Older versions more complete but.... Umm less complete. I'm hopefully putting the pieces back together for the final edition. The Costello Constant (CC) base (e/phi - 1/pi), and Costello sequence governed by n(+1) = n + f(n), f(n) is the Greatest Proper Divisor of n(-1); f(n1) = 1, mapped onto the complex plan Y(ix) = (e/phi -1/pi)^(0±ix) using x as a time function for an. added dimention, forms a single helix that bifurcrates into. duel helix where intersection of the 2 spiraling lines cancel out from complete annihilation at value of the first zero~(14) this helix is anchored to the origin by raising the base to the power of zero, The even exponent of i are one helical arm, the negative value of i is the odd value helical arm. Points where they annihilate the x values are the zeta zeros value with a frequeny ~ 10.33715124⊠the slope of the sequence on a semi logarithmic graph align perfectly straight⊠or the inverse of... when joining sequential odds treating the O O E cycles as only 2 values (plot points, both odds as one single unit, multiplied by the value of CC ~ 1.3616... gives the exact value zeta zero 1, in the sequence this is equivalent to the Attractor a10 (16) when looking at ratios between zero 1 and zero 2 as an x/y it matches exactly to (13+16+17/3)/(17/25/26) this number and it's simplest reduced form 268/183 also are the exact ratio of certain toma in chemicals. And te genes which map a certain protein. I assume other ratios between consecutive numbers and the sequence will reveal some wonders in the universe that have remained untold until this moment. I've been ignored for weeks now which has giving me the time to dive into a level of certainty beyond any shadow of a doubt. On the regular graph when treating odds consecutive as one and evens as one connecting all evens and connecting All Odds creates two distinct lines where are the formula of the Costello constant is right in the middle. Basically turning the Zeta zeros into an algebraic problem by connecting the dots odds and evens where intersects on the equation graphed is the location of the Zeta zeros. Mic drop. V6. Added details about the zero timing overlap with formula being dictated by timing of pair sequential numbers in the sequence being used. V7. Added Defining Costello Constant's Value, Definition, And Symbol. V8. Added Data Set Of Sequence Numbers As T Values V9. Eureka! Offset fixed! "^0 + it" is the golden key it's officially solved. The Costello spiral is the structure, The zeta zeros are mapping the features of it. V10. Added Needed Proof V11. Complete revamp fixing errors in construction. I'm a non-academic... I'm trying here... Alone... V12. Updated Formatting Pages 1 - 2 Finalized V13. Update Pages 1 - 3 Finalized, 4 - 7 Drafted V14. Finalized Doc 1 Current Version Is A Fully Closed Loop System Logic, It's Proof By Fundamental Law. Costello Spiral Diagrams Reflects Older .809... Helix Radius Matching Pre 1.0000 Radius Formula Reduction. "This Fundamental Law is scale-invariant; while earlier diagrams (0.809) and the finalized 1.0000 reduction represent different magnitudes, the underlying closed-loop logic and intersection intersections remain constant. The 1.0000 Unit Radius represents the simplest, normalized state of the Costello Spiral." One last note to whom it may concern... I did this completely independent starting from the ground up with no previous research into other publishments, I started with the desire to make a sequence that was novel, and just kept making connections one after another. I've watched a couple YouTubes in the past that had discussed vaguely The mystery of the Zeta zeros and that's about the extent of my outside knowledge. I didn't set out to discover the secret for it, my series ran into it by its nature itself. V15. Updated format to Latex, added much more vigorous math proof, order of logic still needs tweaking. V16. Added data point charts into Latex pdf. V17. Formatting Fixes V18. Added -1 somewhere... Oops V19. Added how the Costello Spiral solves the Collatz Conjecture too. V20. Added hypothesis of the twin Prime conjecture V21. Fixed Rooke Mistakes... Double Statements... Out of order stuffs.... V22. More Formatting Fixes. V23. Lots better, 25+ years sine education environment, first proof... Getting there... V24. Added formula for ratio relationship of factors to the zero spacing, but messes up my formatt big time... Lullz.. im fixing it. I hate all these loops I have to jump through honestly, taking away from time that I could just be diving further in the numbers as usual. I'm almost giving up a couple times I just went back to my paper notebooks. V25. Well maybe have about 10% of the information out now... Main problem is I don't know what's most important to show I don't know what the world knows or not... Like I don't know what to add next the list is too big... Semi-prime Costello sequence numbers that are close together align with Zeta zeros close together.. eg., 7171... So much work... I've tried showing my math and I get laughed at... I'mma just keep on pushing... It may not be conventional to add your thoughts or whatever... But I'm a break the fifth wall right now... From two weeks now I've tried reaching out... All skepticism.. it just hit me tonight... It's because it's all sounds too good to be true... I didn't know that... I'm trying to do too much at once... I mean on top of my work that I'm doing I had to learn the formal language... I've had to learn how to code... I've had to learn Python script so I can run my old numbers... And for 2 weeks now I've been pushing... To show people ONE of my creations. Maybe the world is just not ready.... .. .. . Maybe. It's hard to forget, everything I regret. So why do I neglect, the chances that I get, To make those things correct... When I've tried to reflect... I just lost more respect... How did i ever let my mindset behind set get so inept. While im On the subject if I may be direct. I digress... It is best to get the rest of my chest. Im blessed but made a mess whats more or less my nest. I feel i failed my quest, I have failed my own test. It's a sure bet soon I'll take my last breath. Back to work... V26. Gtting there... Please use V23 complete copy until i stop mesing up my work with copy pasts twice deleed everything. V Edition2 V27. New formatt next few additions should be coming back to back to back as I string the old with the new. Refer to V22/23 for older complete outline, V Edition2 V28. Brought over some data from my research pfd, order and simplification are needed. V Edition2 V29. Stitching in the dimensional transitions from the number line to a real plane to complex plane to the manifold. Still need smooth transitioning. V Ediion2 V30. Added a good chunk to complex/manifold section, I just want to get it uploaded, I still have to prune it and smooth it. And make sure the stuff at the end is stated the way it's supposed to before I can remove it. Editiom2 V31. Added 10.3 frequency of spiral is the slope of sequence on log xy. Deleted doubles. Edition2 V32 Added dada set at end, refining python code number generator to add next. Edition2 V33 Changed Description on Zenodo added some info to I - III, refer to Ver 23 in tandem as f now after reading to complete the info aquired. Lots more to come... Edition2 V33.2 Keep Pushing Unil The World Listens... Changed Sequence Formula Formatt of f(n) Fixed Order still have to move over more sections from research Pdf. Including making sure pdf reflects duel helix is intersecting as counter clockwise 1 string and clockwise the other, reforming old 180° opposition, to actual intersection. At 0° Edition2 V34. Updated High Precision Value Of Slope using 500 sequence Values, Added bar graph for delta 2 equalization, other minor adjustments. Edition2 V35. Fixing all formulas to compensate for the change of what f(a_n) is.. as befor the rule a_n+1 = a_n + f(a_n-1) when f(a_n) meant a_n's GPD.. but for clearity f(a_n) now means a_n-1's GDP... To remove a LAG extra thought... Royal pain but a necessity.... Almost done converting everything. Edition2 V36 Formalized Pages 1-2 of actual proof after index, added rigor and made it more succinct. Eution2 V37. Showed how 10.337... slight miss alignment snap perfectly to 10.333 and perfectly aligned to zz1 now that start up terms 1-9 are removed from calculations. Edition2 V38 Formed formulas using the costello constant for prime density and how many primes exist in any limit, gives exct answer at 1,000,000. Edition2 v39 Finalized pages 1-4 Edition3.1 Finalize Format Starting To Translate. Page 1 done, Page 2 in progress Edition3.2 Actual Professional Formatt Learned And Applied.Pae 1/2 almost good. Should be a quick transition building back a strong base from dra in previous versions. Edition3.3 Added .6 Parity Limit, Growth Factor & Graph. Edition3.4 Added Symmetry/2-adic Sections & Tables Edition3.5 added the singularit Edition3.6 Formatt ambiguities removed, added minor info, Organized Zenodo Ledger, Edition3.7 Unified formatt formatt & variables, added log/non lomgrph real graphs, n more. Edition3.8 Added Changed To Font/Formatt Added Graphs Other Minor Additions Edition3.9 Bulletproofed Logic up to Lambda parity Density 0.6, 2:3. Edition3.10 Defined Lambda and lambda, added parity density equations and table Edition3.11 Added High Precision Lambda Values, 2 Graphs (1 Custom Expanding Y Axis} Edition3.12 Learned Python... Wrote and added script for producing Verifiable Data, Include plain txt file and 2 Appendix to PDF with Program and sample data. Edition3.13 Streamlined f function by introduction of spa divisor set mapped to n. Defined Tau and some other minor stuffs. Edition3.14 Added plain txt documents of raw Latex Code And Python Sequence Engine Edition3.15 Added Infinit tetration of B = C,, LogB(C) = C, LogC^(1/C)=B,
As outlined in the Paris Agreement, the global commitment to achieving net-zero emissions by 2050 necessitates a multifaceted approach encompassing clean energy initiatives and carbon taxation.Higher education institutions, recognizing their role as key contributors to sustainability, are increasingly focusing on reducing their carbon footprint.The teaching laboratories, essential for various disciplines, contribute significantly to the university's carbon footprint.In this study, we applied the common practices of Life Cycle Analysis (LCA) in the industry to the Unit Operations Laboratory, which resembles the industrial settings yet focuses on teaching and learning that may not have set production scopes nor define operation conditions and processes (i.e. for learning purposes and study impact of various factors on common chemical processes).As learning is the main objective in undergraduate laboratories, LCA methodologies related to laboratory equipment and incorporating technical information on global climate initiatives, clean energy, and the Paris Agreement need to be followed, but some modifications to make such calculations possible.To illustrate the feasibility of this approach, a case study on bioethanol production through yeast fermentation and subsequent distillation processes is employed as a proof-ofconcept.This case study serves as a platform for estimating LCA and redesigning experiments with the aim of reducing the carbon footprint.Since not all chemical process units are designed the same (i.e.sizes, power/production capacity), this project is a collaborative effort internationally amongst universities with similar equipment but different sizes.The carbon footprint approaches, and the preliminary data collected can enable fine-tuning and test the robustness of the approaches and models.The Unit Operations Laboratory emerges as a valuable platform for students to assess their carbon footprint and actively engage in practical LCA applications.This research contributes to the broader goal of embedding sustainability principles within the educational framework, fostering a generation of professionals equipped with the knowledge and skills necessary to address environmental challenges.
By making a state of the art on the regulations and standards, in force and in progress, this deliverable aims to better inform the regulatory aspects of the design of reusable packaging and to analyse the barriers and opportunities to implement the reuse of packaging, so as to spot potential conflicts with constraints linked to this purpose. The first part is dedicated to the main definitions useful to understand the subject of packaging reuse. To make a relevant state of the art in the second part, we investigated two major issues which both concern the reuse of packaging, at European and national levels, in countries of BUDDIE-PACK's partners: hygiene on one hand and packaging on the other hand, in order to identify any pain point in the reuse of packaging. It can be noted that all the hygiene regulations that we have identified relate to the food sector and do not include any mention of non-food products, such as home care products, which are operated in the use case of ASEVI. Regulation (EC) N°852/2004 lays down the general rules on the hygiene of foodstuffs and especially requires that containers used for transporting foodstuffs to be designed so that adequate cleaning is possible, and to be dedicated for the transport of foodstuffs. Complementary good practices are also mentioned in the Codex Alimentarius, an internationally recognized collection of food standards, and in the ISO 22000 and EN 15593:2008 standards. In Directive 98/83/EC on the quality of water likely to be used in the food industry, despite microbiological and chemical requirements, a vagueness can be observed on three parameters impacting hygiene, which are the colour of water, its smell and its taste: indeed, the Directive only requires that these parameters must be âacceptable to consumerâ and that âno unnatural changeâ can be observed, which means that non-compliance thresholds may vary according to the stakeholders. Standard EN 17735:2022 is essential to guarantee the safety of washing, as it specifies the hygiene requirements for the operation of commercial dishwashers in a professional environment and also includes the main guidelines for obtaining hygienic results for treated articles. To close the chapter on hygiene, one must note that a standard exists to assess the efficience of disinfectants in the food area through a quantitative test on a nonporous surface, such as steel, but that such a standard does not exist on plastic surfaces. The third part presents the packaging regulations from four angles (design, food contact, production and recycling, non-food products) and an institutional analysis. Directive 94/62/EC, on Packaging and Packaging Waste (PPW), is currently being revised by the European Commission: it should become a Regulation, directly applicable by all Member States, and shall further support the implementation of reusable packaging. The vote is expected in September 2023. It should be noticed that the restrictions set in Directive (EU) 2019/904 SUP (Single-Use Plastic) only concern single-use plastic packaging. Regulation (EU) N°10/2011 regulates the safety of plastic materials in contact with food. It gives guidance on specific migration test methods, including for reusable materials: its limitation is that it considers a low number of reuses, so it does not take into account the possible degradation of the material, such as scratches which are inherent in the prolonged reuse of packaging and which can impact the migrations of substances. The REACH Regulation, also under review, establishes procedures for evaluating information on the properties and hazards of chemical substances. Due to the many substances used in the manufacture of plastics and required to make them sustainable, REACH revision may have an impact on the development of reusable packaging. In Regulation (EU) 2022/1616 setting the operating rules of all recycling stages, it is interesting to remember that recycling schemes, of any material, in a closed and controlled chain may be considered as suitable to recycle waste plastic into food-contact plastic, in the same way as mechanical PET recycling. This principle could be implemented for any reusable packaging provided that it is used in a closed system and that external non-foodstuffs contaminations are avoided. Regulation (EC) N°648/2004 on detergents, such as ASEVIâs products, does not mention any requirement on the packaging. Some of BUDDIE-PACK's partners countries, France, Spain, Germany and The Netherlands, have passed laws to implement reusable packaging, with a focus on food or beverage consumption, on-site or on-the-go. While France explicitly banned single-use packaging in several sectors in addition to the on-site catering, Germany and The Netherlands set less restrictive incentives for on-site and take-away catering, and Spain addressed quantified reuse targets for take-away beverage and beverage sold in food retail stores. Note that the UK's exit from the EU led to the transposition of most of regulations mentioned in this deliverable into national law, without significant differences with European regulations, except the SUP Directive, for which an equivalent legislation is expected in October 2023. Beyond these regulations already adopted to promote the reuse of packaging, this dynamic is much broader than Europe: thus, the United Nations Environment Assembly has created an Intergovernmental Negotiating Committee responsible for drafting a text "legally binding" by October 2024. The work sessions should result in a first draft text by November 2023. The suggestions of NGOs converge on the development of shared logistics infrastructures and user-friendly packaging, the expansion of DRS to encourage consumer engagement, but also the standardisation of LCA methods to ensure data reliability. The NGO Zero Waste Europe also insists on the need to implement economic levers to encourage companies to offer reusable packaging, and consumers to choose it. The fourth part gives more details on the main expected modifications in the regulations being revised, especially the PPW and the REACH Regulations, which could impact the development of reusable packaging. To help provide answers to BUDDIE-PACK use cases, the fifth part summarises the regulations and standards that cover each use case, in order to find all information sources at a glance, to incorporate them into the packaging design and to produce packaging fully adapted to the needs. To conclude with this deliverable, the sixth part explains the main barriers and above all the opportunities, at regulatory, technical, safety, social and economic levels. As the hygiene regulations establish an obligation of results towards the actors of the value chain, and not of means, the reuse of packaging does not conflict with hygiene constraints on condition that each part provides the required health guarantees on its scope. Our innovation approach and its proof of concept should allow to identify risky points in advance and to develop solutions to scale up without risk. The debate on the revision of the REACH Regulation will have to be considered into the SSbD concept. In addition, discussions on the PPW Regulation and the Global Plastic Pollution Treaty may open new perspectives of strategies to implement reusable packaging by the end of 2024. The two major technical obstacles are the lack of knowledge about the ageing of plastics through cycles of use and washing (degradation of polymer chains after heat treatment, repeated sealing or mechanical stress, water abrasion) and logistics (collection of used packaging, storage, transport). The Digital Product Passport should therefore be an effective lever for optimising the return of packaging and its durability. Moreover, the standardisation of packaging, coordinated at a European level in cooperation with EPRs and business operators shall allow an optimisation of transport and storage. Capitalising on the experience of manufacturing and retailing sectors which already reuse their packaging will be decisive, especially on the logistics. Solving safety obstacles will be also essential to develop the reuse of packaging, i.e. defining compliance criteria on rinsing and drying to ensure there is no residue of detergent or water, and investigating the risks of migration of substances and release of microplastics, from a material which has been used multiple times. On the first point, depending on the sector, industrial means allow to prevent food contamination (ventilation, humidity control, ease to clean premises and equipments, specially trained staff, etc.). Capitalising on the experience of actors already involved is also an important action lever, such as bottlers or school catering. Social barriers are difficult to solve because they require changing deep-rooted habits, for both packagingâs users and consumers. Restaurants may be afraid of wasting time in their daily tasks (additional time to handle, store, wash, wipe, etc.). Some of consumers could be reluctant to use a packaging that they gauge it has already been used (scratch, small stain, discoloration, etc.), even if it is clean and safe, which requires a specific pedagogy. Active consumerism can effectively contribute to the proper functioning of the reuse loop and is very rewarding for the consumer, as we see it with the successful development in Europe of DRS. Giving back an economic value to packaging should also prevent waste from being abandoned. Even if their exact role is not yet defined, business operators will have to be strongly involved in the management of the reuse loop in opposition to the management of waste, which is dealt by local authorities. This involvement and the initial investment in packaging will impact their business model. To help them, public policies should support adequate eco-modulations and the development of shared logistics. Various incentives should be also addressed to consumers to encourage them to ch
This study presents an environmental, social, and governance (ESG) strategic model to manage pharmaceutical supply chains with financial obstacles. ESG environmental, social, and governance research can help managers make informed decisions so that managers can better choose the corresponding operating strategies, pay attention to environmental protection, and actively fulfill social responsibilities. We consider matching strategies between manufacturers and retailers by classifying them into no matching, decentralized matching, and centralized matching strategies between manufacturers and retailers. Under the matching strategy, we consider the decentralized ESG operation strategy and centralized ESG operation strategy, divide the decentralized ESG strategy into a supplier-dominant mode (SD), manufacturer-dominant mode (MD), and retailer-dominant mode (RD), and study the optimal decision-making methods of supply chain members in different modes. The innovation of this study lies in (1) considering financing constraints; (2) the impact of indicators on society and the environment; (3) no matching strategy, decentralized matching strategy, and considerations of centralized matching strategy; (4) decentralized and centralized strategies under relevant ESG indicators to improve the accuracy of the model; (5) the decentralized ESG operation strategy is divided into a supplier-dominant mode (SD), manufacturer-dominant mode (MD), and retailer- dominant mode (RD); and (6) Applying the ESG strategy to Pharmaceutical supply chain Management. The different models are compared and analyzed to find the equilibrium strategy and the optimal solution under different models. Through various analysis, we found that integrating a pharmaceutical supply chain and the ESG governance strategy can effectively promote the innovation of the industrial chain supply chain. A supply chain matching strategy is more effective in managing a supply chain than a no-matching strategy and can improve the financing efficiency of capital-constrained manufacturers. In the matching strategy, centralized matching can better attract consumers who prefer green and âdouble carbonâ products than decentralized matching. Under the lower level of green investment, the centralized ESG governance strategy can better contribute to developing the pharmaceutical supply chain.
XiuâShuang Xing, Cai Sun, Lu Liu, MingâSheng Wang · 5 authors
Open AccessCCS ChemistryRESEARCH ARTICLE1 Nov 2021Light-Responsive Proton Conductor: Record High Gain of Proton Conductivity Achieved by Photoinduced Electron-Transfer Strategy Xiu-Shuang Xingâ , Cai Sunâ , Lu Liu, Ming-Sheng Wang and Guo-Cong Guo Xiu-Shuang Xingâ State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 Henan Key Laboratory of New Optoelectronic Functional Materials, College of Chemistry and Chemical Engineering, Anyang Normal University, Anyang 455000 â X.-S. Xing and C. Sun contributed equally to this work.Google Scholar More articles by this author , Cai Sunâ State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou, Fujian 350108 Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China, Fuzhou, Fujian 350108 â X.-S. Xing and C. Sun contributed equally to this work.Google Scholar More articles by this author , Lu Liu State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 Google Scholar More articles by this author , Ming-Sheng Wang *Corresponding author: E-mail Address: [email protected] State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China, Fuzhou, Fujian 350108 Google Scholar More articles by this author and Guo-Cong Guo State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China, Fuzhou, Fujian 350108 Google Scholar More articles by this author https://doi.org/10.31635/ccschem.021.202000610 SectionsSupplemental MaterialAboutAbstractPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail Light-responsive proton conductors might find applications in both traditional fields (fuel cells, chemical sensors, bio-ionic functions, etc.) and modern high-speed switchable smart systems (Internet of things, robotics, etc.). Previous synthetic methods resulted in low switching contrasts (<two times) or they tended to be limited significantly in solid matrixes due to large structural changes. The photoinduced electron-transfer (PIET) method avoids the influence of stereo space in solid matrixes and capable of achieving high switching contrasts. For the first time, we applied the PIET strategy to design light-responsive proton conductors to achieve the hitherto largest gain of proton conductivity (ca. 54 times) for light-responsive proton conductors in one crystalline photochromic viologen-based H-bonded supramolecule. The weakening of hydrogen-bonding interactions in the proton-transport path after PIET accounted for an increased proton conductivity. These findings would inspire the exploration of photon conductors that display higher proton conductivities or switchable smart systems with high contrasts. Download figure Download PowerPoint Introduction Proton conductors attract extensive attention for applications in fuel cells, chemical sensors, and bio-ionic functions.1â3 Current research endeavors mainly focus on achieving high conductivity in crystalline materials with H-bonded networks such as coordination polymers (CPs) and metalâorganic frameworks (MOFs) by encapsulation of proton carriers, pore surface functionalization, defect introduction, and so on.4â12 However, due to the development and stimulation of high-tech industries such as the Internet of things and robotics, regular proton conductors cannot meet the new stimuli-responsive smart systemsâ requirements. The light mode has advantages of noninvasiveness, high spatial resolution, and easy and quick modulation, and thus, light-responsive proton conductors and related systems have attracted close attention. For example, Wen et al.13 fabricated a bio-inspired photoelectric conversion system based on a cross-membrane pump of proton originating from the light-driven dissociation of a photoacid; the Kitagawa group14 provided a photoacid (pyranine)-doping strategy to increase mobile acidic protons and local defects upon irradiation, and thus, realized the enhancement of proton conductivity (contrast: ca. one time) in a melted CP. Additionally, the Heinke group observed a photoinduced decrease of proton conductivity due to an enhancement of hydrogen-bonding interactions between framework and proton-conducting guests when photochromic azobenzene (contrast: ca. one time)15 or spiropyran (contrast: ca. 100 times)16 moieties were anchored to the linker of a MOF. Further, very recently, Chenâs group17 achieved a dramatic decrease in proton conductivity (contrast: ca. 10,000 times) by encapsulating sulfonated spiropyran into MOF pores, where photoinduced ring open of photochromic spiropyran blocked hydrogen-bonding network and consequently reduced proton-conduction mobility. These studies explored two applicable methods to modify proton conductivities successfully: (1) light-driven dissociation of protons and (2) photoisomerization of photochromic molecules. The former had few stereo space requirements in the solid matrixes but usually resulted in low switching contrasts (<two times). The latter might yield high switching contrasts but are significantly limited in solid matrixes due to extensive structural changes. Thus, it is highly desirable to explore a new method that can combine the advantages of the two known methods. Additionally, high-contrast enhancement efforts of proton conductivity after light irradiation, instead of weakening the process, are appealing for a real application; however, effective strategies to this aim are also lacking. Electrons and protons often work together in natural photosynthetic and enzymatic systems.18,19 Besides, electron transfer usually results in minor structural change.20,21 Inspired by these points, we presume that electron transfer or electron redistribution in a material system could affect the performance of proton conduction significantly and is well adapted to a solid matrix. Suppose one crystalline compound with an infinite hydrogen-bonding network is able to undergo photoinduced electron transfer (PIET), it can act as a good proof-of-concept model to verify our idea and further explore the regulated mechanism involving the interrelationship of electron transfer and proton transport. Diprotonated 4,4âČ-bipyridinium (a typical viologen; abbreviated as H2V hereafter) can accept one electron from an electron donor to yield a stable radical and generate a photochromic phenomenon after irradiation.22 The existence of NâH bonds in H2V offers an opportunity to construct a hydrogen-bonding network. If free or coordinated water molecules and/or hydroxyl groups are further included, then the formation of an H-bonded supramolecule with an infinite hydrogen-bonding network is highly possible. Furthermore, crystalline species particularly favor the study of internal structural information. Therefore, crystalline compounds with âH2V,â âfree or coordinated waterâ and/or âhydroxylâ groups are suitable proof-of-concept models to understand the relationship between the PIET process and proton conduction. Experimental Methods Materials and instruments All chemicals of analytical grade were obtained from commercially available sources and used as received without further purification. Powder X-ray diffraction (PXRD) patterns at room temperature were acquired on a Rigaku Miniflex II Desktop X-ray diffractometer (Tokyo, Japan) using Cu Kα radiation (λ = 1.540598 Ă ) at 40 kV and 40 mA ranging from 5° to 50°. A simulated PXRD pattern was obtained from the Mercury Version 2020.1 software ( http://www.ccdc.cam.ac.uk/products/mercury). Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) analysis experiments were carried out on a Mettler TOLEDO simultaneous TGA/DSC apparatus (Zurich, Switzerland) in N2, heating the sample in an Al2O3 crucible at a heating rate of 10 K·minâ1. Fourier transform infrared (FT-IR) spectra were recorded on a PerkinElmer Spectrum One FT-IR spectrometer (Waltham, MA) using KCl pellets in the 4000â400 cmâ1 range. Electron absorption spectra were measured at room temperature on a PerkinElmer Lambda 900 UV/vis/near-infrared (NIR) spectrophotometer (Waltham, MA) equipped with an integrating sphere and BaSO4 as a reference. Electron paramagnetic resonance (ESR) spectra were recorded on a Bruker-BioSpin ER-420 spectrometer (Rheinstetten, Germany) with a 100 kHz magnetic field in the X band at room temperature. Synthesis of {(H2V)[Ge(ox)2(OH)2]}·2H2O ( 1; ox = oxalate) Compound 1 was synthesized, as described previously.23 The crystal samples for all testing and characterizations were carefully picked with the aid of a microscope, checking their phase purity by PXRD ( Supporting Information Figure S1). Proton conductivity measurements Proton conductivity measurements were performed using a quasi-four-electrode alternating current (AC) impedance technique with a Solartron 1260 impedance/gain-phase analyzer. Our single-crystal measurements revealed the single-crystal shape as a triangular prism, wherein the cross-section area sizes and the length were 0.157 Ă 0.270 mm2 and 0.350 mm, respectively. Gold wires were connected to both ends of the longer axis of each crystal. The single crystal was measured at frequencies ranging from 107 to 1 Hz as the temperatures were varied from 303 to 323 K and the relative humidity (RH) was 95%. The resistances of the crystalline samples were deduced with the operation of a âfit cycleâ from the Debye semicircle in the Nyquist plot. Computational approaches Projected band structure The calculation was based on density functional theory (DFT) in conjunction with the projector augmented wave (PAW) potential, which is implemented in the Vienna ab initio Simulation Package (VASP).24,25 The PerdewâBurkeâErnzerhof (PBE) exchange-correlation functional with an optB86b-vdW correction was used, considering the dispersion interaction between neighboring organic components.26 Single-crystal X-ray diffraction data of 1 were used to build the calculation model. Single-point energy was calculated using plane-wave cutoff energy of 400 eV and a 3 Ă 3 Ă 2 MonkhorstâPack grid of k-points. The dipole moment of a fragment and charge decomposition analysis The calculations indicated above were derived using the Gaussian 09 D01 version and Multiwfn software.27â29 As shown in Supporting Information Figure S8, the molecular model was taken from the single-crystal structure of 1. H atoms in the Ge complex and the water molecule were optimized at the M06-2X/def2-svp level, while other atoms remained unchanged. The dipole moment of a fragment (F) based on the Hirshfeld weighting function given by the equation: D F = â A â F [ Z A R A â â« [ Ï A ( r ) Ï ( r ) ] r d r ] where A is the atomic index in F, ZA, RA, and ÏA(r) are nuclear charge, position, and atomic weighting function of atom A, respectively.28 The charges were set as â2 and â1 for the Ge complex in initial and colored states. The charge decomposition analysis (CDA) proposed by Dapprich and Frenking is used to provide a deep insight into how charges are transferred within fragments in a complex to achieve charge equilibrium.27 In CDA, the fragment orbital (FO) denotes the molecular orbital (MO) of a fragment in its isolated state. Three terms are defined as follows: d i = â m â A occ â n â B vir η i C m , i C n , i S m , n b i = â m â A vir â n â B occ η i C m , i C n , i S m , n r i = â m â A occ â n â B occ η i C m , i C n , i S m , n where i and η are index and occupation number of MO of complex, respectively. S m , n = â« f m ( r ) f n ( r ) d r is an overlap integral between FO m and FO n. Cm,i denotes the coefficient of FO m in MO i of the complex. The superscript âvirâ and âoccâ mean virtual (viz. unoccupied) and occupied, respectively. The term di denotes the amount of electron donated from fragment A to B via MO i of the complex; similarly, the term bi denotes the electron back donated from B to A. The term r reveals closed-shell interaction between two occupied FOs in different fragments; a positive value of ri means that owing to MO i, the electrons of the two fragments are accumulated in their overlap region and shows bonding character, while a negative value indicates that the electrons are depleted from the overlap region, and thus, reflect an electron repulsive effect. In the initial state, the charges for the Ge complex, water, and H2V were set as â2, 0, and +2, respectively, while those in the colored state were set as â1, 0, and +1, respectively. The spin multiplicities were set as 1 and 3 for initial and colored states of the model complex, respectively. Results and Discussion Through screening of the Cambridge Crystallographic Data Center (CCDC) database, 185 structures with âH2V,â âfree or water,â and/or âhydroxylâ were found ( Supporting Information Figures S2 and S3). From these structures, compound 123 was chosen as a proof-of-concept model, considering its well-resolved crystal structure, the presence of an infinite hydrogen-bonding network, and potential electron-transfer photochromic property. Figure 1 shows that compound 1 was constructed by H2V ions, Ge complexes, and free water molecules through intermolecular hydrogen bonds and van der Waals interactions. In the Ge complex, each Ge atom was coordinated by six oxygen atoms from two ox ligands and two hydroxyl groups to form a distorted octahedron. The coordinated O(9) hydroxyl groups and free O(2W) water molecules form an infinite hydrogen-bonding network along a direction that provides 1D proton-transporting channels. Notably, the hydrogen atoms of the O(9) hydroxyl group and the O(2W) water molecule were found to be disordered over two distinct crystallographic positions [H(4W) and H(5W) for the water molecule, and H(9A) and H(9B) for the hydroxyl group].23 This disorder means that the active O(9) hydroxyl group and the O(2W) water molecule can reorient themselves readily to make the oxygen atoms have a proper angle to accept hydrogen atoms for proton transport through the Grotthuss mechanism.30,31 Moreover, it has been reported that the electron on the oxygen atoms of an ox could transfer to H2V after irradiation in a photochromic process.32 The nearest distance between the ox oxygen atom and the H2V nitrogen atom in 1 was about 2.811(3) Ă , which met the distance of typical PIET occurrence.33,34 Therefore, compound 1 has a high probability of exhibiting electron-transfer photochromic properties. Figure 1 | Crystal structure of 1 showing an infinite hydrogen-bonding network along the a axis. Hydrogen bonds: O(2W)âH(4W)âŻO(2W, symmetry codes: âx, 1ây, âz), dO(2W)âŻO(2W) = 2.738(3) Ă , â [O(2W)âH(4W)âŻO(2W)] = 161(4)°; O(9)âH(9B)âŻO(2W), dO(9)âŻO(2W) = 3.188(3) Ă , â [O(9)âH(9B)âŻO(2W)] = 119(3)°; O(9)âH(9B)âŻO(9, symmetry codes: 1âx, 1ây, âz), dO(9)âŻO(9) = 3.004(4) Ă , â [O(9)âH(9B)âŻO(9)] = 133(5)°; O(9)âH(9A)âŻO(2W, symmetry codes: 1âx, 1ây, âz), dO(9)âŻO(2W) = 2.800(3) Ă , â [O(9)âH(9A)âŻO(2W)] = 161(6)°. Partial disordered H atoms are drawn in light green. The green arrows indicate the proton transport channel by the Grotthuss mechanism. Download figure Download PowerPoint Our experimental data could well demonstrate the above speculation. Upon continuous irradiation by a diode-pumped solid-state (DPSS) laser (355 nm, 369 mW·cmâ1) for only 30 s under ambient conditions, the colorless as-synthesized crystalline sample ( 1A) underwent a rapid, apparent color change to a purple sample ( 1B) (Figure 2a). No generation of prominent new peaks or disappearance of old peaks was observed in the PXRD pattern ( Supporting Information Figure S1), indicating no evident structural change during the coloration process. Furthermore, TGA curves before and after the coloration also displayed no noticeable difference, which suggested that the free water molecules were not lost after coloration ( Supporting Information Figure S5). These results excluded the occurrence of photoinduced dissociation after the coloration. Additionally, two characteristic electron absorption bands of viologen radicals35 appeared around 386 and 596 nm after the coloration (Figure 2c). Time-dependent absorption data indicated that the coloration process occurred rapidly and reached saturation after 2 min of irradiation. The colorationâdecoloration process for 1 could be cycled at least four times ( Supporting Information Figure S6), revealing its reversible photochromism character.36 An EPR study revealed no signal for 1A, but a strong, sharp single-line signal at g = 2.0025 for 1B (Figure 2b). Both electron absorption and EPR data demonstrate the occurrence of a PIET process and the formation of H2V radicals after coloration. We confirmed the electron donor by calculating the projected band structure of 1. As illustrated in Figure 2d, the electronic states near the valence band maximum (VBM) were mainly dominated by an ox, while the conduction band minimum (CBM) was exclusively contributed by H2V. These features indicated that ox and H2V were the electron donor and acceptor, respectively. This deduction was consistent with the previous discovery in the literature that ox is an effective electron donor.32 The 1B sample could be bleached by allowing to stand in the dark in air, but complete bleaching required 2 days, as monitored by the EPR study (Figures 2a and 2b). Figure 2 | Photochromism of 1: reversible color change (a) and EPR spectra (b) in a cycle (1A, as-synthesized sample; 1B, colored sample; decolored, color-bleached sample). (c) Time-dependent electron absorption spectra upon irradiation. (d) Projected band structure with the Fermi level was set to zero by default. Download figure Download PowerPoint Proton conductivities (Ï) of a single crystal of 1 were investigated by impedance spectroscopy using silver paste as electrodes with resistance extracted by fitting the corresponding Nyquist plot. As shown in Figure 3a, the Nyquist plot impedance data on the 95% RH at 303 K showed that the 1A sample has a Ï value of 2.83 Ă 10â5 S·cmâ1. After irradiation for 2 min by the DPSS laser to produce the 1B the Ï value increased by about 54 times to Ă S·cmâ1. This is the hitherto largest for light-responsive proton Thus, the above results confirmed that a light-responsive proton could be by the PIET Figure 3 | (a) Nyquist plot of the impedance of 1A and 1B under 303 K and 95% an of (b) proton conductivities of 1A and 1B at 95% of the single-crystal samples Download figure Download PowerPoint gain insight into the electron transfer an increase in proton proton conductivities were TGA revealed that compound 1 could be stable to this the free water molecules to ( Supporting Information Figure 95% the Ï of 1A and 1B increased from 2.83 Ă 10â5 to Ă and from Ă to Ă respectively, with the temperature from 303 to 323 K (Figure The = based on the along with the has often been applied to the proton conduction in The calculated energy of 1A and 1B are around and (Figure and Supporting Information Figure The decrease of after irradiation indicated a in the proton conduction to an increase in the Ï further understand the for increased proton conduction after irradiation FT-IR spectra were recorded (Figure As the irradiation the relative of around cmâ1 for and groups while the of peaks remained unchanged. Moreover, and positions of other peaks not of a mode on the change in dipole moment by the where and were the dipole moment and the respectively. The the in of atoms connected at both ends of one chemical the the change in during and the the one electron transferred from the Ge complex to the electron density of the Ge complex The decrease in electron density the in between and H atoms in the hydroxyl group of the Ge complex, which tended to the value of the hydroxyl with a decrease in the The calculated of the O(9) hydroxyl fragment ( Supporting Information showed that the of the dipole moment reduced from to Debye after electron consistent with the above Therefore, the decrease in the of the hydroxyl group reduced the of the hydrogen bonds between the hydroxyl group and the free water molecule, in increased the proton on the hydroxyl and water groups and the proton conduction Figure | (a) of the of 1 in the upon irradiation. (b) of complex and with green and set at respectively. Download figure Download PowerPoint provides a insight into the electron influence on proton conduction from an electronic structural As shown in Figure the of orbital the overlap region between the hydroxyl group and the water molecule with a large positive r value which indicated a bonding In a in the overlap region in orbital with a large negative r value an electron repulsive (Figure Supporting Information S2 and and Figure The typical bonding and the hydrogen-bonding relationship within the hydroxyl group and water the hydrogen-bonding relationship mainly contributed to charge transfer between the Ge complex and water As shown in the electrons were transferred from the Ge complex to the water molecule due to the corresponding complex orbital This is in with our chemical in that the hydroxyl atom provided electrons to form a hydrogen with the proton in the water molecule, to the formation The decrease in from to between the Ge complex and the water molecule after coloration resulted in hydrogen-bonding the H atoms in the water molecule high and increased proton 1 | Results for a of One Ge and One in 1 d b r state state The term d denotes the number of electrons donated from the Ge complex to the water The term b denotes the electrons donated back from the water molecule to the Ge complex. The term that the Ge complex provides its electrons from occupied FOs to virtual FOs of the water The term r reveals closed-shell interaction between two occupied FOs in different We have shown in a first to modify proton conduction by the PIET Through functional structural we were able to one proof-of-concept crystalline photochromic viologen-based H-bonded supramolecule from the For a real high-contrast enhancement of proton conductivity after light irradiation is highly the of our only one known has shown proton conductivity upon irradiation and the observed of ca. one time, which is In this the proton conductivity for the proof-of-concept compound increased to ca. 54 times after a for light-responsive proton The increased proton conductivity was derived from a decrease in the energy of the proton transport by the weakening of the hydrogen-bonding interaction after A of the relationship between the electron-transfer process and proton conduction and the of high for the PIET method inspire the exploration of photon conductors with higher proton conductivities or switchable smart systems with high contrasts. Supporting Information Supporting Information is available and PXRD screening and TGA impedance the dipole moment of a and of is no of to Information This work was by the Science of and the Research of the Chinese Academy of and and the Key Research of Chinese Academy of The for on the of proton conductivity. 1. in Proton for and Google Scholar A. and and Google Scholar Kitagawa with High Proton Google Scholar as Proton and Google Scholar Kitagawa to Proton Conductivity in a Google Scholar Wang in and Simulation Google Scholar Wang with a High of for Proton Google Scholar Wang Google Scholar and Google Scholar Google Scholar