Engineering Nano/Microscale Chiral Self‑Assembly in 3D Printed Constructs

Helical hierarchy found in biomolecules like cellulose,chitin,and collagen underpins the remarkable mechanical strength and vibrant colors observed in living organisms.This study advances the integration of helical/chiral assembly and 3D printing technology,providing precise spatial control over chiral nano/microstructures of rod-shaped colloidal nanoparticles in intricate geometries.We designed reactive chiral inks based on cellulose nanocrystal(CNC)suspensions and acrylamide monomers,enabling the chiral assembly at nano/microscale,beyond the resolution seen in printed materials.We employed a range of complementary techniques including Orthogonal Superposition rheometry and in situ rheo-optic measurements under steady shear rate conditions.These techniques help us to understand the nature of the nonlinear flow behavior of the chiral inks,and directly probe the flow-induced microstructural dynamics and phase transitions at constant shear rates,as well as their post-flow relaxation.Furthermore,we analyzed the photo-curing process to identify key parameters affecting gelation kinetics and structural integrity of the printed object within the supporting bath.These insights into the interplay between the chiral inks self-assembly dynamics,3D printing flow kinematics and photopolymerization kinetics provide a roadmap to direct the out-of-equilibrium arrangement of CNC particles in the 3D printed filaments,ranging from uniform nematic to 3D concentric chiral structures with controlled pitch length,as well as random orientation of chiral domains.Our biomimetic approach can pave the way for the creation of materials with superior mechanical properties or programable photonic responses that arise from 3D nano/microstructure and can be translated into larger scale 3D printed designs.

First evidence for chiral wobbling of triaxial nuclei

Chirality(Greek“handiness”)is a property of many com-plex molecules.Chiral molecules exist in two forms,one being the mirror image of the other.Like for our hands,it is impossible to make the images identical by a suitable rota-tion.The two forms are called left-handed and right-handed.They have the same binding energy,because the electro-magnetic interaction,which holds the molecule together,does not change under a reflection.Other properties that are insensitive to the geometry are also the same.The different geometry is the reason why the left-handed form turns the polarization plane of transmitted light in one direction by some angle while the right-handed form turns it in the oppo-site direction by the same angle.However,the geometrical differences between the two species may have other conse-quences.The two species of the carvon molecule shown in Fig.1 taste quite differently.

Chiral Pair Density Waves with Residual Fermi Arcs in RbV_(3)Sb_(5)

The chiral 2×2 charge order has been reported and confirmed in the kagome superconductor RbV_(3)Sb_(5),while its interplay with superconductivity remains elusive owing to its lowest superconducting transition temperature Tc of about 0.85K in the AV_(3)Sb_(5) family(A=K,Rb,Cs)that severely challenges electronic spectroscopic probes.Here,utilizing dilution-refrigerator-based scanning tunneling microscopy down to 30 mK,we observe chiral 2×2 pair density waves with residual Fermi arcs in RbV_(3)Sb_(5).We find a superconducting gap of 150 μeV with substantial residual in-gap states.The spatial distribution of this gap exhibits chiral 2×2 modulations,signaling a chiral pair density wave(PDW).Our quasi-particle interference imaging of the zero-energy residual states further reveals arc-like patterns.We discuss the relation of the gap modulations with the residual Fermi arcs under the space-momentum correspondence between PDW and Bogoliubov Fermi states.

Advancing ophthalmic delivery of flurbiprofen via synergistic chiral resolution and ion-pairing strategies

Flurbiprofen(FB),a nonsteroidal anti-inflammatory drug,is widely employed in treating ocular inflammation owing to its remarkable anti-inflammatory effects.However,the racemic nature of its commercially available formulation(Ocufen^(R))limits the full potential of its therapeutic activity,as the(S)-enantiomer is responsible for the desired antiinflammatory effects.Additionally,the limited corneal permeability of FB significantly restricts its bioavailability.In this study,we successfully separated the chiral isomers of FB to obtain the highly active(S)-FB.Subsequently,utilizing ion-pairing technology,we coupled(S)-FB with various counter-ions,such as sodium,diethylamine,trimethamine(TMA),and l-arginine,to enhance its ocular bioavailability.A comprehensive evaluation encompassed balanced solubility,octanol-water partition coefficient,corneal permeability,ocular pharmacokinetics,tissue distribution,and in vivo ocular anti-inflammatory activity of each chiral isomer salt.Among the various formulations,S-FBTMA exhibited superior water solubility(about 1–12 mg/ml),lipid solubility(1<lgP_(ow)<3)and corneal permeability.In comparison to Ocufen^(R),S-FBTMA demonstrated significantly higher in vivo antiinflammatory activity and lower ocular irritability(such as conjunctival congestion and tingling).The findings from this research highlight the potential of chiral separation and ion-pair enhanced permeation techniques in providing pharmaceutical enterprises focused on drug development with a valuable avenue for improving therapeutic outcomes.

Chiral bound states in a staggered array of coupled resonators

We study the chiral bound states in a coupled-resonator array with staggered hopping strengths,which interacts with a two-level small atom through a single coupling point or two adjacent ones.In addition to the two typical bound states found above and below the energy bands,this system presents an extraordinary chiral bound state located within the energy gap.We use the chirality to quantify the breaking of the mirror symmetry.We find that the chirality value undergoes continuous changes by tuning the coupling strengths.The preferred direction of the chirality is controlled not only by the competition between the intracell and the intercell hoppings in the coupled-resonator array,but also by the coherence between the two coupling points.In the case with one coupling point,the chirality values varies monotonously with difference between the intracell hopping and the intercell hoppings.While in the case with two coupling points,due to the coherence between the two coupling points the perfect chiral states can be obtained.

Nonreciprocal transport in the superconducting state of the chiral crystal NbGe_(2)

Due to the lack of inversion,mirror or other roto-inversion symmetries,chiral crystals possess a well-defined handedness which,when combined with time-reversal symmetry breaking from the application of magnetic fields,can give rise to directional dichroism of the electrical transport phenomena via the magnetochiral anisotropy.In this study,we investigate the nonreciprocal magneto-transport in microdevices of NbGe_(2),a superconductor with structural chirality.A giant nonreciprocal signal from vortex motions is observed during the superconducting transition,with the ratio of nonreciprocal resistance to the normal resistanceγreaching 6×10^(5)T^(-1)·A^(-1).Interestingly,the intensity can be adjusted and even sign-reversed by varying the current,the temperature,and the crystalline orientation.Our findings illustrate intricate vortex dynamics and offer ways of manipulation on the rectification effect in superconductors with structural chirality.

Boosting photocatalytic hydrogen evolution enabled by SiO_(2)-supporting chiral covalent organic frameworks with parallel stacking sequence

Two-dimensional covalent organic frameworks(2D COFs)feature extendedπ-conjugation and ordered stacking sequence,showing great promise for high-performance photocatalysis.Periodic atomic frameworks of 2D COFs facilitate the in-plane photogenerated charge transfer,but the precise ordered alignment is limited due to the non-covalentπ-stacking of COF layers,accordingly hindering out-of-plane transfer kinetics.Herein,we address a chiral induction method to construct a parallelly superimposed stacking chiral COF ultrathin shell on the support of SiO_(2) microsphere.Compared to the achiral COF analogues,the chiral COF shell with the parallel AA-stacking structure is more conducive to enhance the built-in electric field and accumulates photogenerated electrons for the rapid migration,thereby affording superior photocatalytic performance in hydrogen evolution from water splitting.Taking the simplest ketoenamine-linked chiral COF as a shell of SiO_(2) particle,the resulting composite exhibits an impressive hydrogen evolution rate of 107.1 mmol g^(-1)h^(-1)along with the apparent quantum efficiency of 14.31% at 475 nm.Furthermore,the composite photocatalysts could be fabricated into a film device,displaying a remarkable photocatalytic performance of 178.0 mmol m^(-2)h^(-1)for hydrogen evolution.Our work underpins the surface engineering of organic photocatalysts and illustrates the significance of COF stacking structures in regulating electronic properties.

A Multifunctional Chiral Metasurface with Asymmetric Transmission and Linear-Polarization Conversion

In this paper,a multifunctional chiral metasurface is presented to achieve asymmetric transmission(AT)and linear-polarization conversion(LPC).The designed metasurface consists of a cross swords-like shape and two holes in the lower side of the unit cell.In the frequency band from 8.3 GHz to 10.4 GHz,AT is realized with more than 90%efficiency and the same chiral metasurface transforms linear polarized wave into its orthogonal counterpart with high efficiency.For LPC,the polarization conversion ratio(PCR)is greater than 95%.The proposed metasurface is stable against the incident angles of striking electromagnetic(EM)waves up to 60°for both operations of AT and LPC.

Enantiodifferentiation of chiral diols and diphenols via recognition-enabled chromatographic^(19)F NMR

A novel and efficient method for distinguishing between chiral diols and diphenols has been established through the use of^(19)F NMR spectroscopy.Central to this system's efficacy is a chiral amine,strategically modified with a CF_(3)group.This amine reacts in-situ with 2-formylphenylboronic acid to create a chiral^(19)F-labeled probe.This probe demonstrates discriminatory capabilities by interacting with hydroxy-containing analytes to form boronic esters.These esters produce distinct^(19)F NMR signals that vary according to their stereoconfiguration,facilitating accurate chiral differentiation.The method's resolution capacity was demonstrated by successfully identifying 12 distinct chiral analytes(six pairs of enantiomers)in complex mixtures,highlighting its extensive potential in diverse chiral analysis applications.

Topology optimization of chiral metamaterials with application to underwater sound insulation

Chiral metamaterials have been proven to possess many appealing mechanical phenomena,such as negative Poisson's ratio,high-impact resistance,and energy absorption.This work extends the applications of chiral metamaterials to underwater sound insulation.Various chiral metamaterials with low acoustic impedance and proper stiffness are inversely designed using the topology optimization scheme.Low acoustic impedance enables the metamaterials to have a high and broadband sound transmission loss(STL),while proper stiffness guarantees its robust acoustic performance under a hydrostatic pressure.As proof-of-concept demonstrations,two specimens are fabricated and tested in a water-filled impedance tube.Experimental results show that,on average,over 95%incident sound energy can be isolated by the specimens in a broad frequency range from 1 k Hz to 5 k Hz,while the sound insulation performance keeps stable under a certain hydrostatic pressure.This work may provide new insights for chiral metamaterials into the underwater applications with sound insulation.

Inverse Electromagnetic Scattering by a Penetrable Chiral Object

We consider the inverse electromagnetic scattering problem of determining the shape of a perfectly conducting core inside a penetrable chiral body. We prove the well-posedness of the corresponding direct scattering problem by the variational method. We focus on a uniqueness result for the inverse scattering problem that is under what conditions an obstacle can be identified by the knowledge of the electric far-field pattern corresponding to all time-harmonic incident planes waves with a fixed wave number. To this end, we establish a chiral mixed reciprocity relation that connects the electric far-field pattern of a spherical wave with the scattered field of a plane wave.

Effect of the mixing of s-wave and chiral p-wave pairings on electrical shot noise properties of normal metal/superconductor tunnel junctions

We study theoretically the electrical shot noise properties of tunnel junctions between a normal metal and a superconductor with the mixture of singlet s-wave and chiral triplet p-wave pairing due to broken inversion symmetry. We investigate how the shot noise properties vary as the relative amplitude between the two parity components in the pairing potential is changed. It is demonstrated that some characteristics of the electrical shot noise properties of such tunnel junctions may depend sensitively on the relative amplitude between the two parity components in the pairing potential, and some significant changes may occur in the electrical shot noise properties when the relative amplitude between the two parity components is varied from the singlet s-wave pairing dominated regime to the chiral triplet p-wave pairing dominated regime. In the chiral triplet p-wave pairing dominated regime, the ratio of noise power to electric current is close to 2e both in the in-gap and in the out-gap region. In the singlet s-wave pairing dominated regime, the value of this ratio is close to 4e in the inner gap region but may reduce to about 2e in the outer gap region as the relative amplitude of the chiral triplet pairing component is increased. The variations of the differential shot noise with the bias voltage also exhibit some significantly different features in different regimes. Such different features can serve as useful diagnostic tools for the determination of the relative magnitude of the two parity components in the pairing potential.

CHIRALPAK AD柱在14种药物手性分离中的应用

目的建立氟比洛芬、班布特罗等14种手性药物的高效液相色谱手性拆分方法。方法利用chiralpak AD手性柱,以正己烷-乙醇为流动相基本成分,调整两者不同比例和添加不同量的三氟乙酸(TFA)或三乙胺(TEA),对氟比洛芬、酮洛芬、扁桃酸、氟伐他汀、邻氯扁桃酸、依托度酸、布洛芬、萘普生等8个酸性手性药物,和班布特罗、普罗帕酮、西替利嗪、非洛地平、尼群地平、尼莫地平等6个碱性手性药物进行了拆分研究。考察了流动相中正己烷和乙醇的比例、TFA或TEA添加量对手性分离的影响。结果在一定色谱条件下,被检样品中大部分手性药物的两个对映体实现了较好分离。在正己烷-乙醇流动相系统中,正己烷含量为90%～99%,TFA含量为0.1%～0.3%的条件下,氟比洛芬、酮洛芬、扁桃酸、氟伐他汀、邻氯扁桃酸、依托度酸、布洛芬两对映体间的分离度(Rs)分别为11.0,12.5,4.70,5.30,1.90,1.50,1.60。但萘普生的两个对映体在上述各条件下始终未获得分离。在正己烷-乙醇-TEA(40∶60∶0.05)流动相体系中,逐渐提高正己烷比例和TEA含量,普罗帕酮、西替利嗪、班布特罗、尼群地平、非洛地平的两个对映体色谱峰达到基线分离,分离度分别为8.20,3.0,1.90,1.90和1.60。但尼莫地平始终未获分离。结论建立的手性HPLC能有效拆分氟比洛芬、班布特罗等12个手性药物对映体。

在Chiral-AGP柱上分离氟布洛芬、罗哌卡因、西替利嗪和反式-2-苯基环丙基硼酸等外消旋体化合物

应用HPLC方法在 10 0mm× 4.6mm的Chiral AGP手性固定相柱上 ,分离氟布洛芬、西替利嗪、罗哌卡因等手性药物和反式 2 苯基环丙基硼酸的对映体混合物 .考察了流动相pH值和缓冲液浓度等对样品在柱上的保留和分离的影响 ,研究了流动相中加入四种不带电荷的有机添加剂乙腈、甲醇、正丙醇和异丙醇以及加入不同浓度的有机添加剂等对对映体分离性的影响 .此方法用于手性药物合成中的对映过量值的测定 ,取得满意的效果 .

用Chiralpak AD-H手性色谱柱HPLC法拆分阿罗洛尔对映体

目的:建立拆分阿罗洛尔手性对映体的手性固定相HPLC法。方法:采用纤维素直链淀粉类手性固定相Chiralpak AD-H色谱柱(250mm×4.6mm,5μm),考察了流动相比例、流速、碱性添加剂等因素对阿罗洛尔手性对映体拆分效果的影响。结果:确定了最佳拆分条件:流动相为正己烷-乙醇-二乙胺-三乙胺=30∶70∶0.1∶0.1(V/V),流速为0.4ml/min,检测波长为315nm,柱温为25℃,阿罗洛尔对映体拆分的分离度为3.033,对映体能够得到良好的拆分。结论:该法操作简便,可用于阿罗洛尔对映体的分离及质量控制。

用MEI—FD方法分析Chiral媒质的电磁散射问题

本文应用不变性测试分程和有限差分方法分析Ｃｈｉｒａｌ媒质的电磁散射问题。应用该方法时，要在所讨论的区域内建立起一组有关电场和磁场的耦合差分方程，并且要在截断边界上应用不变性测试方程建立起有关边界点系数的方程。文中给出了一些非均匀。

CHIRALCEL OD手性柱直接拆分萘普生对映体

以CHIRALCELOD为固定相,建立了在正相条件下直接拆分萘普生对映体的HPLC方法。考察了流动相组成、流速、进样量和温度等因素对对映体分离的影响。优化后的色谱条件为:CHIRACELOD色谱柱(250mm×4.6mm,10μm);流动相:正己烷-异丙醇-冰醋酸(97∶3∶1,V/V);流速:1.0mL/min;紫外检测波长:254nm;柱温:35℃。在此条件下,萘普生对映体可得到基线分离。此方法可用于S-萘普生制备时酶膜反应器中萘普生甲酯动态拆分过程的跟踪分析。

Chiralpak AD和Chiralcel OD-H手性固定相拆分3α-酰氧基-6β-乙酰氧基莨菪烷类化合物

采用高效液相色谱法,以不同配比的正己烷-异丙醇为流动相,在正相色谱条件下,考察了6个3α-酰氧基-6β-乙酰氧基莨菪烷对映体在淀粉型手性固定相Chiralpak AD、纤维素型手性固定相Chiralcel OD-H上的分离情况,以建立该类化合物的手性拆分方法。结果表明,在Chiralpak AD手性柱上,对映体6实现完全分离,而对映体1完全不能分离;在Chiralcel OD-H柱上,对映体1、4、3分别实现完全分离、基线分离和基本分离,对映体6只能实现部分分离;对映体5在两种手性柱上都完全不能被分离。说明固定相手性空腔的结构对化合物的拆分结果影响很大。研究发现,C-3α位取代基团的空间位阻效应主导手性固定相对对映体的选择性识别作用,而化合物与固定相之间的分子间作用力对手性拆分也产生重要影响。研究结果为其他莨菪烷类化合物的手性拆分提供了参考。

Chiralcel OD-RH直接拆分五味子乙素对映体

采用反相手性色谱柱Chiralcel OD-RH(纤维素3,5-二甲基苯基氨基甲酸酯涂敷在5μm硅胶上)建立了五味子乙素对映体的反相高效液相色谱拆分方法。考察了流动相组成、柱温和流速对五味子乙素手性对映体拆分的影响。以甲醇-水(90∶10)为流动相,流速0.5 mL/min,柱温20℃,检测波长254 nm,在Chiralcel OD-RH手性柱上成功拆分了五味子乙素对映体,其中R-构型先出峰。用lnk对1/T作图得到的Van'tHoff曲线具有良好线性,相关系数(r)均大于0.99,计算了对映体与固定相相互作用的焓变以及焓变差值和熵变差值等热力学参数。结果显示,五味子乙素对映体的拆分过程为焓控过程,即氢键、π-π及偶极-偶极等作用方式对对映体的拆分起重要作用。

Chiralpak AD和Chiralcel OD-H柱分离莨菪烷衍生物对映体的研究

目的采用正相手性色谱柱建立莨菪烷衍生物A和B对映体的高效液相色谱法（HPLC）手性分离方法。方法在正相条件下分别使用Chiralpak AD和Chiralcel OD-H手性柱,考察流动相组成、流速和柱温对对映体手性分离的影响;计算对映体与固定相相互作用的焓变差值和熵变差值等热力学参数。结果化合物A在Chiralpak AD柱上得到最佳色谱分离条件。化合物B在Chiralcel OD-H柱上得到最佳色谱分离条件。在15℃~35℃柱温范围内,lnα对1/T呈线性关系,其手性分离过程受焓控制。结论此HPLC手性分离方法可用于化合物A和B的光学纯度分析和鉴定。