Circularly polarized luminescence(CPL)and two-photon absorption(TPA)materials have garnered considerable attentions due to their minimal energy loss and superior optical penetration[1,2].However,the current challenge ...Circularly polarized luminescence(CPL)and two-photon absorption(TPA)materials have garnered considerable attentions due to their minimal energy loss and superior optical penetration[1,2].However,the current challenge lies in the absence of well-developed strategies for designing materials that combine these two exceptional optical properties.展开更多
The objective of this study was to predict,screen,synthesize,and investigate cocrystals of poorly soluble flavonoids that are commonly found in dietary supplements with bipolar compound picolinic acid(PA).To improve t...The objective of this study was to predict,screen,synthesize,and investigate cocrystals of poorly soluble flavonoids that are commonly found in dietary supplements with bipolar compound picolinic acid(PA).To improve the efficiency and success rate of experimental screening,two virtual tools based on hydrogen bond propensity(HBP)and modified molecular electrostatic potential(MEP)maps were used.The prediction accuracy of HBP and MEP is 58.82%and 94.11%,respectively,presenting that the MEP model is very powerful in the discovery of pharmaceutical cocrystals.Among the 12 successfully obtained cocrystals,4 single crystals of PA with luteolin(LUT),genistein(GEN),taxifolin(TAX),dihydromyricetin(DHM)were obtained for the first time.Charged-assisted O-H…O and N-H…O hydrogen bonds appear as main hydrogen bonding synthons,and PA adopts a zwitterionic form after cocrystallization.GEN-PA,TAX-PA,and DHM-PA showed higher DPPH'radical-scavenging capacities;LUT-PA and DHM-PA showed higher ABTS^(+)radical-scavenging capacities;GEN-PA and DHM-PA possessed better protective effects on H9c2 cells from hypoxic injury caused by CoCl_(2)than corresponding pure flavonoids.展开更多
The selected 18 energetic compounds were theoretically investigated by using the density functional theory（DFT） quantum mechanical code,DMol3,and the Hansen solubility parameters（HSPs） analyses.The results showed ...The selected 18 energetic compounds were theoretically investigated by using the density functional theory（DFT） quantum mechanical code,DMol3,and the Hansen solubility parameters（HSPs） analyses.The results showed that 4-nitrotoluene,4-nitrophenol,N N0-dimethyl-N N0-diphenylurea and N N0-diethyl-N N0-diphenylurea contain relatively electron-rich aromatic rings.Four satisfactory energetic precursors with electron-rich rings were quickly and effectively found by electrostatic potential（ESP）surfaces and HSPs analyses.The results also indicated that the absolute value of the lowest unoccupied molecular orbital（LUMO） of the energetic precursors with electron-rich rings often was less than3.00 eV,and the absolute value of LUMO of the energetic precursors with electron deficient rings was often more than 3.00 eV.Additionally,we found that with at least two eutectic points was a prerequisite for two precursors to form a cocrystal.展开更多
Currently,cocrystallization is a promising strategy for tailoring the physicochemical properties of active pharmaceutical ingredients.Theophylline,an alkaloid and the most primary metabolite of caffeine,is a readily a...Currently,cocrystallization is a promising strategy for tailoring the physicochemical properties of active pharmaceutical ingredients.Theophylline,an alkaloid and the most primary metabolite of caffeine,is a readily available compound found in tea and coffee.It functions primarily as a bronchodilator and respiratory stimulant,making it a mainstay treatment for lung diseases like asthma.Theophylline’s additional potential benefits,including anti-inflammatory and anticancer properties,and its possible role in neurological disorders,have garnered significant research interest.Cocrystal formation presents a viable approach to improve the physicochemical properties of theophylline and potentially mitigate its toxic effects.This review comprehensively explores several successful studies that utilized cocrystallization to favorably alter the physicochemical properties of theophylline or its CCF.Notably,cocrystals can not only enhance the solubility and bioavailability of theophylline but also exhibit synergistic effects with other APIs.The review further delves into the hydrogen bonding sites within the theophylline structure and the hydrogen bonding networks observed in cocrystal structures.展开更多
The pharmaceutical cocrystals and its engineering is widely accepted phenomenon regarding to the enhancement of aqueous solubility of poorly soluble drugs. The pharmaceutical cocrystals have the great ability to impro...The pharmaceutical cocrystals and its engineering is widely accepted phenomenon regarding to the enhancement of aqueous solubility of poorly soluble drugs. The pharmaceutical cocrystals have the great ability to improve the physicochemical properties of drug substance. Cocrystals are formed by the stoichiometric combination of drug substance and the coformer. The drug glimepiride is a third generation oral hypoglycemic sulfonylurea class. Glimepiride is a drug which is get classified as biopharmaceutical classification system (BCS) class II which indicates the glimepiride having low aqueous solubility and high permeability. Cocrystal engineering is a perfect way to increases glimepiride solubility without changing its therapeutic property. The cocrystals were synthesized by the solvent drop grinding as a green chemistry approach. The coformers used to form the cocrystals are succinic acid (SA), Theobromine (TB), caffeine (CF). The synthesized cocrystals are get characterized by vibrational spectroscopy, thermal analysis, molecular crystallography, and optical microscopy. The obtained results shows the formation of cocrystal phase between the drug glimepiride and its coformers.展开更多
Recently,drug-drug cocrystal attracts more and more attention.It offers a low risk,low-cost but high reward route to new and better medicines and could improve the physiochemical and biopharmaceutical properties of a ...Recently,drug-drug cocrystal attracts more and more attention.It offers a low risk,low-cost but high reward route to new and better medicines and could improve the physiochemical and biopharmaceutical properties of a medicine by addition of a suitable therapeutically effective component without any chemical modification.Having so many advantages,to date,the reported drug-drug cocrystals are rare.Here we review the drug-drug cocrystals that reported in last decade and shed light on the opportunities and challenges for the development of drug-drug cocrystals.展开更多
Charge-transfer(CT)stoichiometric cocrystals are promising choice of organic materials for unveiling the structure-property relationship.However,due to the contradiction between large CT degree required for strong NIR...Charge-transfer(CT)stoichiometric cocrystals are promising choice of organic materials for unveiling the structure-property relationship.However,due to the contradiction between large CT degree required for strong NIR absorption and flexible molecular stacking,construction of stoichiomorphism-based cocystals with near-infrared(NIR)photothermal property remains challenging.Herein,the first example of stoichiomorphism-based photothermal cocrystals were accomplished through the adaptive assembly of 3,3,5,5-tetramethylbenzidine(TMB)donor and 1,2,4,5-tetracyanobenzene(TCNB)acceptor.The selective cocrystallization could be controlled by varying the donor-acceptor stoichiometries via a surfactantassisted method,resulting in two cocrystals with 1:1(T1C1)and 1:2(T2C1)stoichiometries.The absorbance intensity of T1C1 at 808 nm was nearly twice that of T2C1,while the photothermal conversion efficiency(PCE)of the former was 60.3%±0.6%,approximately 80%of that for the latter(75.5%±2.6%),which might be caused by the different intermolecular interactions in distinct molecular stacking patterns.Notably,both excellent PCEs of stoichiometric cocrystals were attributed to the nonradiative transition process,including internal conversion and charge dissociation processes,as elucidated by femtosecond transient absorption spectroscopy measurements.Furthermore,T1C1 was used as an NIR heater for preparing agarose-based photothermal hydrogel,showing great potential for light-controlled in-situ gelation.This strategy of balancing the CT degree and molecular packing orientation not only uncovered the relationship between stoichiometric stacking and photothermal property,but also provided an opportunity to develop advanced organic optoelectronic materials.展开更多
Organic photothermal cocrystals have garnered considerable attention owing to their diverse applications in photoacoustic imaging,seawater desalination,and photothermoelectric conversion.Herein,we synthesize an organi...Organic photothermal cocrystals have garnered considerable attention owing to their diverse applications in photoacoustic imaging,seawater desalination,and photothermoelectric conversion.Herein,we synthesize an organic cocrystal,Tri-F_(4)TCNQ,which consists of a donor triphenylene and an acceptor F_(4)TCNQ with a wide absorption wavelength range from visible light to 1800 nm.Furthermore,the Tri-F_(4)TCNQ cocrystal has superior photothermal properties,making it highly promising for photothermal imaging applications.When illuminated with a laser of 1064 nm,the Tri-F_(4)TCNQ cocrystal achieves a high photothermal conversion efficiency(PCE)of 63.6%,which is attributed to the dominant nonradiative pathways and suppressed radiative decay channels.Notably,the Tri-F_(4)TCNQ crystals exhibit magnetism,and a magnetic field can effectively promote photothermal conversion.This is a highly uncommon report about magnetic-responsive photothermal effects in organic cocrystals.Moreover,the Tri-F_(4)TCNQ cocrystal demonstrates remarkable structural stability,photosensitivity,and magnetic field responsiveness,laying a solid foundation for future applications.展开更多
The field of molecular charge transfer cocrystals(CTCs)has advanced rapidly in recent years,with much work focused on their use in optoelectronic devices,photoacoustic imaging,photothermal therapy(PTT),opticalwaveguid...The field of molecular charge transfer cocrystals(CTCs)has advanced rapidly in recent years,with much work focused on their use in optoelectronic devices,photoacoustic imaging,photothermal therapy(PTT),opticalwaveguides,seawater desalination,and more.Organic photothermal CTCs are of particular interest because of their unique phototherapeutic effects in phototherapy and their remarkable imaging capabilities in fluorescence,magnetic resonance,and photoacoustic imaging,further enhancing their significance in medical applications.However,the use of photothermal CTCs in biomedicine has been limited,with few reported biological applications.Hence,there is a growing interest in CT-derived functional photothermal cocrystals potential contenders for targeted and controlled biomedical applications such as bacteria inhibition,cancer eradication,and tissue regeneration.This review offers insight into the recent advancements in crafting and producing CT-based materials with biomedical attributes.In addition,it outlines the current obstacles and future prospects in this burgeoning research domain,aiming to propel the continued advancement of CT-based biomaterials toward enhanced biomedical utilities.Overall,cocrystal-based near-infrared(NIR)photothermal materials have the potential to revolutionize a wide range of medical and technological applications and are an active area of research in chemistry,materials science,and nanotechnology.展开更多
Organic donor-acceptor cocrystals ofπ-conjugated molecues have shown diverse applications in materials science.However,most cocrystals exist in neutral forms dominated byπ-πinteractions,while the ionic congeners an...Organic donor-acceptor cocrystals ofπ-conjugated molecues have shown diverse applications in materials science.However,most cocrystals exist in neutral forms dominated byπ-πinteractions,while the ionic congeners and corresponding properties are rarely studied due to difficulties in harnessing the degree of charge transfer.Herein,we report cocrystals of axially N-embedded quasi-carbon nanohoops(DPP-D and DPP-T)with electron deficient vips.By modulating the electron affinity of the acceptor vips,the electronic structures of the complexes can be tuned from neutral to ionic states.Specifically,DPP-D interacts with TCNB molecules to form neutral superstructures via intermolecularπ-πinteractions,giving rise to a deep-red emission in the solid state.In contrast,an ionic complex showing near-infrared region absorptions and paramagnetic character on account of strong charge-transfer interactions is generated when DDQ molecules are involved.Their unique properties can be explained by different degrees of charge transfer and assembly modes,which have clearly been manifested by crystal structures and theoretical calculations.Our studies provide rare examples ofπ-conjugated macrocycle-based donor-acceptor cocrystals in both neutral and ionic forms,and give insight to the design of multicomponent carbon nanomaterials.展开更多
As an emerging functional material system,organic cocrystals in the near-infrared(NIR)window drive the innovation of novel material systems.In recent years,it has made breakthroughs in optoelectronics,energy conversio...As an emerging functional material system,organic cocrystals in the near-infrared(NIR)window drive the innovation of novel material systems.In recent years,it has made breakthroughs in optoelectronics,energy conversion,and biomedicine,thanks to its unique molecular assembly strategy,charge-transfer characteristics,and multi-dimensional application potential.This paper systematically reviews the design strategies,preparation methods,structure relationships,characterization methods,and cutting-edge applications of this type of material.Finally,it presents prospects for future research directions and challenges.展开更多
Pharmaceutical cocrystals are multicomponent systems in which at least one component is an active pharmaceutical ingredient and the others are pharmaceutically acceptable ingredients.Cocrystallization of a drug substa...Pharmaceutical cocrystals are multicomponent systems in which at least one component is an active pharmaceutical ingredient and the others are pharmaceutically acceptable ingredients.Cocrystallization of a drug substance with a coformer is a promising and emerging approach to improve the performance of pharmaceuticals,such as solubility,dissolution profile,pharmacokinetics and stability.This review article presents a comprehensive overview of pharmaceutical cocrystals,including preparation methods,physicochemical properties,and applications.Furthermore,some examples of drug cocrystals are highlighted to illustrate the effect of crystal structures on the various aspects of active pharmaceutical ingredients,such as physical stability,chemical stability,mechanical properties,optical properties,bioavailability,sustained release and therapeutic effect.This review will provide guidance for more efficient design and manufacture of pharmaceutical cocrystals with desired physicochemical properties and applications.展开更多
Near-infrared organic phototransistors have wide application prospects in many fields.The active materials with the high mobility and near-infrared response are critical to building high-performance near-infrared orga...Near-infrared organic phototransistors have wide application prospects in many fields.The active materials with the high mobility and near-infrared response are critical to building high-performance near-infrared organic phototransistors,which are scarce at present.Herein,a new charge transfer cocrystal using 5,7-dihydroindolo[2,3-b]carbazole(5,7-ICZ)as the donor and 2,2’-(benzo[1,2-b:4,5-b’]dithiophene-4,8-diylidene)dimalononitrile(DTTCNQ)as the acceptor is properly designed and prepared in a stoichiometric ratio(D:A=1:1),which not only displays a high electron mobility of 0.15 cm^(2)V^(-1)s^(-1) and very low dark current,but also can serve as the active layer materials in the region of near-infrared detection due to the narrowed band gap and good charge transport properties.A high photosensitivity of 1.8×10^(4),the ultrahigh photoresponsivity of 2,923 A W-1and the high detectivity of 4.26×10^(11)Jones of the organic near-infrared phototransistors are obtained.展开更多
The organic cocrystal strategy has provided a convenient and efficient platform for preparing organic photothermal materials.However,the rapidly directional preparation of cocrystals with desirable photothermal proper...The organic cocrystal strategy has provided a convenient and efficient platform for preparing organic photothermal materials.However,the rapidly directional preparation of cocrystals with desirable photothermal properties remains challenging due to a lack of suitable design ideas.Here,two new photothermal cocrystals,MTC and MFC,based on acceptor molecules(TCNQ and F4TCNQ)with different electron-withdrawing capacities were quickly prepared by the coprecipitation method,aiming to explore the effect of charge transfer(CT)interaction on photothermal properties.Compared with MTC,the stronger intermolecular CT interaction in MFC facilitates extending the absorption range(from the NIR-I to the NIR-II region)and enhancing the non-radiative transition process.Under the 808 nm laser irradiation,the photothermal conversion efficiency(PCE)of MFC is 54.6%,whereas MTC displays a mere 36.8%.The MFC cocrystal was further combined with a flexible polymer substrate(HPDMS)to prepare a flexible wearable heater(HPDMS@MFC),which exhibits excellent NIR-II photothermal performance.This work points out a research direction for the rapid assembly of efficient photothermal cocrystals and additionally provides an extensive application prospect for organic photothermal cocrystals in the field of wearable devices.展开更多
Pharmaceutical cocrystals are a promising technology that can be used to improve the solubility of poor aqueous compounds. The objective of this study was to systematically investigate the solubility of myricetin(MYR)...Pharmaceutical cocrystals are a promising technology that can be used to improve the solubility of poor aqueous compounds. The objective of this study was to systematically investigate the solubility of myricetin(MYR) cocrystals, including their kinetic solubility, thermodynamic solubility, and intrinsic dissolution rate(IDR). The effects of pH, surfactant, ion concentration, and coformers on the cocrystal solubility were evaluated. Furthermore, single crystal structures of MYR, myricetin–isonicotinamide(MYR–INM) and myricetin–caffeine(MYR–CAF) cocrystals were analyzed to discuss the possible reasons for the enhancement of cocrystal solubility from the perspective of the spatial structure.The results indicated that the kinetic solubility of MYR cocrystals was modulated by pH and cocrystal coformer(CCF) ionization in buffer solution, while it primarily depended on the CCF solubility in pure water. In addition, the solubility of MYR cocrystals was increased in a concentration dependent fashion by the surfactant or ion concentration. The thermodynamic solubility of MYR–INM(1:3) cocrystals decreased with the increases of the pH value of the dissolution media. The IDR of MYR cocrystals was faster than that of MYR in the same medium and extremely fast in pH 4.5 buffer. The improved solubility of MYR cocrystals was probably related to the alternate arrangements of MYR and INM/CAF molecules and increased intermolecular distance. The present study provides some references to investigate the solubility behavior of pharmaceutical cocrystals.展开更多
Organic cocrystals are crystalline,single-phase materials composed of two or more molecular and/or ionic compounds,generally,in a stoichiometric ratio.A feature of organic cocrystals is that special optoelectronic pro...Organic cocrystals are crystalline,single-phase materials composed of two or more molecular and/or ionic compounds,generally,in a stoichiometric ratio.A feature of organic cocrystals is that special optoelectronic properties such as ferroelectricity are easy to realize in these materials.In this perspective,we systematically introduce the recent research advances in organic cocrystal ferroelectrics,and we study in depth the molecular structure and self-assembling behaviors of cocrystals for ferroelectric applications.Finally,combined with an understanding of recent progress and achievements in this field,we discuss the challenges and opportunities for ferroelectric materials based on organic cocrystals,as well as the promising applications of these materials.展开更多
Carbamazepine(CBZ)is an anticonvulsant with very low water solubility,presenting as a white crystalline powder with poor mechanical properties and is hard to bend.To enhance CBZ's physicochemical properties,such a...Carbamazepine(CBZ)is an anticonvulsant with very low water solubility,presenting as a white crystalline powder with poor mechanical properties and is hard to bend.To enhance CBZ's physicochemical properties,such as water solubility and mechanical properties,we selected six cocrystal coformers(CCFs):nicotinamide(NIC),benzamide(BZM),salicylic acid(SCA),fumaric acid(FMA),trimesic acid(TMA),and hesperetin(HPE).Six CBZ cocrystals were successfully prepared using the solution method.Fourier transform infrared spectroscopy(FT-IR),powder X-ray diffraction(PXRD),differential scanning calorimetry(DSC),and single crystal X-ray diffraction(SCXRD)were used to characterize the crystal structures and gain comprehensive insights into the six cocrystals.The mechanical,fluorescence,and solubility properties of the six cocrystals were tested.The results reveal that most of the prepared cocrystals exhibit improved water solubility and mechanical properties when compared to CBZ.Among them,the dissolution rate of cocrystals excluded from CBZ-HPE has increased by an average of 3 or 4 times compared to CBZ,while CBZ-HPE exhibits superior mechanical properties.Moreover,all six cocrystals possess better fluorescence performance than CBZ.We thoroughly evaluated the mechanical properties of the cocrystals through both experimental and theoretical approaches.This work provides a new direction for studying drug cocrystals to improve the physicochemical properties of drugs.展开更多
The nucleation and growth mechanism and polymorph-property correlations in the molecular cocrystal field are widely sought but currently remain unclear. Herein, a new wire-like morphology of phenazine(Phz)-chloranilic...The nucleation and growth mechanism and polymorph-property correlations in the molecular cocrystal field are widely sought but currently remain unclear. Herein, a new wire-like morphology of phenazine(Phz)-chloranilic acid(H2ca) cocrystal(PHC) is demonstrated for the first time, and the self-assembly of Phz and H2ca is controlled to selectively prepare kinetically stable wires and thermodynamically stable plates. Specifically, low precursor concentration is beneficial for one-dimensional(1D) self-assembly along the [010] crystallographic direction, while only supersaturation can trigger 2D self-assembly along the [100] and [010] directions, respectively. This is understandable in terms of the(020) face showing the largest attachment energy(Eatt) and the(002) face possessing the smallest surface energy(Esurf). Moreover, anisotropic Raman spectra related to the mode symmetry and atomic displacements in two types of PHCs are revealed, and the same Raman-active vibrational bands of PHC wire and plate show different polarization responses, which is intrinsically ascribed to their different molecular orientations.Overall, this is the first case that morphologies of cocrystal are precisely tuned with comprehensive investigations of their anisotropic vibrational characteristics.展开更多
Advancements in organic electronics are propelling the development of new material systems,where organic materials stand out for their unique benefits,including tunability and cost-effectiveness.Organic single crystal...Advancements in organic electronics are propelling the development of new material systems,where organic materials stand out for their unique benefits,including tunability and cost-effectiveness.Organic single crystals stand out for their ordered structure and reduced defects,enhancing the understanding of the relationship between structure and performance.Organic cocrystal engineering builds upon these foundations,exploring intermolecular interactions within multicomponent-ordered crystalline materials to combine the inherent advantages of single-component crystals.However,the path to realizing the full potential of organic cocrystals is fraught with challenges,including structural mismatches,unclear cocrystallization mechanisms,and unpredictable property alterations,which complicate the effective cocrystallization between different molecules.To deepen the understanding of this promising area,this review introduces the mechanism of organic cocrystal formation,the various stacking modes,and different growth techniques,and highlights the advancements in cocrystal engineering for multifunctional applications.The goal is to provide comprehensive guidelines for the cocrystal engineering of highperformance molecular materials,thereby expanding the applications of organic cocrystals in the fields of optoelectronics,photothermal energy,and energy storage and conversion.展开更多
Pure drug nanomedicines(PDNs)encompass active pharmaceutical ingredients(APIs),including macromolecules,biological compounds,and functional components.They overcome research barriers and conversion thresholds associat...Pure drug nanomedicines(PDNs)encompass active pharmaceutical ingredients(APIs),including macromolecules,biological compounds,and functional components.They overcome research barriers and conversion thresholds associated with nanocarriers,offering advantages such as high drug loading capacity,synergistic treatment effects,and environmentally friendly production methods.This review provides a comprehensive overview of the latest advancements in PDNs,focusing on their essential components,design theories,and manufacturing techniques.The physicochemical properties and in vivo behaviors of PDNs are thoroughly analyzed to gain an in-depth understanding of their systematic characteristics.The review introduces currently approved PDN products and further explores the opportunities and challenges in expanding their depth and breadth of application.Drug nanocrystals,drug-drug cocrystals(DDCs),antibody-drug conjugates(ADCs),and nanobodies represent the successful commercialization and widespread utilization of PDNs across various disease domains.Self-assembled pure drug nanoparticles(SAPDNPs),a next-generation product,still require extensive translational research.Challenges persist in transitioning from laboratory-scale production to mass manufacturing and overcoming the conversion threshold from laboratory findings to clinical applications.展开更多
基金supported by NSFC(22271282)the Self-deployment Project Research Program of Haixi Institutes,Chinese Academy of Sciences with the grant number of CXZX-2022-JQ04.
文摘Circularly polarized luminescence(CPL)and two-photon absorption(TPA)materials have garnered considerable attentions due to their minimal energy loss and superior optical penetration[1,2].However,the current challenge lies in the absence of well-developed strategies for designing materials that combine these two exceptional optical properties.
基金supported by the Beijing Natural Science Foundation(No.7222261)CAMS Innovation Fund for Medical Sciences(No.2022-I2M-1-015)。
文摘The objective of this study was to predict,screen,synthesize,and investigate cocrystals of poorly soluble flavonoids that are commonly found in dietary supplements with bipolar compound picolinic acid(PA).To improve the efficiency and success rate of experimental screening,two virtual tools based on hydrogen bond propensity(HBP)and modified molecular electrostatic potential(MEP)maps were used.The prediction accuracy of HBP and MEP is 58.82%and 94.11%,respectively,presenting that the MEP model is very powerful in the discovery of pharmaceutical cocrystals.Among the 12 successfully obtained cocrystals,4 single crystals of PA with luteolin(LUT),genistein(GEN),taxifolin(TAX),dihydromyricetin(DHM)were obtained for the first time.Charged-assisted O-H…O and N-H…O hydrogen bonds appear as main hydrogen bonding synthons,and PA adopts a zwitterionic form after cocrystallization.GEN-PA,TAX-PA,and DHM-PA showed higher DPPH'radical-scavenging capacities;LUT-PA and DHM-PA showed higher ABTS^(+)radical-scavenging capacities;GEN-PA and DHM-PA possessed better protective effects on H9c2 cells from hypoxic injury caused by CoCl_(2)than corresponding pure flavonoids.
基金financial support from National Natural Science Foundation of China–CAEP project (No. 11076002)Science and Technology Found of CAEP (No. 2012A0302013)
文摘The selected 18 energetic compounds were theoretically investigated by using the density functional theory（DFT） quantum mechanical code,DMol3,and the Hansen solubility parameters（HSPs） analyses.The results showed that 4-nitrotoluene,4-nitrophenol,N N0-dimethyl-N N0-diphenylurea and N N0-diethyl-N N0-diphenylurea contain relatively electron-rich aromatic rings.Four satisfactory energetic precursors with electron-rich rings were quickly and effectively found by electrostatic potential（ESP）surfaces and HSPs analyses.The results also indicated that the absolute value of the lowest unoccupied molecular orbital（LUMO） of the energetic precursors with electron-rich rings often was less than3.00 eV,and the absolute value of LUMO of the energetic precursors with electron deficient rings was often more than 3.00 eV.Additionally,we found that with at least two eutectic points was a prerequisite for two precursors to form a cocrystal.
基金Xinjiang Uygur Autonomous Region Innovation Environment Construction Special Fund and Technology Innovation Base Construction Key Laboratory Open Project(Grant No.2022D04016)the Key R&D Program of Shan Dong Province(Grant No.2021ZDSYS26)+3 种基金CAMS Innovation Fund for Medical Sciences(Grant No.2022-I2M-1-015)Chinese Pharmacopoeia Commission Drug Standard Promoting Fund(Grant No.2023Y11)Independent Innovation and Achievement Transformation Plan Project of Zaozhuang City(Grant No.2022GH15)2023 Xinjiang Uygur Autonomous Region Innovation Tianchi Talent Introduction Program for financial support.
文摘Currently,cocrystallization is a promising strategy for tailoring the physicochemical properties of active pharmaceutical ingredients.Theophylline,an alkaloid and the most primary metabolite of caffeine,is a readily available compound found in tea and coffee.It functions primarily as a bronchodilator and respiratory stimulant,making it a mainstay treatment for lung diseases like asthma.Theophylline’s additional potential benefits,including anti-inflammatory and anticancer properties,and its possible role in neurological disorders,have garnered significant research interest.Cocrystal formation presents a viable approach to improve the physicochemical properties of theophylline and potentially mitigate its toxic effects.This review comprehensively explores several successful studies that utilized cocrystallization to favorably alter the physicochemical properties of theophylline or its CCF.Notably,cocrystals can not only enhance the solubility and bioavailability of theophylline but also exhibit synergistic effects with other APIs.The review further delves into the hydrogen bonding sites within the theophylline structure and the hydrogen bonding networks observed in cocrystal structures.
文摘The pharmaceutical cocrystals and its engineering is widely accepted phenomenon regarding to the enhancement of aqueous solubility of poorly soluble drugs. The pharmaceutical cocrystals have the great ability to improve the physicochemical properties of drug substance. Cocrystals are formed by the stoichiometric combination of drug substance and the coformer. The drug glimepiride is a third generation oral hypoglycemic sulfonylurea class. Glimepiride is a drug which is get classified as biopharmaceutical classification system (BCS) class II which indicates the glimepiride having low aqueous solubility and high permeability. Cocrystal engineering is a perfect way to increases glimepiride solubility without changing its therapeutic property. The cocrystals were synthesized by the solvent drop grinding as a green chemistry approach. The coformers used to form the cocrystals are succinic acid (SA), Theobromine (TB), caffeine (CF). The synthesized cocrystals are get characterized by vibrational spectroscopy, thermal analysis, molecular crystallography, and optical microscopy. The obtained results shows the formation of cocrystal phase between the drug glimepiride and its coformers.
文摘Recently,drug-drug cocrystal attracts more and more attention.It offers a low risk,low-cost but high reward route to new and better medicines and could improve the physiochemical and biopharmaceutical properties of a medicine by addition of a suitable therapeutically effective component without any chemical modification.Having so many advantages,to date,the reported drug-drug cocrystals are rare.Here we review the drug-drug cocrystals that reported in last decade and shed light on the opportunities and challenges for the development of drug-drug cocrystals.
基金supported by the National Natural Science Foundation of China(Nos.22001006,22375002,22273057,22225401)the Anhui Provincial Natural Science Foundation(No.2308085Y10)+4 种基金the Open Project of Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Anhui University,Ministry of EducationThe National Key Research and Development Program of China(Nos.2022YFC_(2)403500,2020YFA0210800)The Universities Joint Laboratory of Guangdong,Hong Kong and Macao(No.130/07422011)the Natural Science Foundation of Guangdong Province(No.2022A1515011661)the China Postdoctoral Science Foundation(Nos.2023M730760,2023M740010)。
文摘Charge-transfer(CT)stoichiometric cocrystals are promising choice of organic materials for unveiling the structure-property relationship.However,due to the contradiction between large CT degree required for strong NIR absorption and flexible molecular stacking,construction of stoichiomorphism-based cocystals with near-infrared(NIR)photothermal property remains challenging.Herein,the first example of stoichiomorphism-based photothermal cocrystals were accomplished through the adaptive assembly of 3,3,5,5-tetramethylbenzidine(TMB)donor and 1,2,4,5-tetracyanobenzene(TCNB)acceptor.The selective cocrystallization could be controlled by varying the donor-acceptor stoichiometries via a surfactantassisted method,resulting in two cocrystals with 1:1(T1C1)and 1:2(T2C1)stoichiometries.The absorbance intensity of T1C1 at 808 nm was nearly twice that of T2C1,while the photothermal conversion efficiency(PCE)of the former was 60.3%±0.6%,approximately 80%of that for the latter(75.5%±2.6%),which might be caused by the different intermolecular interactions in distinct molecular stacking patterns.Notably,both excellent PCEs of stoichiometric cocrystals were attributed to the nonradiative transition process,including internal conversion and charge dissociation processes,as elucidated by femtosecond transient absorption spectroscopy measurements.Furthermore,T1C1 was used as an NIR heater for preparing agarose-based photothermal hydrogel,showing great potential for light-controlled in-situ gelation.This strategy of balancing the CT degree and molecular packing orientation not only uncovered the relationship between stoichiometric stacking and photothermal property,but also provided an opportunity to develop advanced organic optoelectronic materials.
基金supported by the National Natural Science Foundation of China(12204067)the Natural Science Foundation of Jiangsu Province(BK20220689)+2 种基金the Natural Science Research Project of the Education Department of Jiangsu Province(22KJB140006)the China Postdoctoral Science Foundation(2024M750301)the startup fund of Suzhou University of Technology(KYZ2021055Q,KYZ2021056Q)。
文摘Organic photothermal cocrystals have garnered considerable attention owing to their diverse applications in photoacoustic imaging,seawater desalination,and photothermoelectric conversion.Herein,we synthesize an organic cocrystal,Tri-F_(4)TCNQ,which consists of a donor triphenylene and an acceptor F_(4)TCNQ with a wide absorption wavelength range from visible light to 1800 nm.Furthermore,the Tri-F_(4)TCNQ cocrystal has superior photothermal properties,making it highly promising for photothermal imaging applications.When illuminated with a laser of 1064 nm,the Tri-F_(4)TCNQ cocrystal achieves a high photothermal conversion efficiency(PCE)of 63.6%,which is attributed to the dominant nonradiative pathways and suppressed radiative decay channels.Notably,the Tri-F_(4)TCNQ crystals exhibit magnetism,and a magnetic field can effectively promote photothermal conversion.This is a highly uncommon report about magnetic-responsive photothermal effects in organic cocrystals.Moreover,the Tri-F_(4)TCNQ cocrystal demonstrates remarkable structural stability,photosensitivity,and magnetic field responsiveness,laying a solid foundation for future applications.
基金supported by the King Abdullah International Medical Research Center(KAIMRC)Sauid Arabia:Grant NRC23R/746/11.
文摘The field of molecular charge transfer cocrystals(CTCs)has advanced rapidly in recent years,with much work focused on their use in optoelectronic devices,photoacoustic imaging,photothermal therapy(PTT),opticalwaveguides,seawater desalination,and more.Organic photothermal CTCs are of particular interest because of their unique phototherapeutic effects in phototherapy and their remarkable imaging capabilities in fluorescence,magnetic resonance,and photoacoustic imaging,further enhancing their significance in medical applications.However,the use of photothermal CTCs in biomedicine has been limited,with few reported biological applications.Hence,there is a growing interest in CT-derived functional photothermal cocrystals potential contenders for targeted and controlled biomedical applications such as bacteria inhibition,cancer eradication,and tissue regeneration.This review offers insight into the recent advancements in crafting and producing CT-based materials with biomedical attributes.In addition,it outlines the current obstacles and future prospects in this burgeoning research domain,aiming to propel the continued advancement of CT-based biomaterials toward enhanced biomedical utilities.Overall,cocrystal-based near-infrared(NIR)photothermal materials have the potential to revolutionize a wide range of medical and technological applications and are an active area of research in chemistry,materials science,and nanotechnology.
基金supported by the National Natural Science Foundation of China(22025503,22220102004)。
文摘Organic donor-acceptor cocrystals ofπ-conjugated molecues have shown diverse applications in materials science.However,most cocrystals exist in neutral forms dominated byπ-πinteractions,while the ionic congeners and corresponding properties are rarely studied due to difficulties in harnessing the degree of charge transfer.Herein,we report cocrystals of axially N-embedded quasi-carbon nanohoops(DPP-D and DPP-T)with electron deficient vips.By modulating the electron affinity of the acceptor vips,the electronic structures of the complexes can be tuned from neutral to ionic states.Specifically,DPP-D interacts with TCNB molecules to form neutral superstructures via intermolecularπ-πinteractions,giving rise to a deep-red emission in the solid state.In contrast,an ionic complex showing near-infrared region absorptions and paramagnetic character on account of strong charge-transfer interactions is generated when DDQ molecules are involved.Their unique properties can be explained by different degrees of charge transfer and assembly modes,which have clearly been manifested by crystal structures and theoretical calculations.Our studies provide rare examples ofπ-conjugated macrocycle-based donor-acceptor cocrystals in both neutral and ionic forms,and give insight to the design of multicomponent carbon nanomaterials.
基金financially supported by the National Natural Science Foundation of China(52173182 and 52250610221).
文摘As an emerging functional material system,organic cocrystals in the near-infrared(NIR)window drive the innovation of novel material systems.In recent years,it has made breakthroughs in optoelectronics,energy conversion,and biomedicine,thanks to its unique molecular assembly strategy,charge-transfer characteristics,and multi-dimensional application potential.This paper systematically reviews the design strategies,preparation methods,structure relationships,characterization methods,and cutting-edge applications of this type of material.Finally,it presents prospects for future research directions and challenges.
基金the financial support to this work from the National Natural Science Foundation of China(Nos.81872813)the Outstanding Youth Fund of Jiangsu Province of China(BK20190029)+2 种基金Natural Science Foundation of Jiangsu Province(BK 20200576,China)Fundamental Research Funds for the Central Universities(No.2632020PY04)the Program of State Key Laboratory of Natural Medicines-China Pharmaceutical University(No.SKLNMZZ202031)
文摘Pharmaceutical cocrystals are multicomponent systems in which at least one component is an active pharmaceutical ingredient and the others are pharmaceutically acceptable ingredients.Cocrystallization of a drug substance with a coformer is a promising and emerging approach to improve the performance of pharmaceuticals,such as solubility,dissolution profile,pharmacokinetics and stability.This review article presents a comprehensive overview of pharmaceutical cocrystals,including preparation methods,physicochemical properties,and applications.Furthermore,some examples of drug cocrystals are highlighted to illustrate the effect of crystal structures on the various aspects of active pharmaceutical ingredients,such as physical stability,chemical stability,mechanical properties,optical properties,bioavailability,sustained release and therapeutic effect.This review will provide guidance for more efficient design and manufacture of pharmaceutical cocrystals with desired physicochemical properties and applications.
基金supported by the Ministry of Science and Technology of China(2018YFA0703200 and 2017YFA0204503)the National Natural Science Foundation of China(52121002,51733004,U21A6002,51725304 and 21875158)+1 种基金Tianjin Natural Science Foundation(20JCJQJC00300)China Postdoctoral Science Foundation(2021M692381)。
文摘Near-infrared organic phototransistors have wide application prospects in many fields.The active materials with the high mobility and near-infrared response are critical to building high-performance near-infrared organic phototransistors,which are scarce at present.Herein,a new charge transfer cocrystal using 5,7-dihydroindolo[2,3-b]carbazole(5,7-ICZ)as the donor and 2,2’-(benzo[1,2-b:4,5-b’]dithiophene-4,8-diylidene)dimalononitrile(DTTCNQ)as the acceptor is properly designed and prepared in a stoichiometric ratio(D:A=1:1),which not only displays a high electron mobility of 0.15 cm^(2)V^(-1)s^(-1) and very low dark current,but also can serve as the active layer materials in the region of near-infrared detection due to the narrowed band gap and good charge transport properties.A high photosensitivity of 1.8×10^(4),the ultrahigh photoresponsivity of 2,923 A W-1and the high detectivity of 4.26×10^(11)Jones of the organic near-infrared phototransistors are obtained.
基金the National Key R&D Program(2022YFB3603800)the National Natural Science Foundation of China(52121002,U21A6002)+1 种基金Tianjin Natural Science Foundation(20JCJQJC00300)the Fundamental ResearchFunds forthe Central Universities.
文摘The organic cocrystal strategy has provided a convenient and efficient platform for preparing organic photothermal materials.However,the rapidly directional preparation of cocrystals with desirable photothermal properties remains challenging due to a lack of suitable design ideas.Here,two new photothermal cocrystals,MTC and MFC,based on acceptor molecules(TCNQ and F4TCNQ)with different electron-withdrawing capacities were quickly prepared by the coprecipitation method,aiming to explore the effect of charge transfer(CT)interaction on photothermal properties.Compared with MTC,the stronger intermolecular CT interaction in MFC facilitates extending the absorption range(from the NIR-I to the NIR-II region)and enhancing the non-radiative transition process.Under the 808 nm laser irradiation,the photothermal conversion efficiency(PCE)of MFC is 54.6%,whereas MTC displays a mere 36.8%.The MFC cocrystal was further combined with a flexible polymer substrate(HPDMS)to prepare a flexible wearable heater(HPDMS@MFC),which exhibits excellent NIR-II photothermal performance.This work points out a research direction for the rapid assembly of efficient photothermal cocrystals and additionally provides an extensive application prospect for organic photothermal cocrystals in the field of wearable devices.
基金sponsored by the "Shu Guang" project supported by Shanghai Education Development Foundation and Shanghai Municipal Education Commission (15SG39, China)the Shanghai Pujiang Program (16PJD044, China)+1 种基金National Natural Science Foundation of China (81573814)the science and technology project supported by the Science and Technology Commission of Huangpu District (ZYKC201603008, China)
文摘Pharmaceutical cocrystals are a promising technology that can be used to improve the solubility of poor aqueous compounds. The objective of this study was to systematically investigate the solubility of myricetin(MYR) cocrystals, including their kinetic solubility, thermodynamic solubility, and intrinsic dissolution rate(IDR). The effects of pH, surfactant, ion concentration, and coformers on the cocrystal solubility were evaluated. Furthermore, single crystal structures of MYR, myricetin–isonicotinamide(MYR–INM) and myricetin–caffeine(MYR–CAF) cocrystals were analyzed to discuss the possible reasons for the enhancement of cocrystal solubility from the perspective of the spatial structure.The results indicated that the kinetic solubility of MYR cocrystals was modulated by pH and cocrystal coformer(CCF) ionization in buffer solution, while it primarily depended on the CCF solubility in pure water. In addition, the solubility of MYR cocrystals was increased in a concentration dependent fashion by the surfactant or ion concentration. The thermodynamic solubility of MYR–INM(1:3) cocrystals decreased with the increases of the pH value of the dissolution media. The IDR of MYR cocrystals was faster than that of MYR in the same medium and extremely fast in pH 4.5 buffer. The improved solubility of MYR cocrystals was probably related to the alternate arrangements of MYR and INM/CAF molecules and increased intermolecular distance. The present study provides some references to investigate the solubility behavior of pharmaceutical cocrystals.
基金supported by the National Natural Science Foundation of China(91222203,91233205,51222306,91027043 and 91433115)the Ministry of Science and Technology of China(2013CB933403,2013CB933500 and 2014CB643600)+1 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB12030300)the Chinese Academy of Sciences
文摘Organic cocrystals are crystalline,single-phase materials composed of two or more molecular and/or ionic compounds,generally,in a stoichiometric ratio.A feature of organic cocrystals is that special optoelectronic properties such as ferroelectricity are easy to realize in these materials.In this perspective,we systematically introduce the recent research advances in organic cocrystal ferroelectrics,and we study in depth the molecular structure and self-assembling behaviors of cocrystals for ferroelectric applications.Finally,combined with an understanding of recent progress and achievements in this field,we discuss the challenges and opportunities for ferroelectric materials based on organic cocrystals,as well as the promising applications of these materials.
基金National Natural Science Foundation of China(grant No.22068002 and 22178054)Training plan for academic and technical leaders of major disciplines in Jiangxi Province-Youth Talent Project(grant No.20212BCj23001)+1 种基金Jiangxi Provincial Natural Science Foundation(grant No.20224ACB213007,20212ACB203002,and 20232BBH80015)Jiangxi Province Key Laboratory of Synthetic Chemistry(grant No.JXSC202209).
文摘Carbamazepine(CBZ)is an anticonvulsant with very low water solubility,presenting as a white crystalline powder with poor mechanical properties and is hard to bend.To enhance CBZ's physicochemical properties,such as water solubility and mechanical properties,we selected six cocrystal coformers(CCFs):nicotinamide(NIC),benzamide(BZM),salicylic acid(SCA),fumaric acid(FMA),trimesic acid(TMA),and hesperetin(HPE).Six CBZ cocrystals were successfully prepared using the solution method.Fourier transform infrared spectroscopy(FT-IR),powder X-ray diffraction(PXRD),differential scanning calorimetry(DSC),and single crystal X-ray diffraction(SCXRD)were used to characterize the crystal structures and gain comprehensive insights into the six cocrystals.The mechanical,fluorescence,and solubility properties of the six cocrystals were tested.The results reveal that most of the prepared cocrystals exhibit improved water solubility and mechanical properties when compared to CBZ.Among them,the dissolution rate of cocrystals excluded from CBZ-HPE has increased by an average of 3 or 4 times compared to CBZ,while CBZ-HPE exhibits superior mechanical properties.Moreover,all six cocrystals possess better fluorescence performance than CBZ.We thoroughly evaluated the mechanical properties of the cocrystals through both experimental and theoretical approaches.This work provides a new direction for studying drug cocrystals to improve the physicochemical properties of drugs.
基金supported by the National Natural Science Foundation of China (51303185, 21021091, 51033006, 51222306, 51003107, 61201105, 3591027043, 91222203, 91233205, 21473222 and 21773040)the Ministry of Science and Technology of China (2011CB808400, 2011CB932300, 2013CB933403, 2013CB933500 and 2014CB643600)the Chinese Academy of Sciences (Y42D0A12D1 and Y42D0412D1)。
文摘The nucleation and growth mechanism and polymorph-property correlations in the molecular cocrystal field are widely sought but currently remain unclear. Herein, a new wire-like morphology of phenazine(Phz)-chloranilic acid(H2ca) cocrystal(PHC) is demonstrated for the first time, and the self-assembly of Phz and H2ca is controlled to selectively prepare kinetically stable wires and thermodynamically stable plates. Specifically, low precursor concentration is beneficial for one-dimensional(1D) self-assembly along the [010] crystallographic direction, while only supersaturation can trigger 2D self-assembly along the [100] and [010] directions, respectively. This is understandable in terms of the(020) face showing the largest attachment energy(Eatt) and the(002) face possessing the smallest surface energy(Esurf). Moreover, anisotropic Raman spectra related to the mode symmetry and atomic displacements in two types of PHCs are revealed, and the same Raman-active vibrational bands of PHC wire and plate show different polarization responses, which is intrinsically ascribed to their different molecular orientations.Overall, this is the first case that morphologies of cocrystal are precisely tuned with comprehensive investigations of their anisotropic vibrational characteristics.
基金Ministry of Science and Technology of the People’s Republic of China,Grant/Award Number:2022YFB3603804Natural Science Foundation of Shanghai Municipality,Grant/Award Number:22ZR1407800。
文摘Advancements in organic electronics are propelling the development of new material systems,where organic materials stand out for their unique benefits,including tunability and cost-effectiveness.Organic single crystals stand out for their ordered structure and reduced defects,enhancing the understanding of the relationship between structure and performance.Organic cocrystal engineering builds upon these foundations,exploring intermolecular interactions within multicomponent-ordered crystalline materials to combine the inherent advantages of single-component crystals.However,the path to realizing the full potential of organic cocrystals is fraught with challenges,including structural mismatches,unclear cocrystallization mechanisms,and unpredictable property alterations,which complicate the effective cocrystallization between different molecules.To deepen the understanding of this promising area,this review introduces the mechanism of organic cocrystal formation,the various stacking modes,and different growth techniques,and highlights the advancements in cocrystal engineering for multifunctional applications.The goal is to provide comprehensive guidelines for the cocrystal engineering of highperformance molecular materials,thereby expanding the applications of organic cocrystals in the fields of optoelectronics,photothermal energy,and energy storage and conversion.
基金supported by the National Natural Science Foundation of China(Nos.82073782 and 82241002)。
文摘Pure drug nanomedicines(PDNs)encompass active pharmaceutical ingredients(APIs),including macromolecules,biological compounds,and functional components.They overcome research barriers and conversion thresholds associated with nanocarriers,offering advantages such as high drug loading capacity,synergistic treatment effects,and environmentally friendly production methods.This review provides a comprehensive overview of the latest advancements in PDNs,focusing on their essential components,design theories,and manufacturing techniques.The physicochemical properties and in vivo behaviors of PDNs are thoroughly analyzed to gain an in-depth understanding of their systematic characteristics.The review introduces currently approved PDN products and further explores the opportunities and challenges in expanding their depth and breadth of application.Drug nanocrystals,drug-drug cocrystals(DDCs),antibody-drug conjugates(ADCs),and nanobodies represent the successful commercialization and widespread utilization of PDNs across various disease domains.Self-assembled pure drug nanoparticles(SAPDNPs),a next-generation product,still require extensive translational research.Challenges persist in transitioning from laboratory-scale production to mass manufacturing and overcoming the conversion threshold from laboratory findings to clinical applications.
