Spacer Length Research Articles

Naphthalene-based symmetrical liquid crystalline dimers: Synthesis, characterization, mesomorphic behaviour and DFT studies

The reactions of different α,ω-dibromo alkanes with (E)-4-(naphthalen-2-yldiazenyl)phenol and (E)-4-(naphthalen-2-ylimino)methyl)phenol, respectively, led to the synthesis of two new homologous series of liquid crystalline symmetrical dimers with azobenzene or azomethine central linkage and containing the naphthalene moiety as a rigid core. Spectroscopic techniques like FT-IR, 1H NMR, 13C NMR and elemental analysis confirmed their structure. These dimers exhibited mesomorphic phases, studied through POM and DSC. Their photophysical behaviour was explored using UV–visible spectroscopy. Remarkably, dimers with even spacer units (n = 2, 4, 6, 8, 10, 12) displayed excellent liquid crystalline properties as nematic phases, with extended mesophase lengths and thermal stability for both series. The study revealed the vital role of spacer length in determining liquid crystalline behaviour. The computational studies employed the B3LYP method and electron density method for optimization.

On the computation of some code sets of the added Sierpinski triangle

In recent years, the intrinsic metrics have been formulated on the classical fractals. In particular, Sierpinski-like triangles such as equilateral, isosceles, scalene, added and mod$-3$ Sierpinski triangle have been considered in many different studies. The intrinsic metrics can be defined in different ways. One of the methods applied to obtain the intrinsic metric formulas is to use the code representations of the points on these self-similar sets. To define the intrinsic metrics via the code representations of the points on fractals makes also possible to investigate different geometrical, topological properties and geodesics of these sets. In this paper, we investigate some circles and closed sets of the added Sierpinski triangle and express them as the code sets by using its intrinsic metric.

Azobenzene‐containing liquid crystalline poly(methacrylates) with different spacer length as media for holographic grating recording

AbstractLiquid crystalline (LC) poly(methacrylates) with azobenzene moieties in their side chains have been synthesized and their chemical structure has been confirmed with nuclear magnetic resonance spectroscopy and gel permeation chromatography. Azobenzene moieties are linked to polymer backbone via an alkyl spacer with length from 2 to 10 methylene units. Photooptical processes in thin amorphized polymer films are examined through measurements of optical anisotropy and holographic grating recording. Birefringence values induced with a linearly polarized green (532 nm) laser beam has strongly depended from the spacer length. Irradiation with two circularly polarized green laser beams leads to the formation of polarization and surface relief gratings, which have been visualized with polarized optical and atomic force microscopy, respectively. Diffraction efficiency of the recorded gratings is in correlation with the spacer length, namely, the shorter the spacer, the higher diffraction efficiency can be achieved. For polymers with short spacers polarization gratings can be easily erased by circularly polarized light, but only partial erasing of surface relief gratings is observed. The results presented offer the possibility of tailoring the chemical structure of azobenzene‐containing polymers for designing high‐efficiency media for the holographic recording.

The preparation of permanent antistatic additive based on poly(ether-b-amide) copolymers and its modification effect on polyamide 6

Abstract Conventional polymers have typically been used in the packaging of various electronic devices; however, due to the inherent electrically insulating properties these materials fail to dissipate static charges. To address this issue, novel poly(ether-b-amide) (PEBA) segmented copolymers consisting of uniform rigid oxalamide and flexible polyethylene glycol (PEG) were synthesized via melt polycondensation. The influence of PEG molecular weight and the spacer length separating two oxalamide units on the condensed structure, mechanical performance, and antistatic properties was systematically investigated. Fourier-transform infrared (FTIR) demonstrated strongly hydrogen bonded and highly ordered oxalamide hard segments with the degree of ordering between 71 and 85 % even at low levels. Mechanical behavior results showed that segmented copolymers have an obvious yield point, an elastic modulus between 20 and 30 MPa, and strain at break exceeding 2000 %. Meanwhile, such copolymers possessed low surface resistivity, as low as 107 Ω, which is significantly less than that of commercial antistatic additives. The antistatic effect of PEBA on polyamide 6 (PA6) was also investigated, revealing that when the content reached 30 wt%, the surface resistivity of the alloys decreased from 1013 Ω to 1011 Ω and remained stable after 40 days, even after water washing treatment. Overall, these findings illustrate that the newly synthesized PEBA copolymers demonstrate outstanding long-term antistatic properties and provide valuable insights for the development of polyether-based multiblock copolymer antistatic agents.

Numerical investigation and parameter optimization on a rib-grooved liquid-cooled plate for lithium battery thermal management system

To increase the effectiveness of liquid-cooled battery thermal management systems (BTMS) in electric vehicles, a unique liquid-cooled plate with a discrete, inclined, and alternating arrangement of ribs and grooves inside the plate was invented during this study. A numerical study was carried on to analyze the thermal performance between this rib-grooved liquid-cooled plate and a conventional straight-channel one. Firstly, a battery module's 1D/3D electrochemical-thermal coupled model was constructed to analyze the thermal performance in the case of actual electrochemical heat production. Then numerical results were obtained by solving this coupled model with different plates. The results indicated that ribs effectively equalize the flows between different channels and multiple longitudinal swirl flows are formed due to grooves, which improves the liquid-cooled system's temperature control performance with a small increase in pressure drop. The maximum battery temperature is 0.74 °C lower, the temperature standard deviation of the contact surface is 0.18 °C lower, and the pressure drop is 55.37 Pa higher in the BTMS with the rib-grooved liquid-cooled plate than it is in the conventional one. After that, an orthogonal design of experiments was used to investigate the effect of four features, including rib-groove tilt angle, column spacing, row spacing, and rib-groove length, on the thermal performance and energy consumption of the battery module. The optimum structure of the rib-grooved liquid-cooled plate is obtained through range analysis: the rib-groove inclination angle is 45°, the row spacing is 13.5 mm, the column spacing is 11.5 mm, and the rib-groove length is 9 mm. This research on the rib-grooved liquid-cooled plate offers a fresh concept that considerably enhances its capacity to regulate the temperature of the liquid-cooled BTMS.

Study on the Arc Additive Manufacturing Process and Mechanical Properties of Inconel 625 Nickel-Based Alloy Bulk

_ The melt-inert gas-shielded arc additive manufacturing experiment of Inconel 625 nickel-based alloy bulk was carried out. The influence of current mode, current, travel speed, weld bead spacing, deposition path, and arc length on the formation of overlapping weld beads was studied. The incomplete fusion near the bottom weld toe of adjacent weld beads was the main defect. The optimized parameters for bulk additive manufacturing obtained from the experiment were as follows: pulse current of 70 A, travel speed of 200 mm/min, weld bead spacing of 3 mm, dry extension of 10 mm, continuous deposition, and arc length of 1 mm. Due to the thermal influence during the deposition of adjacent weld beads, directional grains were formed inside the weld bead and at the boundary with adjacent weld beads. However, the direction of grain growth was not uniform throughout the entire weld bead, and a consistent texture of the entire weld bead was not formed. The tensile strengths of the specimens in the X, Y, and Z directions were 858.5, 838.7, and 827.2 MPa, respectively, and the fracture elongations were 53.3%, 37.6%, and 42.1%, respectively. The strength in the Z direction, which is the vertical direction, was the lowest. Keywords arc additive manufacturing; nickel-based alloy; incomplete fusion; texture

Assessment of Cellulose Nanofiber-Based Elastase Biosensors to Inflammatory Disease as a Function of Spacer Length and Fluorescence Response.

Inflammatory disease biomarker detection has become a high priority in point-of-care diagnostic research in relation to chronic wounds, with a variety of sensor-based designs becoming available. Herein, two primary aspects of biosensor design are examined: (1) assessment of a cellulose nanofiber (CNF) matrix derived from cotton ginning byproducts as a sensor transducer surface; and (2) assessment of the relation of spacer length and morphology between the CNF cellulose backbone and peptide fluorophore as a function of sensor activity for porcine pancreatic and human neutrophil elastases. X-ray crystallography, specific surface area, and pore size analyses confirmed the suitability of CNF as a matrix for wound care diagnostics. Based upon the normalized degree of substitution, a pegylated-linker connecting CNF transducer substrate to peptide fluorophore showed the greatest fluorescence response, compared to short- and long-chain alkylated linkers.

Innovative twist design for solar water heaters: Experimental findings and implications

More effective use of solar energy in hot water systems is made possible by optimising heat transfer and flow resistance. In light of this, Research has been conducted to enhance convective heat transfer while analysing flow friction characteristics for best performance, resulting in the design of novel inserts known as customised twists, which increase the efficiency of the solar hot water system. A conventional, plain tube heater is used as a baseline for the study on thermal characteristics, heat transportation and flow friction attributes. A thorough analysis and comparison of the thermal behaviour of the system with customised twist inserts that have been modified using rods and spacers of different lengths is performed. As a result of the induced disturbance in the fluid particle flow pattern throughout the length of risers, a significant improvement in the coefficient of convective heat transfer is observed. The study validated the correlations for the convective heat transfer coefficient and the resistance coefficient against previous research findings. The findings indicated that the thermal efficiency of the full-length twist-inserted system is almost three times greater than that of a plain collector while doubling its pressure drop. The findings of this research could be useful in designing low-cost, compact solar water heaters.

Impact of Implant Size and Position on Subsidence Degree after Anterior Cervical Discectomy and Fusion: Radiological and Clinical Analysis.

Implant subsidence is recognized as a complication of interbody stabilization, although its relevance remains ambiguous, particularly in terms of relating the effect of the position and depth of subsidence on the clinical outcome of the procedure. This study aimed to evaluate how implant positioning and size influence the incidence and degree of subsidence and to examine their implications for clinical outcomes. An observational study of 94 patients (157 levels) who underwent ACDF was conducted. Radiological parameters (implant position, implant height, vertebral body height, segmental height and intervertebral height) were assessed. Clinical outcomes were evaluated using the Visual Analogue Scale (VAS) and Neck Disability Index (NDI). Subsidence was evaluated in groups according to its degree, and statistical analyses were performed. The findings revealed that implant-to-endplate ratio and implant height were significant risk factors associated with the incidence and degree of subsidence. The incidence of subsidence varied as follows: 34 cases (41.5%) exhibited displacement of the implant into the adjacent endplate by 2-3 mm, 32 cases (39%) by 3-4 mm, 16 cases (19.5%) by ≥4 mm and 75 (47.8%) cases exhibited no subsidence. The findings underscore that oversized or undersized implants relative to the disc space or endplate length elevate the risk and severity of subsidence.

Sexual dimorphism in hypopharyngeal airway space and effective length of mandible with twin block appliance therapy: A prospective study

To evaluate changes in hypopharyngeal airway space and effective length of mandible in skeletal Class II patients following Twin Block Appliance (TBA) therapy. Further, the study also aims to compare the post functional changes being observed between males and females. This is a prospective study on 15 Pre-adolescents (08 males and 07 females; mean age: 10.75 ± 0.91years) who underwent functional jaw orthopaedics with TBA. Lateral cephalogram at Pre treatment stage (T1) and post functional phase of TBA (T2) were obtained. The cephalometric parameters were measured and paired t test was done for comparison of pre and post functional changes. The mean period of functional phase of TBA therapy was 18 ± 02 months. The cephalometric changes post functional jaw orthopaedics were statistically insignificant when compared males Vs females (P > 0.05). However, mean increase of in the effective length of mandible and hypopharyngeal space (T2-T1) was 4.0± 1.16 mm and 1.47±0.57 mm respectively, which were statistically highly significant (P<0.5). 1. TBA therapy in skeletal Class II patients significantly increases the effective mandibular length and hypo-pharyngeal space post functional phase; 2. No significant differences were observed between males and females with respect to post functional cephalometric changes in mandibular length and hypopharyngeal space.

Photocontrol of small GTPase Ras fused with a photoresponsive protein.

The small GTPase Ras plays an important role in intracellular signal transduction and functions as a molecular switch. In this study, we used a photoresponsive protein as the molecular regulatory device to photoregulate Ras GTPase activity. Photo zipper (PZ), a variant of the photoresponsive protein Aureochrome1 developed by Hisatomi etal. was incorporated into the C-terminus of Ras as a fusion protein. The three constructs of the Ras-PZ fusion protein had spacers of different lengths between Ras and PZ. They were designed using an Escherichia coli expression system. The Ras-PZ fusion proteins exhibited photoisomerization upon blue light irradiation and in the dark. Ras-PZ dimerized upon light irradiation. Moreover, Ras GTPase activity, which is accelerated by the Ras regulators guanine nucleotide exchange factors and GTPase-activating proteins, is controlled by photoisomerization. It has been suggested that light-responsive proteins are applicable to the photoswitching of the enzymatic activity of small GTPases as photoregulatory molecular devices.

Spacer-Programmed Two-Dimensional DNA Origami Assembly.

Two-dimensional (2D) DNA origami assembly represents a powerful approach to the programmable design and construction of advanced 2D materials. Within the context of hybridization-mediated 2D DNA origami assembly, DNA spacers play a pivotal role as essential connectors between sticky-end regions and DNA origami units. Here, we demonstrated that programming the spacer length, which determines the binding radius of DNA origami units, could effectively tune sticky-end hybridization reactions to produce distinct 2D DNA origami arrays. Using DNA-PAINT super-resolution imaging, we unveiled the significant impact of spacer length on the hybridization efficiency of sticky ends for assembling square DNA origami (SDO) units. We also found that the assembly efficiency and pattern diversity of 2D DNA origami assemblies were critically dependent on the spacer length. Remarkably, we realized a near-unity yield of ∼98% for the assembly of SDO trimers and tetramers via this spacer-programmed strategy. At last, we revealed that spacer lengths and thermodynamic fluctuations of SDO are positively correlated, using molecular dynamics simulations. Our study thus paves the way for the precision assembly of DNA nanostructures toward higher complexity.

Regio- and Enantioselective Asymmetric Transfer Hydrogenation of One Carbonyl Group in a Diketone through Steric Hindrance.

On the basis of steric hindrance, one carbonyl group in a diketone can be reduced in a regioselective manner, with high enantioselectivity. The methodology can be extended to ketones with varied length of hydrocarbon chain spacing, and the products can be converted by oxidation to hydroxy esters or lactones without loss of enantiopurity.

Comparative analysis of changes in spinal dimensions following different correction methods in adult spinal deformity surgery.

Background: Adult spinal deformity (ASD) surgery has gained popularity, with significant improvements in patient-reported outcomes. Posterior lumbar interbody fusion with multiple grade II osteotomies (PLIF + MOs) and lateral lumbar interbody fusion (LLIF) have been utilized to correct ASD; however, no studies have compared these methods with regard to the pre- and postoperative changes in length and volume of the spinal canal. This study aimed to investigate the 3-dimensional changes in the anterior vertical column length (AVCL), spinal canal length (SCL), and spinal canal volume (SCV) in patients with ASD after surgery, employing LLIF and PLIF + MOs. Methods: This retrospective study examined 44 patients with ASD who underwent surgery between 2010 and 2021 using two corrective surgical methods, LLIF and PLIF + MOs. Radiographic parameters and clinical outcomes were assessed, and three-dimensional models were created from computed tomography images to analyze changes in AVCL, SCL, and SCV. Results: We compared the effects of LLIF and PLIF + MOs on spinal canal dimensions during ASD surgery. LLIF demonstrated an increase in lumbar segment (L1-S1) AVCL and whole spine (T1-S1) SCL by 6.5 ± 8.0mm and 13.8 ± 7.6mm, respectively, compared with PLIF + MOs. However, PLIF + MOs exhibited a reduction in the lengths of the lumbar segment AVCL. Postoperative differences were significant for AVCL (L1-S1), SCL fusion level, and first-standing lumbar lordosis between the groups (p < 0.0001, 0.002, and 0.016, respectively). LLIF significantly increased the SCV at the fusion level and whole spine T1-S1 by 14.5% and 10.6%, respectively, outperforming PLIF + MOs. Despite changes in dimensions, the postoperative Oswestry disability index scores showed no significant difference between the two groups. Conclusions: Our study suggests that LLIF can increase spinal canal space, lumbar lordosis, and anterior column length in the lumbar spinal segment. Knowledge of these variations may be critical for enhancing surgical outcomes and preventing neurological complications.

A precise modeling method of three‐dimensional discrete fracture network based on rectangular joint model

AbstractAs the weak structure and main seepage channel of rock mass, the discrete fracture network (DFN) has a significant influence on the physical and mechanical properties of rock mass. In this paper, based on the rectangular joint model, two algorithms are proposed to realize the precise modeling of the DFN in any polyhedron. First, the equivalence of DFN modeling with the rectangular joint model and the elliptical joint model is theoretically deduced. On this basis, the chain splicing algorithm suitable for the rectangular joint model is proposed, which can generate the DFN model according to the actual distribution of joint spacing, trace, and bridge length. Aiming at the concave boundary in the model domain, the segmentation‐stitching operation is put forward, and the continuity of the joint when passing through the interface is ensured. Finally, the effectiveness of the above algorithm is verified by several simple cases, and the relationship between the size of the geometrical representative elementary volume (REV) and discontinuity parameters is discussed. The results show that when the mean values of the joint distribution parameters are the same, even if the distribution rules are different, the number of joints generated in the same spatial region is approximately equal. The size of the geometrical REV is independent of the spacing and bridge length and is approximately three to five times the mean of the trace. The relevant algorithms and conclusions in this paper can be used as the basis for subsequent rock mass stability analysis and seepage calculation.

The Influence of the Molecular Structure of Compounds on Their Properties and the Occurrence of Chiral Smectic Phases.

We have designed new chiral smectic mesogens with the -CH2O group near the chiral center. We synthesized two unique rod-like compounds. We determined the mesomorphic properties of these mesogens and confirmed the phase identification using dielectric spectroscopy. Depending on the length of the oligomethylene spacer (i.e., the number of methylene groups) in the achiral part of the molecules, the studied materials show different phase sequences. Moreover, the temperature ranges of the observed smectic phases are different. It can be seen that as the length of the alkyl chain increases, the liquid crystalline material shows more mesophases. Additionally, its clearing (isotropization) temperature increases. The studied compounds are compared with the structurally similar smectogens previously synthesized. The helical pitch measurements were performed using the selective reflection method. These materials can be useful and effective as chiral components and dopants in smectic mixtures targeted for optoelectronics and photonics.

Enhanced gene transfection and induction of apoptosis in melanoma cells by branched poly(β-amino ester)s with uniformly distributed branching units

Melanoma, one of the most devastating forms of skin cancer, currently lacks effective clinical treatments. Delivery of functional genes to modulate specific protein expression to induce melanoma cell apoptosis could be a promising therapeutic approach. However, transfecting melanoma cells using non-viral methods, particularly with cationic polymers, presents significant challenges. In this study, we synthesized three branched poly(β-amino ester)s (HPAEs) with evenly distributed branching units but varying space lengths through a two-step “oligomer combination” strategy. The unique topological structure enables HPAEs to condense DNA to form nano-sized polyplexes with favorable physiochemical properties. Notably, HPAEs, especially HPAE-2 with intermediate branching unit space length, demonstrated significantly higher gene transfection efficiency than the leading commercial gene transfection reagent, jetPRIME, in human melanoma cells. Furthermore, HPAE-2 efficiently delivered the Bax-encoding plasmid into melanoma cells, leading to a pronounced pro-apoptotic effect without causing noticeable cytotoxicity. This study establishes a potent non-viral platform for gene transfection of melanoma cells by harnessing the distribution of branching units, paving the way for potential clinical applications of gene therapy in melanoma treatment.

Selenium-linked cyanobiphenyl-based liquid crystal dimers: the effects of chalcogen linkage and spacer length on the twist-bend nematic phase

ABSTRACT We synthesised selenium-linked liquid crystal dimers and examined their phase behaviour to determine the effects of chalcogen linkage and spacer length on the formation of a twist-bend nematic (NTB) phase. Two new homologous series of nonsymmetric selenoether- and ether- or thioether-linked cyanobiphenyl-based dimers (CBSenOCB and CBSenSCB, respectively) comprising an alkyl spacer chain with a carbon number (n) of 3, 5, 6, 7, 9, and 11 were developed. We also synthesised n = 6 and 11 of previously reported symmetrically selenoether-linked CBSenSeCB homologues. Conventional nematic (N) and NTB phases were observed for nearly all odd-n CBSenSeCB, CBSenOCB, and CBSenSCB dimers. The phase transition behaviours of the three homologous series were compared with those of the known symmetric ether-linked CBOnOCB, thioether-linked CBSnSCB, and asymmetric thioether- and ether-linked CBSnOCB dimers. Replacing ether with thioether or selenoether resulted in lower LC phase-transition temperatures, particularly for selenoether. Single-crystal structural analyses revealed that CBS3SCB and CBSe3SeCB exhibited folded U-shaped molecular shapes that were bent more than the V-shapes of CBOnOCB (n = 3 and 5) and CBS5SCB. In addition, thioether and selenoether linkages rendered the molecular forms of odd-spacer dimers in the crystals more bent.

The chemoenzymatic synthesis of glycan-terminated oligo(Leu)x

Introduction: Glycopeptides contain carbohydrate moieties (glycans) covalently attached to the side chain and/or terminal peptide units. Since glycans are present on cell surfaces, these constructs can potentially address a wide array of therapeutic functions. To overcome the deficiencies associated with current synthetic routes to glycopeptides, such as costly processes and toxic reagents, this work aimed to develop versatile environmentally friendly protease-catalyzed peptide synthesis routes to peptides decorated with a glycan at their N-terminus.Methods: “Grafters” were first synthesized that consist of a glycan conjugated directly, or through a spacer, to the amine group of L-Phe-ethyl ester (Phe-OEt). The role of Phe-OEt is to increase the conjugate’s recognition by the protease (papain) catalytic active site. A series of grafters were synthesized with variation of the glycan structure, linkage-chemistry, and presence of an oligo (ethylene glycol) “spacer” of varied length between the glycan and Phe-OEt moiety. High grafter efficiency will result by the successful acceptance of the grafter at the enzymes S1/S2 subsites, formation of an acyl enzyme complex and subsequent conversion to glycan-terminated oligo(Leu)x (x ≥ 1), as opposed to construction of non-glycan N-terminated oligo(Leu)x.Results and discussion: While glycan-Phe-OEt grafters without a spacer between the glycan and Phe-OEt resulted in low grafter efficiency (8.3% ± 2.0%), insertion of a short oligo (ethylene glycol) spacer between the glycan and Phe-OEt moieties (glycan-PEGn-Phe-OEt, n ≥ 3) increased the grafter efficiency by 3-fold–24.5% ± 1.8%. In addition, computational modeling was performed using Rosetta software provided insights on a molecular level of how grafter efficiency is influenced by the PEG spacer length.

Design and analysis of gate all around stacked nanosheet-DRAM for future technology node

This paper reports a stacked Dynamic random-access transistor (DRAM) memory structure that is based on gate all-around nanosheet access transistor. A TCAD study is done to compare nanosheet DRAM and conventional saddle fin recessed channel access transistor (SRCAT) in terms of DRAM electrical characteristics and its row hammer-induced leakage. The nanosheet DRAM shows superior characteristics in terms of current driving capability, speed, and refresh than SRCAT. The nanosheet DRAM also shows significantly lower hammer-induced failure as compared to SRCAT because the original leakage path from the cell to the neighboring cell gets blocked due to the nanosheet device structure. We also investigate the effect of spacer length on nanosheet DRAM characteristics and show that extended spacer length is favorable for having better DRAM characteristics due to the floating body effect. Our study demonstrates the potential, and advantages of nanosheet DRAM architecture compared to the conventional SRCAT DRAM.