydroxymethyl
groups. Upon cooling, the phase transition, experimentally known as
reversible, was found to be irreversible in the MD simulation when
using current GROMOS 53a6 force field parameters. By varying one of
these, related to the potential energy of the hydroxymethyl conformers,
a reversible phase transition could be observed <i>in silico</i>. From the linear dependence of the transition temperature on the
dihedral energy of the different conformers, the entropy change due
to the phase transition could be estimated to be about 26 JK<sup>â1</sup> mol<sup>â1</sup>. This value essentially reflects the additive
contribution of the torsional entropies of the exocyclic moieties,
as other conformational parameters appeared to have little effect
on the phase transition
Pd-Catalyzed Arylperfluoroalkylation of Unactivated Olefins for the Synthesis of Heterocycles
An
efficient and highly practical palladium-catalyzed arylperfluoroalkylation
of unactivated olefins is presented here. A variety of perfluoroalkylated
heterocyclic derivatives can be obtained in high regioselectivity.
The reaction proceeds mildly without the electronic activation of
the aryl group and features high generality, low-cost fluoroalkylated
sources and good functional-group compatibility
Pd-Catalyzed Arylperfluoroalkylation of Unactivated Olefins for the Synthesis of Heterocycles
An
efficient and highly practical palladium-catalyzed arylperfluoroalkylation
of unactivated olefins is presented here. A variety of perfluoroalkylated
heterocyclic derivatives can be obtained in high regioselectivity.
The reaction proceeds mildly without the electronic activation of
the aryl group and features high generality, low-cost fluoroalkylated
sources and good functional-group compatibility
Data_Sheet_1_Efficacy and safety of parecoxib and flurbiprofen axetil for perioperative analgesia in children: a network meta-analysis.docx
ObjectiveThe aim of this study was to systematically review the efficacy and safety of parecoxib and flurbiprofen axetil for perioperative analgesia in children through Bayesian network meta-analysis.MethodsWe systematically searched PubMed, Embase, Cochrane Library, Web of Science, Sinomed, CNKI, VIP, and Wanfang Data databases on 18 July 2022 to obtain randomized controlled trials comparing perioperative parecoxib or flurbiprofen with placebo or standard treatment for pediatric analgesia. The outcomes were the postoperative pain score and the incidence of adverse events. The Gemtc package of R-4.0.3 and Stata 17.0 were used for Bayesian network meta-analysis.ResultsWe retrieved 942 articles and 49 randomized controlled trials involving 3,657 patients who met the inclusion criteria. Compared with children who received placebo treatment, those who received flurbiprofen axetil had lower pain sores at each time point within 24 h postoperatively, and those who received parecoxib had lower pain sores at each time point within 12 h postoperatively. Compared with children who received tramadol treatment, both the children who received flurbiprofen axetil or parecoxib had lower pain scores at 8 h postoperatively. The ranking results demonstrated that flurbiprofen axetil had significant superiority in reducing pain scores at 2, 4, and 12 h postoperatively, and parecoxib had significant superiority in reducing pain scores at 0, 0.5, 1, 6, 8, and 24 h postoperatively. In terms of safety, compared with children who received placebo, those who received flurbiprofen axetil or parecoxib had a lower incidence of total adverse events and postoperative agitation. Compared with tramadol, flurbiprofen axetil and parecoxib both significantly reduced the incidence of total adverse events and postoperative nausea and vomiting. Compared with flurbiprofen axetil or fentanyl, parecoxib significantly reduced the incidence of postoperative nausea and vomiting. The ranking results showed that parecoxib was advantageous in decreasing the incidence of total adverse events and postoperative nausea and vomiting.ConclusionFlurbiprofen axetil was most effective at reducing pain scores at 2, 4, and 12 h postoperatively. Parecoxib had an advantage in terms of reducing pain scores at 0, 0.5, 1, 6, 8, and 24 h postoperatively, as well as the incidence of total adverse events and postoperative nausea and vomiting.Systematic trial registrationhttps://www.crd.york.ac.uk/PROSPERO/display_record.php?RecordID=348886, PROSPERO (CRD42022348886).</p
Hydration-Dependent Dynamical Modes in Xyloglucan from Molecular Dynamics Simulation of <sup>13</sup>C NMR Relaxation Times and Their Distributions
Macromolecular
dynamics in biological systems, which play a crucial
role for biomolecular function and activity at ambient temperature,
depend strongly on moisture content. Yet, a generally accepted quantitative
model of hydration-dependent phenomena based on local relaxation and
diffusive dynamics of both polymer and its adsorbed water is still
missing. In this work, atomistic-scale spatial distributions of motional
modes are calculated using molecular dynamics simulations of hydrated
xyloglucan (XG). These are shown to reproduce experimental hydration-dependent <sup>13</sup>C NMR longitudinal relaxation times (<i>T</i><sub>1</sub>) at room temperature, and relevant features of their broad
distributions, which are indicative of locally heterogeneous polymer
reorientational dynamics. At low hydration, the self-diffusion behavior
of water shows that water molecules are confined to particular locations
in the randomly aggregated XG network while the average polymer segmental
mobility remains low. Upon increasing water content, the hydration
network becomes mobile and fully accessible for individual water molecules,
and the motion of hydrated XG segments becomes faster. Yet, the polymer
network retains a heterogeneous gel-like structure even at the highest
level of hydration. We show that the observed distribution of relaxations
times arises from the spatial heterogeneity of chain mobility that
in turn is a result of heterogeneous distribution of waterâchain
and chainâchain interactions. Our findings contribute to the
picture of hydration-dependent dynamics in other macromolecules such
as proteins, DNA, and synthetic polymers, and hold important implications
for the mechanical properties of polysaccharide matrixes in plants
and plant-based materials
Aesthetic Cellulose Filaments with Water-Triggered Switchable Internal Stress and Customizable Polarized Iridescence Toward Green Fashion Innovation
Healthy,
convenient, and aesthetic hair dyeing and styling
are
essential to fashion trends and personalâsocial interactions.
Herein, we fabricate green, scalable, and aesthetic regenerated cellulose
filaments (ACFs) with customizable iridescent colors, outstanding
mechanical properties, and water-triggered moldability for convenient
and fashionable artificial hairdressing. The fabrication of ACFs involves
cellulose dissolution, cross-linking, wet-spinning, and nanostructured
orientation. Notably, the cross-linking strategy endows the ACFs with
significantly weakened internal stress, confirmed by monitoring the
offset of the CâOâC group in the cellulose molecular
chain with Raman imaging, which ensures a tailorable orientation of
the nanostructure during wet stretching and tunable iridescent polarization
colors. Interestingly, ACFs can be tailored for three-dimensional
shaping through a facile water-triggered adjustable internal stress:
temporary shaping with low-level internal stress in the wet state
and permanent shaping with high-level internal stress in the dry state.
The health, convenience, and green aesthetic filaments show great
potential in personal wearables
MXene-Mediated Cellulose Conductive Hydrogel with Ultrastretchability and Self-Healing Ability
Constructing natural polymers such as cellulose, chitin,
and chitosan
into hydrogels with excellent stretchability and self-healing properties
can greatly expand their applications but remains very challenging.
Generally, the polysaccharide-based hydrogels have suffered from the
trade-off between stiffness of the polysaccharide and stretchability
due to the inherent nature. Thus, polysaccharide-based hydrogels (polysaccharides
act as the matrix) with self-healing properties and excellent stretchability
are scarcely reported. Here, a solvent-assisted strategy was developed
to construct MXene-mediated cellulose conductive hydrogels with excellent
stretchability (âŒ5300%) and self-healability. MXene (an emerging
two-dimensional nanomaterial) was introduced as emerging noncovalent
cross-linking sites between the solvated cellulose chains in a benzyltrimethylÂammonium
hydroxide aqueous solution. The electrostatic interaction between
the cellulose chains and terminal functional groups (O, OH, F) of
MXene led to cross-linking of the cellulose chains by MXene to form
a hydrogel. Due to the excellent properties of the celluloseâMXene
conductive hydrogel, the work not only enabled their strong potential
in both fields of electronic skins and energy storage but provided
fresh ideas for some other stubborn polymers such as chitin to prepare
hydrogels with excellent properties
Hydration-Dependent Dynamical Modes in Xyloglucan from Molecular Dynamics Simulation of <sup>13</sup>C NMR Relaxation Times and Their Distributions
Macromolecular
dynamics in biological systems, which play a crucial
role for biomolecular function and activity at ambient temperature,
depend strongly on moisture content. Yet, a generally accepted quantitative
model of hydration-dependent phenomena based on local relaxation and
diffusive dynamics of both polymer and its adsorbed water is still
missing. In this work, atomistic-scale spatial distributions of motional
modes are calculated using molecular dynamics simulations of hydrated
xyloglucan (XG). These are shown to reproduce experimental hydration-dependent <sup>13</sup>C NMR longitudinal relaxation times (<i>T</i><sub>1</sub>) at room temperature, and relevant features of their broad
distributions, which are indicative of locally heterogeneous polymer
reorientational dynamics. At low hydration, the self-diffusion behavior
of water shows that water molecules are confined to particular locations
in the randomly aggregated XG network while the average polymer segmental
mobility remains low. Upon increasing water content, the hydration
network becomes mobile and fully accessible for individual water molecules,
and the motion of hydrated XG segments becomes faster. Yet, the polymer
network retains a heterogeneous gel-like structure even at the highest
level of hydration. We show that the observed distribution of relaxations
times arises from the spatial heterogeneity of chain mobility that
in turn is a result of heterogeneous distribution of waterâchain
and chainâchain interactions. Our findings contribute to the
picture of hydration-dependent dynamics in other macromolecules such
as proteins, DNA, and synthetic polymers, and hold important implications
for the mechanical properties of polysaccharide matrixes in plants
and plant-based materials
Image1_Exploring the influence of DNA methylation and single nucleotide polymorphisms of the Myostatin gene on growth traits in the hybrid grouper (Epinephelus fuscoguttatus (female) Ă Epinephelus polyphekadion (male)).TIF
Investigations into the correlation between growth characteristics and DNA methylation levels, along with genetic variations, can provide fundamental insights to enhance growth performance in groupers. The Myostatin (mstn) gene plays a vital role in regulating skeletal muscle development and growth. This study scrutinized the DNA methylation levels of the mstn gene across hybrid groupers (E. fuscoguttatus (â) Ă E. polyphekadion (â)) and their parental species, to evaluate its impact on growth attributes in grouper fish. The nucleotide sequence of the mstn gene was directly sequenced in the hybrid grouper, exhibiting different growth performance to identify the single nucleotide polymorphisms (SNPs) of the mstn gene and explore their correlation with growth characteristics. The findings revealed no significant differences in global DNA methylation levels within muscle tissue among the hybrid grouper and parents. However, significant differences in DNA methylation sites were discovered between the hybrid grouper and E. polyphekadion at sites 824 and 1521 (located at exon 2 and intron 2, respectively), and between E. fuscoguttatus and E. polyphekadion at site 1521. These variations could potentially influence the mRNA expression of the mstn gene. The study also identified that SNP g.1003 T > C in exon 2 of the mstn gene was significantly associated with various growth traits including body weight, total length, body length, head length, caudal peduncle height, and body height (p < 0.01). Specimens with the TT genotype at site 1003 demonstrated superior growth performance compared to those with the TC genotype. Furthermore, microstructural analyses of muscle tissue showed that the average area and diameter of muscle fibers in TT genotype individuals were significantly greater than those in TC genotype individuals. Therefore, this research provides robust evidence linking the DNA methylation level and polymorphisms of the mstn gene with growth traits, which could be beneficial for grouper breeding programs.</p
Image2_Exploring the influence of DNA methylation and single nucleotide polymorphisms of the Myostatin gene on growth traits in the hybrid grouper (Epinephelus fuscoguttatus (female) Ă Epinephelus polyphekadion (male)).TIF
Investigations into the correlation between growth characteristics and DNA methylation levels, along with genetic variations, can provide fundamental insights to enhance growth performance in groupers. The Myostatin (mstn) gene plays a vital role in regulating skeletal muscle development and growth. This study scrutinized the DNA methylation levels of the mstn gene across hybrid groupers (E. fuscoguttatus (â) Ă E. polyphekadion (â)) and their parental species, to evaluate its impact on growth attributes in grouper fish. The nucleotide sequence of the mstn gene was directly sequenced in the hybrid grouper, exhibiting different growth performance to identify the single nucleotide polymorphisms (SNPs) of the mstn gene and explore their correlation with growth characteristics. The findings revealed no significant differences in global DNA methylation levels within muscle tissue among the hybrid grouper and parents. However, significant differences in DNA methylation sites were discovered between the hybrid grouper and E. polyphekadion at sites 824 and 1521 (located at exon 2 and intron 2, respectively), and between E. fuscoguttatus and E. polyphekadion at site 1521. These variations could potentially influence the mRNA expression of the mstn gene. The study also identified that SNP g.1003 T > C in exon 2 of the mstn gene was significantly associated with various growth traits including body weight, total length, body length, head length, caudal peduncle height, and body height (p < 0.01). Specimens with the TT genotype at site 1003 demonstrated superior growth performance compared to those with the TC genotype. Furthermore, microstructural analyses of muscle tissue showed that the average area and diameter of muscle fibers in TT genotype individuals were significantly greater than those in TC genotype individuals. Therefore, this research provides robust evidence linking the DNA methylation level and polymorphisms of the mstn gene with growth traits, which could be beneficial for grouper breeding programs.</p
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