Zwitterionic Polysulfobetaine Inhibits Cancer Cell Migration Owing to Actin Cytoskeleton Dynamics.

Cell migration is an essential dynamic process for most living cells, mainly driven by the reorganization of actin cytoskeleton. To control actin dynamics, a molecular architecture that can serve as a nucleator has been designed by polymerizing sulfobetaine methacrylate. The synthesized zwitterionic polymer, poly(sulfobetaine methacrylate) (PZI), effectively nucleates the polymerization process of G-actin and substantially accelerates the rate of polymerization. Isothermal titration calorimetry (ITC) and bioinformatics analysis indicated binding between PZI and monomeric G-actin. Thus, in vitro actin dynamics was studied by dynamic light scattering (DLS), pyrene-actin polymerization assay, and total internal reflection fluorescence microscopy (TIRFM). Furthermore, a 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) fluorophore-containing monomeric unit was incorporated into the sulfobetaine zwitterionic architecture to visualize the effect of polymer in the cellular environment. The BODIPY-containing zwitterionic sulfobetaine polymer (PZI-F) successfully penetrated the cell and remained in the lysosome with minimal cytotoxicity. Confocal microscopy revealed the influence of this polymer on the cellular actin cytoskeleton dynamics. The PZI-F polymer was successfully able to inhibit the collective migration of the human cervical cancer cell line (HeLa cell) and breast cancer cell line (MDA-MB-231 cell), as confirmed by a wound healing assay. Therefore, polyzwitterionic sulfobetaine could be explored as an inhibitor of cancer cell migration.

Origin of Strong Hydrogen Bonding and Preferred Orientation of Water at Uncharged Polyethylene Glycol Polymer/Water Interface.

Polyethylene glycol (PEG), a water-soluble non-ionic polymer, finds diverse applications from Li-ion batteries to drug delivery. The effectiveness of PEG in these contexts hinges on water's behavior at PEG/water interfaces. Employing heterodyne-detected vibrational sum frequency generation and Raman spectroscopy along with a novel analytical approach, termed difference spectroscopy with simultaneous curve-fitting analysis, we observed that water exhibits both "hydrogen-up" and "hydrogen-down" orientations at PEG(≥400u)/water interfaces. As the molar mass of PEG increases, the contribution of the strongly hydrogen-bonded and H-up-oriented water rises. We propose that the PEG-affected interfacial water originates from the asymmetrical hydration of the surface-adsorbed PEG, as evidenced by the resemblance between the water spectra in the hydration shell of PEG and those at the PEG/water interface. These findings elucidate the molecular mechanism underlying PEG's catalytic role in water splitting at membrane interfaces.

Electron transfer catalysis mediated by 3d complexes of redox non-innocent ligands possessing an azo function: a perspective.

It was first reported almost two decades ago that ligands with azo functions are capable of accepting electron(s) upon coordination to produce azo-anion radical complexes, thereby exhibiting redox non-innocence. Over the past two decades, there have been numerous reports of such complexes along with their structures and diverse characteristics. The ability of a coordinated azo function to accept one or more electron(s), thereby acting as an electron reservoir, is currently employed to carry out electron transfer catalysis since they can undergo redox transformation at mild potentials due to the presence of energetically accessible energy levels. The cooperative involvement of redox non-innocent ligand(s) containing an azo group and the coordinated metal centre can adjust and modulate the Lewis acidity of the latter through selective ligand-centred redox events, thereby manipulating the capacity of the metal centre to bind to the substrate. We have summarized the list of first row transition metal complexes of iron, cobalt, nickel, copper and zinc with redox non-innocent ligands incorporating an azo function that have been exploited as electron transfer catalysts to effectuate sustainable synthesis of a wide variety of useful chemicals. These include ketazines, pyrimidines, benzothiazole, benzoxazoles, N-acyl hydrazones, quinazoline-4(3)H-ones, C-3 alkylated indoles, N-alkylated anilines and N-alkylated heteroamines. The reaction pathways, as demonstrated by catalytic loops, reveal that the azo function of a coordinated ligand can act as an electron sink in the initial steps to bring about alcohol oxidation and thereafter, they serve as an electron pool to produce the final products either via HAT or PCET processes.

Adsorption of SARS-CoV-2 Spike (N501Y) RBD to Human Angiotensin-Converting Enzyme 2 at a Lipid/Water Interface.

The receptor binding domain (RBD) of spike proteins plays a crucial role in the process of severe acute respiratory syndrome corona virus 2 (SARS-CoV-2) attachment to the human angiotensin-converting enzyme 2 (ACE2). The N501Y mutation and later mutations introduced extra positive charges on the spike RBD and resulted in higher transmissibility, likely due to stronger binding with the highly negatively charged ACE2. Consequently, many studies have been devoted to understanding the molecular mechanism of spike protein binding with the ACE2 receptor. Most of the theoretical studies, however, have been done on isolated proteins. ACE2 is a transmembrane protein; thus, it is important to understand the interaction of spike proteins with ACE2 in a lipid matrix. In this study, the adsorption of ACE2 and spike (N501Y) RBD at a lipid/water interface was studied using the heterodyne-detected vibrational sum frequency generation (HD-VSFG) technique. The technique is a non-linear optical spectroscopy which measures vibrational spectra of molecules at an interface and provides information on their structure and orientation. It is found that ACE2 is effectively adsorbed at the positively charged 1,2-dipalmitoyl-3-trimethylammonium-propane (DPTAP) lipid monolayer via electrostatic interactions. The adsorption of ACE2 at the DPTAP monolayer causes a reorganization of interfacial water (D2O) from the D-down to the D-up orientation, indicating that the originally positively charged DPTAP interface becomes negatively charged due to ACE2 adsorption. The negatively charged interface (DPTAP/ACE2) allows further adsorption of positively charged spike RBD. HD-VSFG spectra in the amide I region show differences for spike (N501Y) RBD adsorbed at D2O, DPTAP, and DPTAP/ACE2 interfaces. A red shift observed for the spectra of spike RBD/DPTAP suggests that spike RBD oligomers are formed upon contact with DPTAP lipids.

From small molecules to polymeric probes: recent advancements of formaldehyde sensors.

Formaldehyde is a well-known industrial material regularly used in fishery, vegetable markets, and fruit shops for maintaining their freshness. But due to its carcinogenic nature and other toxic effects, it is very important to detect it in very low concentrations. In recent years, amine-containing fluorescent probes have gained significant attention for designing formaldehyde sensors. However, the major drawbacks of these small molecular probes are low sensitivity and long exposure time, which limits their real-life applications. In this regard, polymeric probes have gained significant attention to overcome the aforementioned problems. Several polymeric probes have been utilized as a coating material, nanoparticle, quartz crystal microbalance (QCM), etc., for the selective and sensitive detection of formaldehyde. The main objective of this review article is to comprehensively describe the recent advancements in formaldehyde sensors based on small molecules and polymers, and their successful applications in various fields, especially in situ formaldehyde sensing in biological systems.

Headgroup-Specific Interaction of Biological Lipid Monolayer/Water Interface with Perfluorinated Persistent Organic Pollutant (f-POP): As Observed with Interface-Selective Vibrational Spectroscopy.

Perfluoro compounds are widely used in various manufacturing processes, which leads to their bioaccumulation and subsequent adverse effects on human health. Using interface-selective vibrational spectroscopy (heterodyne-detected vibrational sum frequency generation (HD-VSFG)), we have elucidated the molecular mechanism of the perturbation of lipid monolayers on the water surface using a prototype perfluorinated persistent organic pollutant, perfluoroheptanoic acid (PFHA). PFHA disrupts the well-ordered all-trans conformation of a cationic lipid (1,2-dipalmitoyl-3-trimethylammonium propane (DPTAP)) monolayer and reduces the interfacial electric field at the lipid/water interface. In contrast, the hydrophobic packing of an anionic lipid (1,2-dipalmitoyl-sn-glycero-3-phospoglycerol (DPPG)) monolayer remains largely unaffected in the presence of PFHA, though the interfacial electric field is reduced. For a zwitterionic lipid (1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC))/water interface, both alkyl chain ordering and interfacial electric field are fairly perturbed by PFHA. Lipid headgroup-specific interaction of PFHA and the repulsive interaction of oleophobic fluoroalkyl chain with the lipid alkyl chains govern these distinct perturbations of the lipid monolayers on the water surface.

Interaction of Zwitterionic Osmolyte Trimethylamine N-oxide (TMAO) with Molecular Hydrophobes: An Interplay of Hydrophobic and Electrostatic Interactions.

Interaction of trimethylamine N-oxide (TMAO) with charged/uncharged moieties of proteins and lipids is an important elementary step toward the multifaceted biofunctions of TMAO. Using minimum area Raman difference spectroscopy (MA-RDS) of aqueous TMAO (1.0 M) in the presence of deuterated molecular hydrophobes (e.g., deuterated tetramethylammonium cation (d-TMA+) and tert-butylalcohol (d-TBA)), we show that TMAO exhibits two distinct motifs of interaction with the cationic (d-TMA+) and uncharged (d-TBA) hydrophobes. Specifically, the trimethylammonium moiety of TMAO undergoes van der Waals attraction with the tert-butyl group of d-TBA, which is governed by their mutual hydrophobic interaction with water. This makes their methyl groups less exposed to water. In contrast, for the cationic hydrophobe (d-TMA+), TMAO interacts electrostatically via its negatively charged-oxygen, which in turn orients the TMAO-methyls away from the hydrophobe (d-TMA+), keeping them exposed to water.

Kosmotropic Electrolyte (Na2CO3, NaF) Perturbs the Air/Water Interface through Anion Hydration Shell without Forming a Well-Defined Electric Double Layer.

The ion-driven electric double layer (EDL) and the structural transformation of interfacial water are implicated in unusual reaction kinetics at the air/water interface. By combining heterodyne-detected vibrational sum frequency generation (HD-VSFG) with differential spectroscopy involving simultaneous curve fitting (DS-SCF) analysis, we retrieve electrolyte (Na2CO3 and NaF)-correlated OH-stretch spectra of water at the air/water interface. Vibrational mapping of the perturbed interfacial water with the hydration shell spectra (obtained by DS-SCF analysis of Raman spectra) of the corresponding anion discloses that the kosmotropic electrolytes do not form well-defined EDL at the air/water interface. Instead, the interfacial water forms a stronger hydrogen-bond with the surface-expelled anions (CO32- and F-) and becomes more inhomogeneous than the pristine air/water interface. Together, the results reveal that the perturbation of interfacial water by the kosmotropic electrolyte is a "local phenomenon" confined within the hydration shell of the surface-expelled anion.

"Breaking" and "Making" of Water Structure at the Air/Water-Electrolyte (NaXO3; X = Cl, Br, I) Interface.

The prevalence of ions at the aqueous interface has been widely recognized, but their effect on the structure of interfacial water (e.g., hydrogen (H)-bonding) remains enigmatic. Using heterodyne-detected vibrational sum frequency generation (HD-VSFG) and Raman difference spectroscopy with simultaneous curve fitting (DS-SCF) analysis, we show that the ion-induced perturbations of H-bonding at the air/water interface and in the bulk water are strongly correlated. Specifically, the structure-breaking anions such as ClO3- decrease the average H-bonding of water at the air/water interface, as it does to the water in its hydration shell in the bulk. The structure-making anion of the same series (IO3-) does exactly the reverse. None of the electrolytes (NaXO3; X = Cl, Br, I) form well-defined electric double layers that significantly increase or reverse the hydrogen-down (H-down) orientation of water at the air/water interface. These results provide a unified picture of specific anion effect at the air/water interface and in the bulk water.

Solvent-Induced Reversible Spin-Crossover in a 3D Hofmann-Type Coordination Polymer and Unusual Enhancement of the Lattice Cooperativity at the Desolvated State.

The new 3D Hofmann-type coordination polymer [Fe(dpyu){Pt(CN)4}]·9H2O [dpyu = 1,3-di(pyridin-4-yl)urea] exhibits reversible interchange between two- and one-step spin-crossover behavior, associated with desorption/resorption of lattice water molecules. Solvent water removal also induces an increase of the spin-transition temperature, indicating strong lattice cooperativity, observed for the first time in a 3D Hofmann-type coordination polymer.

Interaction of α-Synuclein with Phospholipids and the Associated Restructuring of Interfacial Lipid Water: An Interface-Selective Vibrational Spectroscopic Study.

Interaction of α-Synuclein (αS) with biological lipids is crucial for the onset of its fibrillation at the cell membrane/water interface. Probed herein is the interaction of αS with membrane-mimicking lipid monolayer/water interfaces. The results depict that αS interacts negligibly with zwitterionic lipids, but strongly affects the pristine air/water and charged lipid/water interfaces by perturbing the structure and orientation of the interfacial water. The net negative αS (-9 in bulk water; pH 7.4) reorients the water as hydrogen-up (H-up) at the air/water interface, and electrostatically interacts with positively charged lipids, making the interface nearly net neutral. αS also interacts with negatively charged lipids: the net H-up orientation of the interfacial water decreases at the anionic lipid/water interface, revealing a domain-specific interaction of net negative αS with the negatively charged lipids at the membrane surface.

Restructuring of Hydration Shell Water due to Solvent-Shared Ion Pairing (SSIP): A Case Study of Aqueous MgCl2 and LaCl3 Solutions.

Hydration of ions plays a crucial role in interionic interactions and associated processes in aqueous media, but selective probing of the hydration shell water is nontrivial. Here, we introduce Raman difference with simultaneous curve fitting (RD-SCF) analysis to extract the OH-stretch spectrum of hydration shell water, not only for the fully hydrated ions (Mg2+, La3+, and Cl-) but also for the ion pairs. RD-SCF analyses of diluted MgCl2 (0.18 M) and LaCl3 (0.12 M) solutions relative to aqueous NaCl of equivalent Cl- concentrations provide the OH-stretch spectra of water in the hydration shells of fully hydrated Mg2+ and La3+ cations relative to that of Na+. Integrated intensities of the hydration shell spectra of Mg2+ and La3+ ions increase linearly with the salt concentration (up to 2.0 M MgCl2 and 1.3 M LaCl3), which suggests no contact ion pair (CIP) formation in the MgCl2 and LaCl3 solutions. Nevertheless, the band shapes of the cation hydration shell spectra show a growing signature of Cl--associated water with the rising salt concentration, which is a manifestation of the formation of a solvent-shared ion pair (SSIP). The OH-stretch spectrum of the shared/intervening water in the SSIP, retrieved by second-round RD-SCF analysis (2RD-SCF), shows that the average H-bonding of the shared water is weaker than that of the hydration water of the fully hydrated cation (Mg2+ or La3+) but stronger than that of the anion (Cl-). The shared water displays an overall second-order dependence on the concentration of the interacting ions, unveiling 1:1 stoichiometry of the SSIP formed between Mg2+ and Cl- as well as La3+ and Cl-.

Adsorption of Iodine Species (I3-, I-, and IO3-) at the Nuclear Paint Monolayer-Water Interface and Its Relevance to a Nuclear Accident Scenario.

Following a nuclear accident, radioactive iodine causes great concern to public health and safety. Organic iodide, because of its ability to escape reactor containment building and high environmental mobility, constitutes a predominant fraction of airborne radioiodine at places far away from the accident site. As the iodine released from a reactor core is inorganic iodine, it is vital to understand the mechanism of organic iodide formation inside reactor containment. In this context, we investigated the surface prevalence and adsorption of various inorganic iodines, I-, I3-, and IO3-, at a nuclear paint (used in nuclear installations) monolayer-water interface, mimicking the painted inner walls of an accident-affected containment building that are exposed to the iodine-containing condensed water layer. Vibrational sum frequency generation (VSFG) measurements in the OH and CH stretch regions reveal that the paint-water interface changes its charge characteristics with the pH of the water that affects the degree of interaction with the iodine species. At the acidic condition (bulk pH < 7), the paint becomes positively charged and strongly adsorbs the negatively charged iodine species dissolved in the aqueous phase, whereas at the alkaline condition (bulk pH > 9.5), the paint becomes net neutral and weakly interacts with the iodine species. These interactions change the conformation of the paint such that its hydrophobic alkyl groups orient increasingly away from the aqueous phase. The order of adsorption increases as IO3- < I- < I3- for the different iodine species studied.

Remarkable Energy Barrier for Magnetization Reversal in 3D and 2D Dysprosium-Chloranilate-Based Coordination Polymers.

Herein, two coordination polymers (CPs) [{Dy(Cl2 An)1.5 (CH3 OH)}⋅4.5 H2 O]n (1) and [Dy(Cl2 An)1.5 (DMF)2 ]n (2), in which Cl2 An is chloranilate (2,5-dihydroxy-1,4-benzoquinone dianion), exhibiting field-induced single-molecule magnet behavior with moderate barrier of magnetization reversal are reported. Detailed structural and topological analysis disclosed that 1 has a 3D network, whereas 2 has a 2D layered-type structure. In both CPs, magnetic measurements showed weak antiferromagnetic exchange interaction between the dysprosium centers and field-induced slow magnetic relaxation with barriers of 175(9)K and 145(7)K for 1 and 2, respectively. Notably, the energy barriers of magnetization reversal of 1 and 2 are remarkable for metal-chloranilate-based 3D (1) and 2D (2) CPs. The temperature and field dependence of relaxation time indicate the presence of multiple relaxation pathways, such as direct, quantum tunneling of magnetization, Raman, and Orbach processes, in both CPs. Ab initio theoretical calculations reinforced the experimentally observed higher energy barrier in 1 as compared with 2 due to the presence of large transverse anisotropy in the ground state in the latter. The average transition magnetic moment between the computed low-lying spin-orbit states also rationalized the relaxation as Orbach and Raman processes through the first excited state. BS-DFT calculations were carried out for both CPs to provide more insight into the exchange interaction.

On the Behavior of Perfluorinated Persistent Organic Pollutants (POPs) at Environmentally Relevant Aqueous Interfaces: An Interplay of Hydrophobicity and Hydrogen Bonding.

The behavior of perfluorinated persistent organic pollutants (POPs), especially perfluoroalkyl carboxylic and sulfonic acids, at aqueous interfaces is crucial for their transport and speciation in the environment and subsequent immunotoxicity. Here, we investigate the surface prevalence and interfacial interaction of a prototype perfluorinated-POP, perfluoroheptanoic acid (PFHA), with environmentally relevant amphiphiles of varying hydrophobicity and head groups (CnH2n+1-X; n: 8 vs 16; -X: -OH vs -COOH) using interface-selective vibrational sum frequency generation (VSFG) spectroscopy. SFG intensity spectra in the CH- and OH-stretch regions reveal that PFHA prevails at aqueous interfaces that contain amphiphiles of intermediate chain length such as 1-octanol (n = 8) and heptanoic acid (n = 6). PFHA partially expels as well as increases the alkyl chain order of octanol on the water surface. Whereas heptanoic acid, though less hydrophobic than octanol, is retained at the water surface through hydrogen-bonding with the PFHA head group ((PFHA)COO-···HOOC(heptanoic-acid)). Long chain amphiphiles (n = 16) such as hexadecanol and palmitic acid expel PFHA from the water surface regardless of the difference in their head groups. Interestingly, the dangling OH (3710 cm-1) which is diminished at the hydrogenated-amphiphile-water interface is preserved at the perfluorinated-POP-water interface.

Probing through-space and through-bond magnetic exchange couplings in a new benzotriazinyl radical and its metal complexes.

The synthesis and characterization of a new chelating benzotriazinyl radical (Rad2) are described. Crystallographic studies coupled with SQUID magnetometry on Rad2 reveal the presence of discrete radical pairs which are antiferromagnetically coupled. The reaction of Rad2 with the 3d transition metal complexes M(hfac)2·xH2O (hfac- = hexafluoroacetylacetonate) led to mononuclear metal complexes of general formula M(hfac)2(Rad2) [M = Zn(ii) (1); Ni(ii) (2) and Co(ii) (3)] whose structures have been determined by single crystal X-ray diffraction. Compounds 1-3 are isostructural and crystallize in the monoclinic space group P21/n with two molecules in the asymmetric unit. In the case of the Zn(ii) complex (1) through-space intermolecular radicalradical antiferromagnetic exchange interactions viaπ*π* contacts are observed, whereas strong intramolecular through-bond metal-radical ferromagnetic interactions [J = +59.3(9) cm-1] are observed for the Ni(ii) complex (2). For the Co(ii) complex (3), computational and magnetic studies reveal substantial zero field splitting and ferromagnetic metal-radical interactions.

Polyatomic Iodine Species at the Air-Water Interface and Its Relevance to Atmospheric Iodine Chemistry: An HD-VSFG and Raman-MCR Study.

Iodine plays a key role in tropospheric ozone destruction, atmospheric new particle formation, as well as growth. Air-water interface happens to be an important reaction site pertaining to such phenomena. However, except iodide (I-), the behavior of other iodine species, for example, triiodide (I3-) and iodate (IO3-, the most abundant iodine species in seawater) at the aqueous interface and their effect on the interfacial water are largely unknown. Using interface-specific vibrational spectroscopy (heterodyne-detected vibrational sum frequency generation), we recorded the imaginary-χ(2) spectra (Imχ(2); χ(2) is the second-order electric susceptibility in OH stretch region) of the air-water interface in the presence of IO3-, I3-, and I- (≤0.3 M) in the aqueous subphase. The Imχ(2) spectra reveal that the chaotropic I3- is the most surface-active anion among the iodine species studied and decreases the vibrational coupling and hydrogen-bonding of interfacial water. Interestingly, the IO3-, even being a kosmotrope, is quite prevalent in the interfacial region and preferentially orients the interfacial water as "H-down" (i.e., water dipole moment is pointed toward the bulk water). Mapping of the OH stretch response of ion-affected water at interface (i.e., ΔImχ(2) = Imχ(2)air-water-iodine salt - Imχ(2)air-water) with that in the hydration shell of the respective ion (hydration shell water response is obtained by Raman multivariate curve resolution spectroscopy) reveals a correlative link between the ion's influence on the interfacial water and their hydration shell structure. The distinct water structure of stronger as well as weaker H-bonding in the hydration shell of the polyatomic IO3- anion promotes the anion to stay at the interfacial region. Thus, the surface prevalence of the iodine species and their effect on the interfacial water are perceived to be crucial for the transfer of iodine from seawater to the atmosphere across the marine boundary layer and the chemistry of iodine at aqueous aerosol surface.

Above Room Temperature Spin Transition in Thermally Stable Mononuclear Fe(III) Complexes.

Two solvent-free mononuclear Fe(III) complexes [Fe(L)2]NO3 (1) and [Fe(L)2]ClO4 (2) have been synthesized by employing a new π-conjugated azo-phenyl substituted ligand, 2-(( E)-((2-(ethylamino)ethyl)imino)methyl)-4-(2-phenyldiazenyl)phenol (HL). The noncoordinated azo-phenyl part of the ligand adopts two different conformations which can exert a varied local distortion around the metal center affecting the spin crossover behavior. The magnetic data (2-450 K) reveal that complex 1 displays spin crossover above room temperature where the ligand is in linear form, while complex 2 shows an incomplete spin transition where the ligand adopts a skew form in the solid state. These complexes represent rare examples of high-temperature spin transition for mononuclear Fe(III) complexes with T1/2 > 350 K with very high thermal stability. Presence of strong intermolecular interactions and solvent-free nature of the complexes leads to exceptional thermal stability up to 485 K (for 1) and 496 K (for 2) as revealed by thermogravimetric analysis. The magnetic data for complex 1 have been analyzed by employing an Ising-like model with vibrations yielding the enthalpy change Δ H and entropy change Δ S of the spin transition along with the critical temperature T1/2 and the solid-state cooperativeness Γ. Spin crossover behavior of complex 1 has also been characterized by differential scanning calorimetry and electron paramagnetic resonance measurements. Ab initio calculations have been performed to analyze the difference in energies of the ground state and excited states of the complexes.

A Green Approach for Organic Transformations Using Microwave Reactor.

Microwave-assisted organic transformation (MAOR) is presently gaining wide popularity in the field of organic synthesis. The conventional heating technique is gradually being removed from the laboratory and a novel microwave heating technique established to be used in both academia and industry. As compared to the classical organic methodology, the green technology tools have several advantages like dramatically reduced reaction times, improved yields, site selectivity, and the increased product purities with simplification of work-up procedures. In the current study, we have briefly described the overview of recent developments and applications of microwave irradiation in organic transformation with schematic compiling of the organic reactions, bioactive heterocyclic compounds, and so on. This review also presents a critical analysis of the various advantages of microwave irradiation in organic synthesis/transformation compared to the classical or conventional heating. So, we believe that our current study of the green microwave heating technique will be highly beneficial for the researchers from both academia and industry in their near future.

3D isomorphous lanthanide coordination polymers displaying magnetic refrigeration, slow magnetic relaxation and tunable proton conduction.

Four new isostructural lanthanide-based three-dimensional (3D) coordination polymers (CPs), {[Ln4(OH)4(L)2(H2O)8]·4.6H2O·1.4CH3CN}n (Ln3+ = Gd3+ (1), Dy3+ (2), Ho3+ (3) and Er3+ (4)), have been constructed using a sulfonate-carboxylate-based ligand (Na2H2L = disodium-2,2'-disulfonate-4,4'-oxydibenzoic acid) and the corresponding lanthanide metal(iii) nitrates. All the CPs 1-4 contain [Ln4(µ3-OH)4]8+ cubane-like cores interconnected through L4- ligands to give rise to 3D coordination frameworks with 1D hydrophilic channels along the crystallographic c direction. From the topological perspective, the underlying 3D nets of the CPs can be classified as a 3,6,6-c net with an undocumented topology. Magnetic studies display that CP 1 exhibits a magnetocaloric effect with a significant magnetic entropy change (-ΔSm) = 34.6 J kg-1 K-1 for ΔH = 7 T at 3 K. CP 2 shows field-induced slow magnetic relaxation properties with energy barrier (Ueff/kB) = 30.40 K and relaxation time (τ0) = 2.47 × 10-7 s. Theoretical calculations have been performed to corroborate the magnetic exchange coupling constant value for CP 1 and to obtain a deeper understanding of the field-induced slow magnetic relaxation behavior of CP 2. Impedance analyses display high values of proton conductivity which reach 2.02 × 10-6, 2.96 × 10-6, 4.56 × 10-3 and 6.59 × 10-3 S cm-1 for CPs 1-4, respectively at high temperature (>75 °C) and 95% relative humidity (RH) in the order CP 1 < CP 2 < CP 3 < CP 4. Notably, the proton conductivities for CPs 3 and 4 are a few orders of magnitude higher than those of CPs 1 and 2 (10-3 S cm-1vs. 10-6 S cm-1), and the conductivity increases periodically following the decreasing order of ionic radius (Gd3+ > Dy3+ > Ho3+ > Er3+). This demonstrates the effective employment of the lanthanide contraction strategy to tune proton conductivity while preserving proton-conducting pathways.