Charged Sites Research Articles

Effect of Coordination Environment Surrounding a Single Pt Site on the Liquid-Phase Aerobic Oxidation of 5-Hydroxymethylfurfural.

As the frontier in heterogeneous catalyst, a monomer and positively charged active sites in the single-atom catalyst (SAC), anchored by high electronegative N, O, S, P, etc., atoms, may not be active for the multispecies (O2, substrates, intermediates, solvent etc.) involved liquid-phase aerobic oxidation. Here, with catalytic, aerobic oxidation of 5-hydroxymethylfurfural as an example, Pt SAC (Pt1-N4) was synthesized and tested first. With commercial Pt/C (Pt loading of 5 wt %) as a benchmark, 2,5-furandicarboxylic acid (FDCA) yield of 97.6% was obtained. Pt SAC (0.56 wt %) gave a much lower FDCA yield (28.8%). By changing the coordination atoms from highly electronegative N to low electronegative Co atoms, the prepared Pt single-atom alloy (SAA, Pt1-Co3) catalyst with ultralow Pt loading (0.06 wt %) gave a much high FDCA yield (99.6%). Density functional theory (DFT) calculations indicated that positively charged Pt sites (+0.712e) in Pt1-N4 almost lost the capability for oxygen adsorption and activation, as well as the adsorption for the key intermediate. In Pt1-Co3 SAA, the central negatively charged Pt atom (-0.446e) facilitated the adsorption of the key intermediate; meanwhile, the nearby Co atoms around the Pt atom constituted the O2-preferred adsorption/activation sites. This work shows the difference between the SAC with NPs and the SAA during liquid-phase oxidation of HMF and gives a useful guide in the future single-atom catalyst design in other related reactions.

Day-Ahead Forecast of Electric Vehicle Charging Demand with Deep Neural Networks

The increasing penetration rate of electric vehicles, associated with a growing charging demand, could induce a negative impact on the electric grid, such as higher peak power demand. To support the electric grid, and to anticipate those peaks, a growing interest exists for forecasting the day-ahead charging demand of electric vehicles. This paper proposes the enhancement of a state-of-the-art deep neural network to forecast the day-ahead charging demand of electric vehicles with a time resolution of 15 min. In particular, new features have been added on the neural network in order to improve the forecasting. The forecaster is applied on an important use case of a local charging site of a hospital. The results show that the mean-absolute error (MAE) and root-mean-square error (RMSE) are respectively reduced by 28.8% and 19.22% thanks to the use of calendar and weather features. The main achievement of this research is the possibility to forecast a high stochastic aggregated EV charging demand on a day-ahead horizon with a MAE lower than 1 kW.

Fabrication of high performance Mg2+/Li+ nanofiltration membranes by surface grafting of quaternized bipyridine

A new monomer (quaternized bipyridine, QBPD) was synthesized to modify the interfacially polymerized polyethyleneimine (PEI) membranes. The QBPD monomer, containing binary charge sites and amine groups (NH2), was anchored to the pristine PEI membrane through the “amine ∼ acyl chloride” amidation reaction. Pure water flux of the QBPD membrane is ∼ 96.6 L m−2h−1 while the MgCl2 rejection is maintained at 92%±3. Noteworthy, the flux is ∼ 2.8 times as high as that of the pristine PEI membrane (∼34.0 L m−2h−1 at 0.6 MPa). Meanwhile, separation performance of the QBPD membrane remains stable in 162 h operation time at 0.6 MPa. When filtrating 50:1 Mg2+/Li+ mixture, the flux of the QBPD membrane is 81.6 L m−2h−1, and the Mg/Li ratio in the permeate was reduced to 8.5:1. Collectively, the QBPD membrane shows good performance compared with recent nanofiltration membranes for Mg2+/Li+ separation, exhibiting considerable potential for lithium extraction from salt lakes with high Mg2+/Li+ ratio.

Network‐adaptive and capacity‐efficient electric vehicle charging site

The adaptive charging algorithms of today divide the available charging capacity of a charging site between the electric vehicles without knowing how much current each vehicle draws in reality. Thus, they are not able to detect deviations between the current set point at the charging station and the real charging current. This leads to a situation where the charging capacity of the charging site is not used optimally. This paper presents an algorithm including a novel feature, Expected Characteristic Expectation and tested under realistic circumstances. It is demonstrated that the proposed algorithm enhances the adaptability of the charging site, increasing the efficiency of the used network capacity up to about 2 kWh per charging point per day in comparison with the previous benchmark algorithm. The algorithm is able to increase the average monetary benefits of the charging operators by up to around 5.8%, that is 0.6 € per charging point per day. No input, such as departure time, is required from the user. The proposed algorithm has been tested with real electric vehicles and charging stations and is compatible with the IEC 61851 charging standard. The charging algorithm is applicable in practice as it is described in this paper.

Targeted Redesign of Suramin Analogs for Novel Antimicrobial Lead Development.

The emergence of new viral infections and drug-resistant bacteria urgently necessitates expedient therapeutic development. Repurposing and redesign of existing drugs against different targets are one potential way in which to accelerate this process. Suramin was initially developed as a successful antiparasitic drug but has also shown promising antiviral and antibacterial activities. However, due to its high conformational flexibility and negative charge, suramin is considered quite promiscuous toward positively charged sites within nucleic acid binding proteins. Although some suramin analogs have been developed against specific targets, only limited structure-activity relationship studies were performed, and virtual screening has yet to be used to identify more specific inhibitor(s) based on its scaffold. Using available structures, we investigated suramin's target diversity, confirming that suramin preferentially binds to protein pockets that are both positively charged and enriched in aromatic or leucine residues. Further, suramin's high conformational flexibility allows adaptation to structurally diverse binding surfaces. From this platform, we developed a framework for structure- and docking-guided elaboration of suramin analog scaffolds using virtual screening of suramin and heparin analogs against a panel of diverse therapeutically relevant viral and bacterial protein targets. Use of this new framework to design potentially specific suramin analogs is exemplified using the SARS-CoV-2 RNA-dependent RNA polymerase and nucleocapsid protein, identifying leads that might inhibit a wide range of coronaviruses. The approach presented here establishes a computational framework for designing suramin analogs against different bacterial and viral targets and repurposing existing drugs for more specific inhibitory activity.

Experimental and theoretical investigation of high- concentration elution bands in ion-pair chromatography

The effective separation of many solutes, including pharmaceuticals, can be performed using an ion-pair reagent (IPR) in the mobile phase. However, chromatographic separation and mathematical modelling are a challenge in ionpair chromatography (IPC), especially in preparative mode, due to the complicated chromatographic process. In this study, we present a retention mechanism and a mathematical model that predict overloaded concentration profiles in IPC using a system with X-Bridge C18 as stationary phase and tetrabutylammonium bromide in the 0 - 15 mM concentration range as the IPR. Two different mobile phases were used: (i) 15/85 [v/v] acetonitrile/water, (ii) 25/75 methanol/water. The model compounds were sodium salts of organic compounds with sulfonic acid functions. The analytical and preparative elution profiles were obtained for specified conditions. The analytical data were utilized to calculate the difference in electrical potential between the surface and bulk solution using firm electrostatic theory. In the preparative mode in a certain range of IPR concentrations, complicated U-shaped overloaded profiles were observed. In the other considered cases, Langmuir overloaded elution profiles were recorded. A multilayer adsorption model was derived, which is consistent with the dynamic ion exchange models. The model assumes that lipophilic IPR adsorbs on the stationary phase, creating charged active sites that serve as exchange sites for the solutes. The molecules of the solute can adsorb on the already formed IPR layer. It was also assumed that a subsequent layer of solute can form on the formed layer of complexes due to interactions between the solute molecules. The model takes into account the electrostatic attraction and repulsion of the molecules, depending on the considered situation. The proposed model allowed prediction of the overloaded concentration profiles with very good agreement for the model solute and followed the progression from Langmuirian, through U-shaped, to again Langmuirian profiles.

Tuning the stability and phosphate sorption of novel MnII/IVFeII/III layered double hydroxides

Layered double hydroxides (LDHs) have been intensively studied for phosphate (Pi) removal but suffer from poor stability and low sorption affinity under ambient conditions. In this paper, well crystallized MnIIFeIIFeIII-Cl, MnIIFeIII-CO3 and novel MnIVFeIII-CO3 LDHs were synthesized. The LDHs show fast Pi sorption with 90 % uptake within 20 min, and high Pi sorption capacity of 11 mg P/g at low solution Pi concenrations of 0.1 mg P/L, corresponding to a very high Pi sorption affinity (Kd 1.1 × 105 L/kg). Fast MnII dissolution from the MnIIFeIIFeIII-Cl LDHs and formation of MnFe2O4 at pH 7 were observed in aqueous suspensions of non-oxidized material where up to 70% of total Mn was released within 2 h. However, when interlayer Cl- was exchanged with CO32−, much lower Mn dissolution (5.4%) was observed. Furthermore, after oxidation of MnII to MnIV, the obtained MnIVFeIII-CO3 LDH maintained the layered structure of LDH and the particles were surrounded by birnessite nanorods. The MnIVFeIII-CO3 LDH showed excellent stability but lower Pi sorption capacity. However, a high sorption affinity was maintained which is attributed to more positively charged Fe-centered sorption sites. XPS and ATR-FTIR data together with DFT calculations demonstrated that Pi was mainly sorbed via the formation of mononuclear mono- and bidentate Pi surface complexes on planar LDH particle surfaces.

Formation of the Metal-Binding Core of the ZRT/IRT-like Protein (ZIP) Family Zinc Transporter.

Zinc homeostasis in mammals is constantly and precisely maintained by sophisticated regulatory proteins. Among them, the Zrt/Irt-like protein (ZIP) regulates the influx of zinc into the cytoplasm. In this work, we have employed all-atom molecular dynamics simulations to investigate the Zn2+ transport mechanism in prokaryotic ZIP obtained from Bordetella bronchiseptica (BbZIP) in a membrane bilayer. Additionally, the structural and dynamical transformations of BbZIP during this process have been analyzed. This study allowed us to develop a hypothesis for the zinc influx mechanism and formation of the metal-binding site. We have created a model for the outward-facing form of BbZIP (experimentally only the inward-facing form has been characterized) that has allowed us, for the first time, to observe the Zn2+ ion entering the channel and binding to the negatively charged M2 site. It is thought that the M2 site is less favored than the M1 site, which then leads to metal ion egress; however, we have not observed the M1 site being occupied in our simulations. Furthermore, removing both Zn2+ ions from this complex resulted in the collapse of the metal-binding site, illustrating the "structural role" of metal ions in maintaining the binding site and holding the proteins together. Finally, due to the long Cd2+-residue bond distances observed in the X-ray structures, we have proposed the existence of an H3O+ ion at the M2 site that plays an important role in protein stability in the absence of the metal ion.

Hydrogen as an energy currency: Encapsulation of inorganic Ga12N12 with alkali metals for efficient H2 adsorption as hydrogen storage materials

Demand of efficient energy storage materials increases day by day due to high energy production rate. Hydrogen energy is considered as currency for next generation because it has numerous applications in routine life where industry has safely used hydrogen for decades in petroleum refining, glass purification, fertilizer production, pharmaceuticals, and aerospace applications. In this line, an attempt has been made to design new systems for possible hydrogen storage. Advanced quantum chemical techniques are used by employing Density Functional Theory (DFT) at B3LYP/6-31G(d,p) level. Incorporation of metals in inorganic nanoclusters always enhanced the adsorption of an analyte. In this study, the design of new gallium nitride (G12N12) nanoclusters by encapsulation with alkali metals (Li, Na and K) has been presented. Adsorption of H2 on these deigned systems is examined through various parameters like interaction energy, band gap, dipole moment, natural bonding orbitals analysis, and molecular electrostatic potential analysis. Further, global indices of reactivity are also used to unveil the natural stability and reactivity of these designed systems. Presence of different charge sites in designed systems indicated that the adsorption of hydrogen significantly enhances the charge shifting rate. Large values of natural bonding orbitals also found in support of large dipole moment values. Overall, narrow band gap with maximum charge transfer rate is found in all the designed systems, which suggested that these designed systems are efficient candidates for maximum hydrogen adsorption and storage purposes. Finally, a recommendation has been made for the experimentalists to consider these novel systems for the development of next generation hydrogen storage materials.

Charging powers of the electric vehicle fleet: Evolution and implications at commercial charging sites

Electric vehicle (EV) charging is widely studied in the scientific literature. However, there seems to be a notable research gap regarding the charging power limitations of the on-board chargers of the EVs. In this paper, the present state of the maximum charging powers of the on-board chargers is thoroughly analysed using data from two commercial charging sites. Furthermore, the results of the analysis are used along with an EV fleet development model to form realistic future scenarios, which are then used for a simulation model that couples the charging sessions with measured charging profiles. The results of the simulations show that, due to the evolution of the EV fleet, the average energy consumption in commercial locations will increase by 134% on average from 5.6 to 8.7 kWh/EV to 13.0–19.6 kWh/EV during 2020–2040. Similarly, the peak of the normalized power increases by 77% on average from 1.1 to 1.4 kW/EV to 1.6–2.9 kW/EV. These values are essential to guide long-term decisions such as optimal sizing of charging infrastructure and parking policies.

P-Block Atomically Dispersed Antimony Catalyst for Highly Efficient Oxygen Reduction Reaction.

Main-group (s- and p-block) metals are generally regarded as catalytically inactive due to the delocalized s/p-band. Herein, we successfully synthesized a p-block antimony single-atom catalyst (Sb SAC) with the Sb-N4 configuration for efficient catalysis of the oxygen reduction reaction (ORR). The obtained Sb SAC exhibits superior ORR activity with a half-wave potential of 0.86 V and excellent stability, which outperforms most transition-metal (TM, d-block) based SACs and commercial Pt/C. In addition, it presents an excellent power density of 184.6 mW cm-2 and a high specific capacity (803.5 mAh g-1 ) in Zn-air battery. Both experiment and theoretical calculation manifest that the active catalytic sites are positively charged Sb-N4 single-metal sites, which have closed d shells. Density of states (DOS) results unveil the p orbital of the atomically dispersed Sb cation in Sb SAC can easily interact with O2 -p orbital to form hybrid states, facilitating the charge transfer and generating appropriate adsorption strength for oxygen intermediates, lowering the energy barrier and modulating the rate-determining step. This work sheds light on the atomic-level preparing p-block Sb metal catalyst for highly active ORR, and further provides valuable guidelines for the rational design of other main-group-metal SACs.

Carbon Deposition on Heterogeneous Pt Catalysts Promotes the Selective Hydrogenation of Halogenated Nitroaromatics.

Pt-based heterogeneous metal catalysts are commonly used in the hydrogenation of nitro groups. However, the continuous large metal domain size and the complex interaction between the substrates and metal surface usually inevitably result in side reactions, such as dehalogenation of halogenated nitroaromatics. In this work, by simply treating the Pt-based catalysts with CO at elevated temperature, the Boudouard reaction taking place on Pt surface results in the deposition of carbon species thereon. The carbon deposition not only inhibits the dehalogenation by restricting the planar interaction of the aromatic group with the Pt surface that is segmented by C, the hydrogenation activity of the nitro group is also enhanced on the partially positively charged surface Pt sites created by the electron-withdrawing interstitial C. Such a simple treatment strategy is effective for fabricating Pt-based catalysts on different supports toward the selective hydrogenation of a wide range of halogenated nitroaromatics.

New insights into the allosteric effects of CO2 and bicarbonate on crocodilian hemoglobin.

Crocodilians are unique among vertebrates in that their hemoglobin (Hb) O2 binding is allosterically regulated by bicarbonate, which forms in red blood cells upon hydration of CO2. Although known for decades, this remarkable mode of allosteric control has not yet been experimentally verified with direct evidence of bicarbonate binding to crocodilian Hb, probably because of confounding CO2-mediated effects. Here, we provide the first quantitative analysis of the separate allosteric effects of CO2 and bicarbonate on purified Hb of the spectacled caiman (Caiman crocodilus). Using thin-layer gas diffusion chamber and Tucker chamber techniques, we demonstrate that both CO2 and bicarbonate bind to Hb with high affinity and strongly decrease O2 saturation of Hb. We propose that both effectors bind to an unidentified positively charged site containing a reactive amino group in the low-O2 affinity T conformation of Hb. These results provide the first experimental evidence that bicarbonate binds directly to crocodilian Hb and promotes O2 delivery independently of CO2. Using the gas diffusion chamber, we observed similar effects in Hbs of a phylogenetically diverse set of other caiman, alligator and crocodile species, suggesting that the unique mode of allosteric regulation by CO2 and bicarbonate evolved >80-100 million years ago in the common ancestor of crocodilians. Our results show a tight and unusual linkage between O2 and CO2 transport in the blood of crocodilians, where the build-up of erytrocytic CO2 and bicarbonate ions during breath-hold diving or digestion facilitates O2 delivery, while Hb desaturation facilitates CO2 transport as protein-bound CO2 and bicarbonate.

Removal and surface photocatalytic degradation of methylene blue on carbon nanostructures

Removal and photodegradation of methylene blue on the surface of three distinct carbonaceous materials, pure and nitrogen-doped multi-walled carbon nanotubes, and graphitic nanoribbons, were examined. Carbon nanostructures were characterized by scanning electron microscopy, transmission electron microscopy, thermogravimetric analysis, Raman spectroscopy, X-ray photoelectron spectroscopy, and N2 adsorption/desorption isotherms. Removal and photocatalytic activity were evaluated by static adsorption under UV irradiation. Photocatalytic activity on carbon nanostructure exhibited a pseudo-first-order kinetic model. The adsorption capacity and photocatalytic activity of carbon nanostructures were mainly attributed to their defective and reactive surface. Nitrogen-doped multi-walled carbon nanotubes showed the best adsorption capacity and photocatalytic activity, which can be attributed to the highly reactive sites due to nitrogen doping, also by π–π electron donor-acceptor interaction between sp2 lattice of carbon nanostructure surface and negatively charged sites at methylene blue molecules.

Trinuclear Calcium Site in the C2 Domain of PKCα/γ Is Prone to Lithium Attack.

Lithium (Li+) is the first-line therapy for bipolar disorder and a candidate drug for various diseases such as amyotrophic lateral sclerosis, multiple sclerosis, and stroke. Despite being the captivating subject of many studies, the mechanism of lithium’s therapeutic action remains unclear. To date, it has been shown that Li+ competes with Mg2+ and Na+ to normalize the activity of inositol and neurotransmitter-related signaling proteins, respectively. Furthermore, Li+ may co-bind with Mg2+-loaded adenosine or guanosine triphosphate to alter the complex’s susceptibility to hydrolysis and mediate cellular signaling. Bipolar disorder patients exhibit abnormally high cytosolic Ca2+ levels and protein kinase C (PKC) hyperactivity that can be downregulated by long-term Li+ treatment. However, the possibility that monovalent Li+ could displace the bulkier divalent Ca2+ and inhibit PKC activity has not been considered. Here, using density functional theory calculations combined with continuum dielectric methods, we show that Li+ may displace the native dication from the positively charged trinuclear site in the C2 domain of cytosolic PKCα/γ. This would affect the membrane-docking ability of cytosolic PKCα/γ and reduce the abnormally high membrane-associated active PKCα/γ levels, thus downregulating the PKC hyperactivity found in bipolar patients.

Oxygen vacancy assisted condensation of DNA molecule observed on ZnO thin film

An exotic condensation of DNA molecules is observed on the nanostructured ZnO surface. The ZnO nanostructures (NS) fabricated by thermal vapor deposition technique were associated with a large number of oxygen vacancies on the surface. These oxygen vacancies induced changes in the DNA conformation which further reflected through changes in the persistence length of the DNA molecules. This indicates a reinforcement of the bonds and binding in both the phosphate and the base regions of the DNA molecules with the positively charged core vacancy sites on the ZnO nanostructured surface through strong interaction mediated via long-range electrostatic forces which effectively reduced the end-to-end distance of the λ-DNA molecule. This strongly suggests a transition of the λ-DNA molecule through structural modification into a more compact higher-order fractal dimension from its native state.

Trapped ion mobility spectrometry time-of-flight mass spectrometry for high throughput and high resolution characterization of human milk oligosaccharide isomers

The microbiome and immune system of infants are shaped by various bioactive components of human breastmilk, notably human milk oligosaccharides (HMOs). HMOs represent the third component of breastmilk and exhibit extremely high structural diversity with many isomers. Here, we propose a high throughput and high resolution approach to characterize main oligosaccharides present in breastmilk with high identification level thanks to ion mobility spectrometry. Four pairs of standard HMO isomers, that are (LNT/LNnT), (LNFP I/LNFP V), (3′-SL/6′-SL) and (2′-FL/3-FL), were first investigated under both positive and negative ionization mode using direct introduction-trapped ion mobility spectrometry-time-of-flight mass spectrometry (TIMS-TOF). By examining all the ionic species formed (i.e. protonated and deprotonated ions as well as adduct species), every isomer pair could be distinguished through the separation of at least one species, even with a small difference in collision cross section values (as small as 1.5%) thanks to the flexible resolution capacity of the TIMS instrument. Although multiple mobility peaks resulting from different glycan anomeric conformers, open-ring and/or different ionic isomer structures (i.e. various charge site locations), could be observed for some HMO species. The reduction at the reducing-end of HMOs did not significantly facilitate the isomer distinction. Finally, the unambiguous identification of the studied HMOs in a breastmilk sample showed the potential of the approach combining ion mobility separation and MS/MS experiments for high throughput distinction of HMO isomers in complex breastmilk samples without laborious sample preparation.

Montmorillonite promoted photodegradation of amlodipine in natural water via formation of surface complexes

The photolysis of amlodipine (AML) as a ubiquitous pollutant in natural water has been extensively studied. Montmorillonite (MMT), a major component of suspended particles in surface aquifers, plays key roles in the natural transportation and transformation of organic contaminants in the environment. However, literature has scarcely focused on whether and how suspended particles affect the phototransformation of AML. This study systematically investigated the phototransformation behavior of AML in MMT suspensions under simulated sunlight. The results obtained showed that MMT significantly enhanced the photolysis of AML. The photodegradation of AML in 0.05 g/L MMT suspension reached 92.2 % after 3 h irradiation under the simulated sunlight. The photodecomposition followed the pseudo-first-order kinetic with a rate constant of 0.803 h−1 in the presence of 0.05 g/L MMT, which is about 19 times larger than that in the absence of MMT (0.0421 h−1). Further mechanistic investigation suggested that MMT accelerated the photolysis of AML by the formation of surface complexes between cationic amino groups of AML and the negatively charged sites on MMT surface, which greatly facilitated light absorption and electron transfer for the production of cationic radical AML+·. Meanwhile, the hydroxyl radicals generated by irradiated MMT also played an important role in the photocatalytic degradation of AML. The probable photodegradation pathways of AML in MMT suspension further supported the proposed mechanisms. The toxicity evaluation of phototransformation products of AML with ECOSAR program indicated that photolysis could reduce its potential threats. These findings reveal an important and previously overlooked phototransformation mechanisms of AML in the presence of MMT clays, which is of importance in assessing the environmental fate of other similar organic contaminants.

Electrode and electrolyte regulation to promote coulombic efficiency and cycling stability of aqueous zinc-iodine batteries

Aqueous zinc-iodine batteries are promising electrochemical energy storage systems due to the high safety and low cost. The application of zinc halide solution as the electrolyte allows the dual-plating mechanism on both electrodes, i.e. the redox reactions of Zn2+/Zn and I2/I- at the anode and cathode, respectively. These solid–liquid conversion processes guarantee excellent reaction kinetics. However, soluble polyiodide (I3-, I5-, etc.) are formed at the cathode either during the oxidation of I- or from the reaction between I- and I2. The dissolution of polyiodide in electrolytes causes rapid loss of charged products, leading to poor coulombic efficiency and fast self-discharge. Herein, we apply the synergistic regulation of electrode and electrolyte to confine the charged products. The conducting polymer polyaniline (PANI) is used as the polyiodide binder. It contains positively charged nitrogen sites, allowing the doping and effective binding of polyiodide anions through electrostatic attraction. At the same time, the complex in zinc halide electrolytes is regulated to eliminate free iodide anions and prevent the reaction with I2 to form more polyiodide. The optimized zinc-iodine aqueous battery delivers excellent rate capability thanks to the facile solid–liquid reactions as well as the high electrical conductivity of PANI. More importantly, it achieves a high coulombic efficiency of 99.2% with the capacity of 2 mAh cm−2 at 6 mA cm−2, and an excellent capacity retention of 99.9% after 1000 cycles is realized upon long-term cycling. The work proposes a potential pathway to realize stable energy storage in aqueous zinc-halogen batteries.

Phase Separation of Polyelectrolytes: The Effect of Charge Regulation.

Complex coacervation, known as the liquid–liquid phase separation of solutions with oppositely charged polyelectrolytes, has attracted substantial interest in recent years. We study the effect of the charge regulation (CR) mechanism on the complex coacervation by including short-range interactions between the charged sites on the polymer chains as well as an association–dissociation energy parameter in the CR mechanism. We investigate the phase diagrams of two CR models: (i) the hopping CR model (HCR) and (ii) the asymmetric CR model (ACR). It is shown that during the phase separation that the polymers in the condensed phase are more charged than those in the dilute phase, in accordance with Le Chatelier’s principle. In addition, secondary CR effects also influence the change in the volume fraction of the two phases. The latter can cause the charge difference between the two phases to change nonmonotonically as a function of the CR parameters.