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COMMUNICATIONS 1368 ¹ WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002 1433-7851/02/4108-1368 $ 20.00+.50/0 Angew. Chem. Int. Ed. 2002, 41, No. 8 Additivity and Quantification of Dispersive Interactions–from Cyclopropyl to Nitro Groups: Measurements on Porphyrin Derivatives** Tianjun Liu and Hans-Jˆrg Schneider* The investigation of supramolecular complexes opens up pathways to the identification of noncovalent interactions, such interactions are also of importance for biology and materials science. One example is the discovery of high-order effects in the form of cation ± p interactions in organic host ± guest complexes. [1] Dispersive Van der Waals interactions have hitherto defied a corresponding empirically based characterization. At the same time their theoretical calcula- tion encounters considerable problems largely because of the need to consider polarization. [2] We report here the systematic analysis of host ± guest complexes, with porphyrin derivatives in water as host molecules, which for the first time allows an unambiguous identification of dispersive interactions and provides generally applicable energy increments. Porphyrins are made water soluble by the insertion of pyridinium or sulfonic acid moieties (TPyP or TPS, Scheme 1) into the meso positions, and are then highly suitable for the analysis of noncovalent interactions. [3] They show an intense Scheme 1. Structures of porphyrins TPyP and TPS and the general formulae of the benzoic acids B and pyridines py used as guests. absorption band at about 400 nm (Soret band) which can be readily used as a probe for the UV spectroscopic determi- nation of equilibrium constants. Above all, however, because of their large surface, porphyrins are relatively tolerant of the necessary geometric adaptation between host and guest molecule, as long as the guest is sufficiently small. Moreover, noncovalent interactions with porphyrins and related com- pounds are of considerable importance in biological systems. [4] The identification of noncovalent interactions in supra- molecular structures is of limited value if the interactions cannot be energetically quantified in an adequate number of systems. [5] We have determined the complexation constant K for a number of guests (Tables 1 and 2 and Table I of the Supporting Information) with the porphyrins TPyP and TPS as host molecules by the previously described methodology. [6] In the selection of substrates attention was given to a different combination of components, for example, benzene rings, carboxyl, and nitro groups. Our investigations confirm an astonishing additivity in the complexation energy contribu- tions of the individual groups. This trend is illustrated in Scheme 2 for the nitro compounds investigated: a constant value of DDG 5 kJ mol 1 can be assigned to the ion-pair bonding between the carboxyl group and the positively charged porphyrin, as was found in numerous complexes with the ion strengths used here. [7] A DDG value of about 8 kJ mol 1 is assigned to the bonding contribution of the benzene unit (see Table 3) from previous [6] and more recent measurements (e.g. comparison of benzoic acid B1 and propionic acid Pr1, Table I of the Supporting Information). The DDG value for the ion-pair bond and for benzene confirm the new data: a constant contribution for the nitro group of DDG 5 kJ mol 1 is derived from the K values measured for three nitrobenzoic acids; this even applies, within the error limits, to aliphatic guest molecules such as nitromethane M8 or 3-nitropropionic acid Pr4. As with free energy relation- ships, for instance of the Hammett correlation type, deviations from additive behavior normally arise if substituents are [*] Prof. Dr. H.-J. Schneider, Dr. T. Liu FR Organische Chemie der Universit‰t des Saarlandes and Institut f¸r Neue Materialien 66041 Saarbr¸cken (Germany) Fax: ( 49) 681-302-4105 E-mail: [email protected] [**] This work was supported by the DFG. T.L. thanks the Alexander von Humboldt Stiftung for a stipend. Supporting information for this article is available on the WWW under http://www.angewandte.com or from the author. Table 1. Substituents X of the benzoic acid derivatives B1 ± B29 the complexation of which was investigated with the porphyrin derivatives TPyP and TPS. X X X B1 H B11 4-I B21 3-NO 2 B2 4-CH 3 B12 4-OCH 3 B22 4-NO 2 B3 3,5-dimethyl B13 4-COOCH 3 B23 3,5-dinitro B4 4-CH(CH 3 ) 2 B14 4-COCH 3 B24 3,4-dinitro B5 3-CH 2 Cl B15 3,5-dimethoxy B25 3,4-difluoro B6 4-CH 2 Cl B16 4-NH 2 B26 3,5-difluoro B7 4-CHCH 2 B17 4-SCH 3 B27 3,4-dichloro B8 4-F B18 4-CN B28 3,5-dichloro B9 4-Cl B19 4-CONH 2 B29 3,5-dibromo B10 4-Br B20 2-NO 2 Table 2. Further compounds, the complexation of which was investigated with the porphyrin derivatives TPyP and TPS. X Pyridine Peptides and others py1 H Pp3 Gly-Gly-Gly-OH py2 3-Br Pp4 Gly-Gly-Gly-Gly-OH py3 3-CN Pp5 Gly-Gly-Gly-Gly-Gly-OH py4 3-OCH 3 M1 HCC(CH 2 ) 2 COOH py5 3-I M2 HOCH 2 CCCCCH 2 OH M3 CH 2 CHCOOH M4 CH 3 CHCHCOOH X-CH 2 -CH 2 -COOH M5 cyclopropyl-COOH Pr1 H M6 (cyclopropyl) 2 CHOH Pr2 Br M7 C 6 H 5 CHCHCOOH Pr3 I M8 CH 3 NO 2 Pr4 NO 2 M9 NaNO 3 M10 NaI

Von Rimscha's Transitivity Conditions

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Page 1: Von Rimscha's Transitivity Conditions

Math. Log. Quart. 46 (2000) 4, 549 – 554

Mathematical LogicQuarterly

c© WILEY-VCH Verlag Berlin GmbH 2000

Von Rimscha’s Transitivity Conditions

Paul Howarda, Jean E. Rubinb, and Adrienne Stanleyb

a Department of Mathematics, Eastern Michigan University,Ypsilanti, MI 48197, U. S.A1)

b Department of Mathematics, Purdue University,West Lafayette, IN 47907, U. S.A.2)

Abstract. In Zermelo-Fraenkel set theory with the axiom of choice every set has the samecardinal number as some ordinal. Von Rimscha has weakened this condition to “Every sethas the same cardinal number as some transitive set”. In set theory without the axiom ofchoice, we study the deductive strength of this and similar statements introduced by vonRimscha.

Mathematics Subject Classification: 03E25, 03E35, 03E50, 04A25, 04A30.

Keywords: Axiom of choice, Dedekind finite, Transitive closure, Fraenkel-Mostowskimodels.

We shall use the standard notation and terminology of set theory. In particular werecall that a set x is transitive if for every y ∈ x and every t ∈ y, t ∈ x. The transitiveclosure TC(x) of a set x is the smallest transitive set z such that x ⊆ z. In addition,for any set x, we will use TC′(x) to stand for TC(x) ∪ {x}.

Transitive sets play an important role in set theory. The ordinal numbers, forexample, are transitive sets and under the assumption of the axiom of choice (whichwe shall denote by AC) given any set x, there is a bijection from x to some ordinal. In[3] von Rimscha introduces a similar statement Tr, weakened by replacing the word“ordinal” with the words “transitive set”.

Tr ∀x∃u∃f (u is transitive ∧ f is a bijection from x onto u).

Two strengthenings of Tr are also considered in [3]:

Tr′ ∀x∃u∃f (u is transitive ∧ u ⊆ TC(x) ∧ f is a bijection from x onto u).

Tr′′ ∀x∃u∃f (u is transitive∧ f is a bijection from x onto u∧ (∀s ∈ x) (f(s) ∈ TC′(s))).

Working in Zermelo-Fraenkel set theory without AC (ZF), von Rimscha showsthat AC implies Tr′′, Tr′′ implies Tr′, Tr′ implies Tr, and Tr implies that everyDedekind finite set is finite. We prefer to work in ZF0, where ZF is modified to allow

1)e-mail: [email protected])e-mail {jer, stanley}@math.purdue.edu

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550 Paul Howard, Jean E. Rubin, and Adrienne Stanley

the existence of atoms. The same proofs hold with minormodifications. VonRimschaalso asks whether any of the implications are reversible. In this paper we answer sev-eral of these questions.

We shall prove two theorems:T h e o r em 1. (ZF0). Tr′ implies AC.Th e o r em 2. Tr is true in Mostowski’s linearly ordered model of ZF0.Note that, since ZF0 is a weaker theory than ZF, this gives us the fact that Tr′,

Tr′′ and AC are equivalent in ZF. Also, since there are infinite, Dedekind finite setsin Mostowski’s linearly ordered model, we see that in the theory ZF0, Tr does notimply that all Dedekind finite sets are finite. We have not answered the two questions“Does Tr imply AC in ZF ?” and “Does ‘Every Dedekind finite set is finite’ imply Trin ZF ?” Our conjecture is that in both cases the answer is “no”.

P r o o f o f T h e o r em 1. Let x be a set. Assume x = ∅ and x is not an atom.(The idea of the proof is to construct a set xγ , for any infinite ordinal γ, such thatx and xγ have the same cardinality and that transitive subsets of TC(xγ) which aresmall (that is, have cardinality � |γ|) must be subsets of A ∪ δ, where A is the set ofatoms in TC(x) and δ is a sufficiently large ordinal number. Choosing γ large enoughand applying Tr′ to xγ will give us a well ordering of xγ .)

Let A = {a : a is an atom and a ∈ TC(x)}. Let κ be the least ordinal such thatthere is no function from A onto κ. Let γ be the least ordinal such that |γ| � |x× κ|.We now define {tγ : t ∈ TC({x})} by ∈-induction as follows. For each t ∈ TC({x})define

tγ =

γ if t = ∅,{t, γ} if t ∈ A,{sγ : s ∈ t} otherwise.

Using ∈-induction it is easy to show that for every t, r ∈ TC({x}), if tγ = rγ , thent = r. Consequently, for every t ∈ TC({x}), if t = ∅ and t /∈ A, then |tγ | = |t|.Specifically, |xγ | = |x|. So it is sufficient to well order xγ .

By Tr′, there is a transitive set u ⊆ TC(xγ × κ) and a one to one function f fromxγ ×κ onto u. Since |xγ | = |x|, |xγ ×κ| = |x×κ|. But |x×κ| � |γ|, so |xγ ×κ| � |γ|.Since u is transitive, TC(u) = u and so |TC(u)| = |xγ × κ| � |γ|. Let z ∈ u. Then|TC(z)| � |γ|. Since u ⊆ TC(xγ × κ), z ∈ TC({{{tγ}, {tγ, α}} : t ∈ x ∧ α ∈ κ}).3)

However,

TC(xγ × κ) = {{{tγ}, {tγ, α}} : t ∈ x ∧ α ∈ κ}∪ ⋃

t∈x,α∈κ{{tγ}, {tγ, α}} ∪ TC(xγ) ∪ κ.

Notice that γ ⊆ TC(tγ) for every t ∈ TC({x}). So z = tγ and t � TC(z) for everyt ∈ TC({x}). Thus, z ∈ TC(xγ) ∪ κ. Let δ = max{γ + 1, κ}. We will show thatz ∈ δ ∪ A. Suppose z ∈ TC(xγ). By our construction of xγ , z ∈ sγ for somes ∈ TC({x}). Since z /∈ {tγ : t ∈ TC({x})}, s ∈ A or s = ∅. If s = ∅, thenz ∈ ∅γ = γ ⊆ δ. If s ∈ A, then z ∈ sγ = {s, γ} ⊆ δ ∪ A. Thus z ∈ δ ∪ A and sou ⊆ δ ∪ A.

3)Note that {{tγ}, {tγ, α}} = 〈tγ, α〉.

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Von Rimscha’s Transitivity Conditions 551

Now we define a function g from A into κ. For each a ∈ A let

g(a) ={0 if a /∈ f [xγ × κ],β if a ∈ f [xγ × {β}].

Since f is a one to one function, g is well defined. By our initial choice of κ, g isnot an onto function. Let α ∈ κ be the least ordinal such that α /∈ g[A]. Then,A ∩ f [xγ ×{α}] = ∅. Thus, f [xγ ×{α}] ⊆ δ. So xγ , and consequently, x, can be wellordered. ✷

P r o o f o f T h e o r em 2. We begin with a brief description of Mostowski’slinearly ordered model M. Details may be found in [2] or in [1]. The construction ofM begins with a model M′ of ZF0 + AC in which the set of atoms A is countable.We choose an ordering ≤ of A so that (A,≤) is order isomorphic to the rationalnumbers (with their usual ordering). Let G be the group of all order automorphismsof (A,≤). For each ϕ ∈ G there is a unique automorphism of the model M′ whichextends ϕ. This extension will also be called ϕ. For each x ∈ M′, let fix(x) ={ϕ ∈ G : (∀t ∈ x) (ϕ(t) = t)} and let sym(x) = {ϕ ∈ G : ϕ(x) = x}. ThenM = {x ∈ M′ : (∀t ∈ TC′(x))(∃E ⊆ A) (E is finite and fix(E) ⊆ sym(t))}. If E andF are finite subsets of A we will also use fixE(F ) for the group fix(E ∪ F ). If x ∈ Mand E and F are finite subsets of A such that fixE(F ) ⊆ sym(x), then we say that Fis a support of x relative to E. If F is a support of x relative to ∅, then we will simplysay that F is a support of x. In our argument below we shall use the following factabout M (see [2]):

S u p p o r t L emma . If x ∈ M and E is any finite subset of A, then x has a(unique) minimum support suppE(x) relative to E. This minimum support has thefollowing properties:

(i) suppE(x) ∩ E = ∅;(ii) for all ϕ ∈ fix(E), ϕ ∈ fix(suppE(x)) if and only if ϕ(x) = x;(iii) if E ⊆ E′, then suppE′ (x) = suppE(y) \ E′;(iv) if ϕ ∈ fix(E), then suppE(ϕ(x)) = ϕ(suppE(x)).

(Since supports are finite and the intersection of two supports for an element x ∈ Mis a support of x it follows that the (unique) minimum support of x is the intersectionof all the supports of x.) Assume x ∈ M. We shall construct a one to one functionG which is in M, whose domain is x and whose range is a transitive set. This willsuffice to prove the theorem. Let E = {a0, a1, . . . , an} be a support of x and assumea0 < a1 < · · · < an. For ease of exposition we adjoin a largest and smallest element(∞ and −∞, respectively) to the set of atoms A. In addition if a and b are in Awith a < b, we will use the notation (a, b) for the open interval from a to b. LetI0 = (−∞, a0), I1 = (a0, a1), . . . , In+1 = (an,∞). Before defining the function G itwill be necessary to prove

L emma . We may choose E′ ⊇ E so that for each j, j = 0, . . . , n+ 1, if there isa t ∈ x such that suppE′(t) ∩ Ij = ∅, then there is a t′ ∈ x such that suppE′ (t′) ⊆ Ijand |suppE′(t′)| = 1.

P r o o f . From E we shall construct a support E′ of x which satisfies theconditions of the Lemma. For each j, j = 0, . . . , n+ 1, choose an element tj ∈ x

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552 Paul Howard, Jean E. Rubin, and Adrienne Stanley

such that suppE(tj) ∩ Ij = ∅ if such an element exists, and otherwise lettj = ∅. For each i, i = 0, . . . , n+ 1, choose a (finite) subset Fi ⊆ Ii so that|Fi| = max0≤j≤n+1 |suppE(tj) ∩ Ii|. Let E′ = E ∪ ⋃

0≤i≤n+1 Fi. (Note that iffor each j, j = 0, . . . , n + 1, suppE(tj) ∩ Ij = ∅ for all tj ∈ x, then the support ofeach element of x is a subset of E. Thus, x can be well ordered and so the theoremfollows.)

We must argue that for each interval I determined by E′, if there is a t in xsuch that suppE′(t) ∩ I = ∅, then there is a t′ ∈ x such that suppE′(t′) ⊆ Ij and|suppE′ (t′)| = 1. To simplify the argument we will choose one specific interval I.The argument for the other intervals determined by E′ is similar. Assume thatF1 = {b0, . . . , bk}, where a0 < b0 < b1 < · · · < bk < a1. We will give the argumentfor the interval I = (a0, b0). If there is a t1 ∈ x such that suppE′(t1) ∩ I = ∅,then suppE(t1) ∩ I1 = ∅. (Where, as above, I1 = (a0, a1).) Let suppE(t1) ∩ I1 ={c0, c1, . . . , cm}, where c0 < c1 < · · · < cm. By choice of F1, |suppE(t1) ∩ I1| ≤ |F1|and similarly |suppE(t1) ∩ Ii| ≤ |Fi| for 0 ≤ i ≤ n + 1. We may therefore choose apermutation ϕ ∈ fix(E) so that ϕ(c0) ∈ (a0, b0) \ F1, ϕ({c1, . . . , cm}) ⊆ F1, and forall i, i = 1, ϕ(suppE(t1)) ∩ Ii ⊆ Fi. Then by the Support Lemma

suppE′(ϕ(t1)) = suppE(ϕ(t1)) \ E′ = ϕ(suppE(t1)) \ E′ = {c0}.Therefore t′ = ϕ(t1) satisfies the required condition. ✷

The definition of the function G will involve several components.· For each finite subset F of A we define a function WF from ordinals into M by

recursion on ordinals: WF (0) = F , WF (α + 1) = WF (α) ∪ {WF (α)}, and for limitordinals λ, WF (λ) =

⋃α<λWF (α). It is easy to verify that

(a) for any ordinal α, WF (α) is a transitive set;(b) WF (α) = F ∪ {WF (β) : β < α};(c) if F = H are finite subsets of A, then WF and WH have disjoint ranges;(d) WF is one to one.

· For each t ∈ x we define the E orbit Ob(t) of t by Ob(t) = {ϕ(t) : ϕ ∈ fix(E)}.The set {Ob(t) : t ∈ x} is a partition of x.

· Let J = {j : 0 ≤ j ≤ n and (∃t ∈ x) (suppE(t) ∩ Ij = ∅)}. Assuming that Esatisfies the condition of the Lemma, we choose for each j ∈ J an element tj suchthat suppE(tj) ⊆ Ij and |suppE(tj)| = 1. Let suppE(tj) = {dj}.

· Let C be the set consisting of the orbits other than Ob(tj) for j ∈ J , that is,C = {Ob(t) : t ∈ x ∧ (∀j ∈ J) (t /∈ Ob(tj))}. (C can be well ordered in M because allϕ ∈ fix(E) leave C point-wise fixed.) We partition C using the equivalence relationOb(t) ≡ Ob(s) if and only if (∃ϕ ∈ fix(E)) (ϕ(suppE(t)) = suppE(s)). For each ≡-equivalence class D ∈ C, we let gD be a one to one function from D onto an ordinal.

We begin our definition of the functionG by defining G on⋃

j∈J Ob(tj): For j ∈ J

and ϕ ∈ fix(E), G(ϕ(tj)) = ϕ(dj). (In other words, for s ∈ ⋃j∈J Ob(tj), G(s) is the

single element of suppE(s).) Using the Support Lemma, we see that G restrictedto

⋃j∈J Ob(tj) is one to one. Further the range of this restriction of G is

⋃j∈J Ij .

For t /∈ ⋃j∈J Ob(tj), assume t ∈ D, where D is an ≡-equivalence class in C. Define

G(t) =WsuppE(t)(gD(Ob(t))).

Page 5: Von Rimscha's Transitivity Conditions

Von Rimscha’s Transitivity Conditions 553

We first argue that G is in M. It will suffice to show that G has support E

and to show that G has support E it suffices to show that for any ϕ ∈ fix(E), andany t in x, G(ϕ(t)) = ϕ(G(t)). This is clear for t ∈ ⋃

j∈J Ob(tj). For t ∈ ⋃ C,G(ϕ(t)) = WsuppE(ϕ(t))(gD(Ob(t))) since Ob(ϕ(t)) = Ob(t). On the other hand,ϕ(G(t)) = ϕ(WsuppE(t)(gD(Ob(t)))) = Wϕ(suppE(t)(gD(Ob(t)) (since gD(Ob(t) is anordinal, hence fixed by ϕ) = WsuppE(ϕ(t))(gD(Ob(t))) by the Support Lemma.

Next we argue that the range of G is a transitive set. Assume that y is in therange of G. If y = G(t) for some t ∈ ⋃

j∈J Ob(tj), then y is an atom. Assumey =WsuppE(t)(gD(Ob(t))) for some t ∈ ⋃C and assume z ∈ y. We will show that z isin the range of G. By (b), z ∈ WsuppE (t)(gD(Ob(t))) implies that z ∈ suppE(t) or z isWsuppE(t)(β) for some ordinal β < gD(Ob(t)). If z ∈ suppE(t), we use the facts thatsuppE(t) ⊆

⋃j∈J Ij and

⋃j∈J Ij ⊆ ran(G) to conclude that z is in the range of G.

In the second case we use the fact that gD is a function onto an ordinal to concludethat for some s ∈ D, gD(Ob(s)) = β. Since Ob(s) ≡ Ob(t) we may choose s so thatsuppE(s) = suppE(t). Then G(s) = WsuppE(t)(β) = z. Hence, z is in the range of G.

Finally, we argue that G is one to one. We have already noted that G restrictedto

⋃j∈J Ob(tj) is one to one. We leave to the reader the proof that G restricted to⋃

j∈J Ob(tj) and G restricted to⋃ C have disjoint ranges. It remains to show that G

restricted to⋃ C is one to one. Assume G(s) = G(t), where s and t are in

⋃C. ThenWsuppE(s)(gD(Ob(s))) = WsuppE(t)(gD′ (Ob(t))), where D is the ≡-equivalence classof Ob(s) and D′ is the ≡-equivalence class of Ob(t). By (c) suppE(s) = suppE(t).Therefore, D = D′ and by (d) gD(Ob(s)) = gD(Ob(t)). Since gD is one to one,Ob(s) = Ob(t). But by the Support Lemma, two elements in the same E orbit withthe same support relative to E must be identical. Therefore, s = t. ✷

Since Tr is true in Mostowski’s linearly ordered model (in [1], Mostowski’slinearly ordered model is N3), it follows that in ZF0 not only does Tr not imply that“Every Dedekind finite set is finite”, but it also does not imply any of the followingstatements:

(i) The 2n = n Principle: For any infinite cardinal n, 2n = n. (Form 3 in [1].)

(ii) The Principle of Dependent Choices: If S is a relation on a non-empty set Aand (∀x ∈ A)(∃y ∈ A) (xS y), then there is a sequence a(0), a(1), a(2), . . . of elementsof A such that (∀n ∈ ω) (a(n)S a(n+ 1)). (Form 43 in [1].)

(iii) Every linearly ordered set can be well ordered. (Form 90 in [1].)

(iv) The Partition Principle: If P is a partition of a set X, then there is a one toone function mapping P into X. (Form 101 in [1].)

(v) The Kinna-Wagner Selection Principle for a countable number of sets: For everycountable set X there is a function f such that for all A ∈ X, if |A| > 1, then∅ = f(A) � A. (Form 355 in [1].)

In addition, Tr is false in the basic Cohen model (M1 in [1]), and the followingstatements are all true in M1.

Page 6: Von Rimscha's Transitivity Conditions

554 Paul Howard, Jean E. Rubin, and Adrienne Stanley

(vi) The Boolean prime Ideal Theorem: Every Boolean algebra has a prime ideal.(Form 14 in [1].)

(vii) Every set can be linearly ordered. (Form 30 in [1].)

(viii) The axiom of choice for a family of well orderable sets. (Form 60 in [1].)

Thus, it follows that none of these forms imply Tr in ZF.

References

[1] Howard, P., and J. E. Rubin, Consequences of the Axiom of Choice. The AmericanMathematical Society, Providence 1998.

[2] Jech, T., The Axiom of Choice. North-Holland Publ. Comp., Amsterdam 1973.

[3] vonRimscha, M., Transitivitatsbedingungen. Z. Math. Logik Grundlagen Math. 28(1982), 67 – 74.

(Received: February 8, 1999; Revised: August 9, 1999)