Free Rotation Research Articles

Self-similar solutions and large time behavior to the 2D isentropic compressible Navier–Stokes equations with vacuum free boundary and rotation

This paper is concerned with a class of self-similar analytical solutions to the 2D isentropic compressible Navier–Stokes equations with vacuum free boundary for polytropic gases. It is shown that the free boundary will grow linearly in time (see (1.11)), moreover, both angular velocity uϕ and its derivatives, and the derivative of radial velocity ur will tend to zero as t→+∞, while radial velocity itself is bounded. In particular, it is interesting to see that when the adiabatic exponent γ>2 and for a suitably large time, the rotation plays a dominant role in accelerating the growth of the free boundary compared with the effect of pressure.

Arbitrary controlled re-orientation of a spinning body by evolving its tensor of inertia

Bodies with the nonspherical tensor of inertia (TOI) exhibit a variety of rotational motion patterns, including chaotic motion, stable periodic (quasi-periodic) rotation, unstable rotation around the direction close to the body's second principal axis, featuring a well-known tennis-racket (also known as Garriott-Dzhanibekov [1]) effect – series of seemingly spontaneous 180 degrees flips. These patterns are even more complex if the body's TOI is changing with time. Changing a body's TOI has been discussed recently as a tool to perform controllable Garriott-Dzhanibekov flips and similar maneuvers. In this work, the optimal control of the TOI of the body (spacecraft, or any other device that admits free rotation in three dimensions) is used as a means to perform desirable re-orientations of a body with respect to its angular velocity. Using the spherical TOI as the initial and final point of the maneuver, we optimize the parameters of the maneuver to achieve and stabilize the desired orientation of the body's principal axes with respect to spin angular velocity. It appears that such a procedure allows for finding arbitrarily complex maneuver trajectories of a spinning body. In particular, intermediate axis instability can be used to break the alignment of the body's principal axis and the axis of rotation. Such maneuvers do not require utilization of propellants and could be straightforwardly used for attitude control of a spin-stabilized spacecraft. The capabilities of such a method of angular maneuvering are demonstrated in numerical simulations.

Depth-profiling alkyl chain order in unsaturated lipid monolayers on water.

Unsaturated lipids with C=C groups in their alkyl chains are widely present in the cell membrane and food. The C=C groups alter the lipid packing density, membrane stability, and persistence against lipid oxidation. Yet, molecular-level insights into the structure of the unsaturated lipids remain scarce. Here, we probe the molecular structure and organization of monolayers of unsaturated lipids on the water surface using heterodyne-detected sum-frequency generation (HD-SFG) spectroscopy. We vary the location of the C=C in the alkyl chain and find that at high lipid density, the location of the C=C group affects neither the interfacial water organization nor the tail of the alkyl chain. Based on this observation, we use the C=C stretch HD-SFG response to depth-profile the alkyl chain conformation of the unsaturated lipid. We find that the first 1/3 of carbon atoms from the headgroup are relatively rigid, oriented perpendicular to the surface. In contrast, the remaining carbon atoms can be approximated as free rotators, introducing the disordering of the alkyl chains.

Measuring Rolling Friction at the Nanoscale.

Colloidal probe microscopy, a technique whereby a microparticle is affixed at the end of an atomic force microscopy (AFM) cantilever, plays a pivotal role in enabling the measurement of friction at the nanoscale and is of high relevance for applications and fundamental studies alike. However, in conventional experiments, the probe particle is immobilized onto the cantilever, thereby restricting its relative motion against a countersurface to pure sliding. Nonetheless, under many conditions of interest, such as during the processing of particle-based materials, particles are free to roll and slide past each other, calling for the development of techniques capable of measuring rolling friction alongside sliding friction. Here, we present a new methodology to measure lateral forces during rolling contacts based on the adaptation of colloidal probe microscopy. Using two-photon polymerization direct laser writing, we microfabricate holders that can capture microparticles, but allow for their free rotation. Once attached to an AFM cantilever, upon lateral scanning, the holders enable both sliding and rolling contacts between the captured particles and the substrate, depending on the interactions, while simultaneously giving access to normal and lateral force signals. Crucially, by producing particles with optically heterogeneous surfaces, we can accurately detect the presence of rotation during scanning. After introducing the workflow for the fabrication and use of the probes, we provide details on their calibration, investigate the effect of the materials used to fabricate them, and report data on rolling friction as a function of the surface roughness of the probe particles. We firmly believe that our methodology opens up new avenues for the characterization of rolling contacts at the nanoscale, aimed, for instance, at engineering particle surface properties and characterizing functional coatings in terms of their rolling friction.

Identification of roll damping coefficient using the free rotation method

The free rotation method represents the simplest method for roll damping coefficient identification in experimental aerodynamics. To apply this method, it is necessary to spin the model to a desired angular velocity and then release the model to spin freely under flow conditions, recording the variation in time of the model’s rolling rate. Thus, applying the logarithmic decrement formula at any roll rate between near zero and the desired angular velocity, the roll damping moment will be calculated. This paper presents the application of the free rotation method on raw data obtained for different Mach numbers and incidences, considering different regression functions, time windows and their implications. Last but not least, the necessary correction methods and their impact on the results are presented.

Research advances of cardo fluorene-based polymer based membranes for gas separation

Gas membrane separation has become one of the technologies to solve major problems in energy, environment and other fields. As the foundation and core of membrane separation technology, high performance membrane materials have always been the focus of research. Membranes based on organic polymer materials are the main commercial gas separation membranes due to their advantages of high design freedom, easy membrane formation and low cost. However, the application of most membranes based on polymer materials are limited by the mutual restriction between permeability and selectivity. The introduction of large volume and twisted groups into the polymer chain can effectively improve gas separation performance. Fluorenyl shows unique large space volume and rigid twisted structure, the introduction of which in polymers will limit the free rotation of the polymer backbone, forming loose accumulations of chain to increase the free volume, eventually improving the gas separation performance of the membranes. Therefore, fluorenyl is favored in the field of gas separation membranes. In this paper, the recent studies on membranes based on fluorene-based polymer materials in the field of gas separation are reviewed. These researches are classified by the structure of polymer materials that make up the membranes and introduced in terms of synthesis, separation mechanism and performance. Finally, the future research directions of fluorene-based polymer gas separation membrane is prospected.

Renewable Electrochemiluminescence Biosensor Based on Eu-MOGs as a Highly Efficient Emitter and a DNAzyme-Mediated Dual-drive DNA Walker as a Signal Amplifier for Ultrasensitive Detection of miRNA-222.

Herein, novel europium metal-organic gels (Eu-MOGs) with excellent cathode electrochemiluminescence (ECL) emission are first used to construct biosensors for the ultrasensitive detection of miRNA-222. Impressively, N and O elements of organic ligand 2,2':6,2″-terpyridine 4,4',4″-tricarboxylic acid (H3-tctpy) can perfectly coordinate with Eu3+ to form Eu-MOGs, which not only reduce nonradiative transition caused by the intramolecular free rotation of phenyl rings in other MOGs to enhance the ECL signal with extraordinary ECL efficiency as high as 37.2% (vs the [Ru(bpy)3]2+/S2O82- ECL system) but also reinforce ligand-to-metal charge transfer (LMCT) by the strong affinity between Eu3+ and N and O elements to greatly improve the stability of ECL signals. Besides, an improved nucleic acid cascade amplification reaction is developed to greatly raise the conversion efficiency from target miRNA-222 to a DNAzyme-mediated dual-drive DNA walker as output DNA, which can simultaneously shear the specific recognition sites from two directions. In that way, the proposed biosensor can further enhance the detection sensitivity of miRNA-222 with a linear range of 10 aM-1 nM and a detection limit (LOD) of 8.5 aM, which can also achieve an accurate response in cancer cell lysates of MHCC-97L and HeLa. Additionally, the biosensor can be self-regenerated by the folding/unfolding of related triplets with pH changes to simplify experimental operations and reduce the cost. Hence, this work proposed novel MOGs with stable and intense ECL signals for the construction of a renewable ECL biosensor, supplying a reliable detection method in biomarker analysis and disease diagnosis.

Presurgical Simulation for Brain Arteriovenous Malformation

Surgical extirpation of brain arteriovenous malformations(AVMs)requires precise pre-surgical simulation. Utilizing image software, widely used with picture archiving and communication systems(PACS), surgeons can generate simulation images that precisely illustrate the proper feeders, passing arteries, and drainers. The crucial steps for creating informative simulation images include: (1)the free rotation of reconstructed 3D digital subtraction angiography(DSA)images; (2)removal of irrelevant arteries(the most important procedure); and(3)construction of stereo imagery of the "core images." This article presents a detailed description of these procedures.

Dissecting lysosomal viscosity fluctuations in live cells and liver tissues with an ingenious NIR fluorescent probe

Viscosity is a pivotal component in the cell microenvironment, while lysosomal viscosity fluctuation is associated with various human diseases, such as tumors and liver diseases. Herein, a near-infrared fluorescent probe (BIMM) based on merocyanine dyes was designed and synthesized for detecting lysosomal viscosity in live cells and liver tissue. The increase in viscosity restricts the free rotation of single bonds, leading to enhanced fluorescence intensity. BIMM exhibits high sensitivity and good selectivity, and is applicable to a wide pH range. BIMM has near-infrared emission, and the fluorescent intensity shows an excellent linear relationship with viscosity. Furthermore, BIMM possessing excellent lysosomes-targeting ability, and can monitor viscosity changes in live cells stimulated by dexamethasone, lipopolysaccharide (LPS), and nigericin, and differentiate between cancer cells and normal cells. Noticeably, BIMM can accurately analyze viscosity changes in various liver disease models with HepG2 cells, and is successfully utilized to visualize variations in viscosity on APAP-induced liver injury. All the results demonstrated that BIMM is a powerful wash-free tool to monitor the viscosity fluctuations in living systems.

FRP bending-active gridshells: Numerical simulation and model test

Bending-active gridshells are a distinct category of grid structures achieved through elastic bending of initially straight profiles arranged in perpendicular layers and interconnected by hinge joints. These joints permit free in-plane rotation, thereby enabling the progressive transformation from the initial planar configuration to the desired curved shape. Rigorous modelling of hinge joint behavior is crucial for an accurate simulation of bending-active gridshells. Nevertheless, prior numerical studies have relied on oversimplified approximations in this regard. To overcome these limitations, this study developed an explicit dynamic numerical procedure, where the hinge joints are modelled as rigid links characterized by paired nodes that represent the actual hinge length. The proposed procedure incorporates all six nodal degrees of freedom (DoFs). This not only facilitates modelling the spatial behavior of the constituent profiles but, more importantly, allows for independent treatment of the in-plane rotational DoFs of a hinge joint’s paired nodes. Simultaneously, it addresses the joint’s coupling behavior in relation to the translational and out-of-plane rotational DoFs. The proposed procedure was verified through benchmark numerical tests. Furthermore, validation was conducted through forming and loading tests on a 4.60-m-span bending-active gridshell model constructed from carbon fiber-reinforced polymer (CFRP) strips.

Synthesis of a New Heterocyclic System: Pyrimidine Structural Analogues of Natural Integrastatins A, B

AbstractIn this paper for the first time, we report a simple one-step synthesis of 5-methyl-11,12-dihydro-5H-5,11-epoxybenzo[7,8]oxocino[4,3-d]pyrimidine derivatives by acid-catalyzed cyclization reaction of various 4-methyl-5-acetyl pyrimidine derivatives with salicylic aldehyde. It was shown that 2-substituted 4-methyl-5-acetylpyrimidines successfully react to form a cyclization product. At the same time, 4-methyl-5-acetylpyrimidines with a substituent in the 6th position do not enter into the cyclization reaction. This may be caused by the negative effect of substituents in the 6th position, which hinder the free rotation of the acetyl group and prevent the formation of a stable pre-reaction complex. The structures of the obtained 5-methyl-11,12-dihydro-5H-5,11-epoxybenzo[7,8]oxocino[4,3-d]pyrimidine derivatives were confirmed using 1H NMR and 13C NMR spectroscopy, mass spectrometry, and X-ray diffraction analysis.

Chirality effects in panto-cylindrical structures

In this paper, we apply a numerical integration strategy recently developed for determining the deformation shapes of structures constituted by Cosserat rods, to predict the behavior of panto-cylinders. Panto-cylinders have, as microstructure, a set of two families of helicoidal beams interconnected by perfect or elastic joints. The pivot’s free rotation axis is, in the reference configuration, orthogonal to the cylindrical surfaces spanned by the beams. We perform a series of numerical simulations looking for the mechanical parameters which exalt the chirality effects in the structure. For the performed compression, extensions, shear, and torsion tests, we find chiral deformation patterns with a dependence on the type of joint and its length.

Rational Modified Organic Functional Charge‐Transfer Complexes toward Optical/Photothermal Behavior Tuning through Decay Pathway Regulation

AbstractDoping has been proven to be a good way to regulate the optical and electrical properties of the active elements including both inorganic and organic materials. In this paper, the study demonstrates a bipolar doping strategy for an intrinsic charge‐transfer binary‐complex through the use of p‐ and n‐type dopants, which incorporate toward highly‐ordered ternary complexes. Benefitting from the good lattice matching and energy level tuning, the supramolecular system with a large doping concentration range (0 ≤ x ≤ 50% or 40%) assembles into the original crystal lattice and exhibits tunable luminescence or quenching phenomena even at very low ratio. The 7h‐benzo[c]carbazole (BCZ) dopped cocrystals show yellow–green to red emission due to the Förster resonance energy transfer (FRET); while only 5% 7,7,8,8‐tetracyanoquinodimethane (TCNQ) dopant can bring superior photothermal (PT) behavior with a high PT conversion efficiency up to 75.3%, owing to the efficient non‐radiative decay way contribution. It is believed that the strong π–π interactions and free rotation of −C(C≡N)2 promote this decay way transition. This work on the charge‐transfer complex doping system suggests the great potential in optical, photothermal imaging, and therapy applications as well as information memory and photo sensing.

Modification of Humeral Component Results in Increased Impingement Free Range of Motion in a Reverse Shoulder Arthroplasty Model.

Shoulder arthroplasties have been demonstrated to provide reliable pain relief as well as functional benefits. The advent of the reverse shoulder arthroplasty allowed for expanded indications for shoulder replacement. Several studies comparing the outcomes of anatomic and reverse total shoulder arthroplasties have demonstrated decreased range of motion in the reverse arthroplasty cohort, especially in internal rotation. The authors hypothesized that slight modifications to the humeral component of a reverse shoulder arthroplasty could result in increased impingement free range of motion without significant sacrifices to stability. A reverse shoulder arthroplasty model was fashioned to mimic a setting of anterior mechanical impingement after replacement. Sequential resections were taken from the anterior aspect of the polyethylene up to a resection of 10 mm. A solid modeling software was utilized to compare the experimental group to the control group with regard to impingement free motion. Finite element analysis was subsequently utilized to assess stability of the construct in comparison to the nonmodified polyethylene. Impingement free internal rotation increased minimally at 3 mm of resection but considerably at each further increase in resection. A resection of 10 mm resulted roughly 30% improvement in impingement free internal rotation. Instability in this model increased with modifications beyond 7 mm. Slight alterations to the geometry of the humeral tray and polyethene components can result in improvements in impingement-free internal rotation without substantial increased instability in this model. Further work is needed to determine in vivo implications of modifications to the humeral tray and polyethylene.

Intelligent Tension Correction Method for EME Sensors considering Torsion Effect of Wire Rope Suspender Cables

Long‐term and accurate monitoring of suspender cable tensions is particularly important for safe evaluation of cable suspension bridges or tied‐arch bridges. Torsional deformation, commonly present in wire rope suspender cables (WR cables) during tensioning construction or in‐service, has not been considered in the elasto‐magneto‐electric (EME) sensor system. This study investigated the effects of torsion on tension measurement and proposed an intelligent correction method without measuring the torsion angles per unit length. A calibration platform for full‐scale WR cable is established with a rotation angle fixing device. Tension calibration experiments were carried out under free rotation condition without activating the angle fixing device and under various fixed rotation conditions by setting a series of initial fixed angles at the anchor head. It was found that the relative error for the EME sensor using the traditional calibration method under the free rotation condition could reach 11.72%. To improve the accuracy, an intelligent tension correction method for the torsion effect is proposed, which uses the experimental signals in various fixed conditions and the backpropagation neural network with K‐fold cross‐validation. The parameters of the BPNN were optimized by genetic algorithm, and it was found that the maximum relative error decreases from 11.72% to 5.24% and the maximum absolute error decreases from 21.75 kN to 14.67 kN for the condition of free rotation. Finally, the EME sensor with intelligent tension correction method was applied to a real suspension bridge. The measurement relative error of the field test decreases from 6.60% without the torsion compensation to 2.80% with the torsion compensation, which indicate that the proposed intelligent tension correction method can ensure the accurate tension measurement of the WR cables by the EME sensor.

Accidental triplet harvesting in donor-acceptor dyads with low spin-orbit coupling.

We present an accidental mechanism for efficient intersystem crossing (ISC) between singlet and triplet states with low spin-orbit coupling (SOC) in molecules having donor-acceptor (D-A) moieties separated by a Sigma bond. Our study shows that SOC between the lowest singlet excited state and the higher-lying triplet states, together with nuclear motion-driven coupling of this triplet state with lower-lying triplet states during the free rotation about a Sigma bond, is one of the possible ways to achieve the experimentally observed ISC rate for a class of D-A type photoredox catalysts. This mechanism is found to be the dominant contributor to the ISC process with the corresponding rate reaching a maximum at a dihedral angle in the range of 72°-78° between the D-A moieties of 10-(naphthalen-1-yl)-3,7-diphenyl-10H-phenoxazine and other molecules included in the study. We have further demonstrated that the same mechanism is operative in a specific spirobis[anthracene]dione molecule, where the D and A moieties are interlocked near to the optimal dihedral angle, indicating the plausible effectiveness of the proposed mechanism. The present finding is expected to have implications in strategies for the synthesis of new generations of triplet-harvesting organic molecules.

A microenvironment-sensitive red emissive probe with a large Stokes shift for specific recognition and quantification of serum albumin in complex biofluids and live cells.

Human serum albumin (HSA) is regarded as a useful biomarker for rapid medical diagnosis of various disorders mainly related to the kidneys and liver. Hence, it is crucial to identify and monitor the HSA level in complex biofluids (urine and blood samples) using a simple approach. Herein, we have designed and synthesized an intramolecular charge transfer (ICT) based environment-sensitive fluorescent molecular probe, (E)-2-(3-(2-(5-methoxy-1H-indol-3-yl)vinyl)-5,5-dimethylcyclohex-2-en-1-ylidene)malononitrile (DCI-MIN), that can selectively interact with HSA in PBS buffer solution and exhibit a ∼78-fold enhancement in fluorescence intensity with a significant Stokes shift (∼126 nm), which is important to avoid interference from the excitation light. The significant red fluorescence response can be attributed to the suppression of free intramolecular rotation of the DCI-MIN probe inside the hydrophobic binding cavity of HSA and the low polar microenvironment present within HSA. According to the 3σ/slope method, the detection limit was found to be 1.01 nM (0.0671 mg L-1) in aqueous solutions, which is significantly lower than the normal level of HSA in healthy urine and blood serum, indicating its high sensitivity. DCI-MIN has the ability to exhibit useful applications, including the detection and quantification of HSA concentration in complex biofluids (human urine and blood samples) as well as the imaging of serum albumin in living cells.

Approaching the free rotor limit: extremely low methyl torsional barrier observed in the microwave spectrum of 2,4-dimethylfluorobenzene.

The microwave spectrum of 2,4-dimethylfluorobenzene was recorded using a molecular jet Fourier transform microwave spectrometer in the frequency range from 2.0 to 26.5 GHz. The spectral assignment and modeling were challenging due to the large tunnelling splittings resulting from the very low barrier to internal rotation of the p-methyl group that approaches the free rotor limit. Internal rotation splittings arising from two inequivalent o- and p-methyl groups were observed, analysed and modelled using the modified version of the XIAM code and the BELGI-Cs-2Tops code, giving a root-mean-square deviation of 549.1 kHz and 4.5 kHz, respectively, for a data set of 885 rotational lines. The torsional barriers of the o- and p-methyl groups were determined to be 227.039(51) cm-1 and 3.23(40) cm-1, respectively. The V3 barrier observed for the p-methyl group is lower than in any other para-methyl substituted toluene derivatives with coupled internal rotations, becoming the lowest value ever observed to date. The barrier to internal rotation of the o-methyl group next to a fluorine atom is consistently around 220 cm-1, as confirmed by comparing it to barriers observed in other toluene derivatives. The experimental rotational constants were compared to those obtained by quantum chemical calculations.

Numerical investigation of free rotor aerodynamics

Numerical investigation of free rotor aerodynamics

Inherently chiral nor-heteracalixarenes: design and synthesis via enantioselective intramolecular Suzuki-Miyaura reaction.

There has been a recent upsurge in research aimed at synthesizing inherently chiral molecules devoid of point, axial, planar and helical chiralities. We present herein our design and enantioselective synthesis of a series of inherently chiral macrocycles. These compounds, termed nor-heteracalixaromatics, feature a biaryl bond that replaces one of the aryl-heteroatom-aryl linkages found in classic heteracalix[4]aromatics. Macrocyclization of linear achiral substrates via an intramolecular Suzuki-Miyaura cross-coupling reaction affords the 15-membered cyclophane without any chiral elements in high yields and enantioselectivities. Notably, the formation of the aryl-aryl bond does not induce axial chirality at the biaryl linkage. Instead, it restricts the free rotation of an aromatic ring located four bonds away, leading to the inherent chirality of the macrocycle. The intriguing chiroptical properties of these compounds made them promising platform for the development of CPL emitters.